Chapter 7

USING ENTROPY

Objective:
Introducing entropy and show its use for thermodynamic analysis.

7.1 Introducing Entropy

 Clausius inequality

The Clausius inequality is a corollary of the second law of thermodynamics. It is

applicable to any cycle without regard for the body, or bodies, from which the cycle
receives energy by heat transfer or to which the cycle rejects energy by heat transfer.

 Q 
  T 0 (7.1)
b
Where,
Q : the heat transfer at a part of the system boundary during a portion of the cycle
T : the absolute temperature at that part of the boundary
b : the integrand is evaluated at the boundary of the system executing the cycle

 : the integral is to be performed over all parts of the boundary and over the entire cycle

 Developing the Clausius Inequality:

From the definition of the Kelvin scale, we have the

following relationship between the heat transfers and
temperatures:

 Q ' Tres  Q'   Q  (7.2)

 or  
 Qb Tb Tres  T  b

An energy balance for the combined system is:

dE C   Q ' W C where  W C   W '  W (7.3)

Q 
 W C  Tres    dE C (7.4)
 T b
Q  Q  (7.5)
W C   Tres     dE C  Tres   
 T b  T b

The Kelvin–Planck statement of the second law must be satisfied: Since the combined
system undergoes a cycle then WC 0.
Therefore:
 Q  (7.6)
 0
  T
b
Equation can be expressed equivalently as:
 Q 
  T  b   cycles (7.7)

Where:
cycles as representing the “strength” of the inequality.
cycles = 0 no irreversibilities present within the system
cycles > 0 irreversibilities present within the system
cycles < 0 impossible

 Defining Entropy Change

A quantity is a property if, and only if, its change in value between two states is
independent of the process.

Give attention for these three reversible processes in two cycles executed by a closed
system:
2Q 1Q
  0
1 T A 2 T C

2Q 1Q
  0
1 T B 2 T C

2Q 2Q
 
1 T A 1 T B -

Since A and B are arbitrary, it follows that the integral of Q/T has the same value for
any internally reversible process between the two states. In other words, the value of the
integral depends on the end states only. It can be concluded, therefore, that the integral
represents the change in some property of the system.

Selecting the symbol S to denote this property, which is called entropy, its change is
given by:
2
Q
S 2  S1   int
(7.8)
1
T rev

The unit for entropy is [kJ/K] or [Btu/oR].

Since entropy is a property, the change in entropy of a system in going from one state to
another is the same for all processes, both internally reversible and irreversible, between
these two states. Thus, these equations allow the determination of the change in entropy.
In the term of statistic thermodynamics, entropy has a meaning as “disordered” of
molecules in microscopic scale.

The entropy divided by its mass, and then we get specific entropy:

s = S/m [kJ/kg.K] or [Btu/lbm oR]

or per mol, s’ = S/M [kJ/kgmol.K] or [Btu/lbmol.oR]

7.2 Retrieving Entropy Data

Entropy data for water and several refrigerants refer to Tables A-2 through A-18.

Reference: s = 0 at T = 0,01oC (32,02oF) for water at saturated liquid.

s = 0 at T = - 40oC (- 40oF) for refrigerant at saturated liquid.

 At two phase (mixture) region:

s = sf + x sfg = sf + x (sg – sf) = (1 – x) sf + x sg = sg – (1 – x) sfg (7.9)

 At compressed liquid region:

presented for water in Tables A-5, or
s (T, P)  sf(T) (7.10)

For water and water vapor, we can see the value of entropy from Temperature – entropy
(T-s) diagram or from Enthalpy – Entropy (h-s) diagram (Mollier Diagram). It is
frequently helpful to locate states and plot processes on diagrams having entropy as a
coordinate, but the value cannot be accurate.

Fig 7.1 T-s diagram and h-s diagram

 TdS Equations (GIBBS Equations)

The TdS equations are developed by considering a pure, simple compressible system
undergoing an internally reversible process. In the absence of overall system motion and
the effects of gravity, an energy balance in differential form is
(Q)int rev = dU + (W)int rev (7.11)
By definition of simple compressible system (Sec. 3.1), the work is
(W)int rev = p. dV (7.12)
From Clausius Equations:
dS = (Q/T)int rev (7.13)
then:
(Q)int rev = T dS (7.14)

Substituting into first equation, then the first T dS equation results:

T dS = dU + p dV T ds = du + pdv (7.15)

Since: H = U + pV,
then
dH = dU + d(pV) = dU + pdV + Vdp, or dU + pdV = dH – V dp (7.16)

Therefore, the second T dS equation results:

T dS = dH – Vdp T ds = dh – v dp (7.17)

Both of those equations can be written on per mole basis.

Although the T dS equations are derived by considering an internally reversible process,

the entropy change obtained by integrating these equations is the change for any process,
reversible or irreversible, between two equilibrium states of a system. Because entropy is
a property, the change in entropy between two states is independent of the details of the
process linking the states.

 Entropy Change of an Ideal Gas

From Gibbs Equations:

du p
ds   dv
T T (7.18)
dh v
ds   dp
T T
For an ideal gas:
du = cv(T) dT (7.19)
dh = cp(T) dT (7.20)
pv = RT (7.21)
cp(T) = cv(T) + R (7.22)

then:
ds = cv(T) dT/T + R dv/v (7.23)
ds = cp(T) dT/T – R dp/p (7.24)

Therefore, for an ideal gas:

T2
dT v
s (T2 , v 2 )  s (T1 , v1 )   c v (T )  R ln 2 (7.25)
T1
T v1

T2 p
dT (7.26)
s (T2 , p 2 )  s (T1 , p1 )   c p (T )  R ln 2
T1 T p1
 Using Ideal Gas Tables

By selecting a reference state and reference value, the value of the specific entropy is set
to zero at the state where the temperature is 0 K and the pressure is 1 atmosphere. Then
the specific entropy at a state where the temperature is T and the pressure is 1 atm is
determined relative to this reference state and reference value as:
T
c (T )
s 0 (T )   p dT (7.27)
0
T
Because entropy depends only on temperature, it can be tabulated versus temperature. For
air as an ideal gas, is given in Tables A-22.Values of for several other common gases are
given in Tables A-23.

Since:
T2 T T
dT 2 dT 1 dT
 cp   cp   cp  s 0 (T2 )  s 0 (T1 ) (7.28)
T1
T 0
T 0
T

Then, this equation below, easier to be used by using data from Tables A-22 or A-23:
p
s (T2 , p2 )  s (T1 , p1 )  s 0 (T2 )  s 0 (T1 )  R ln 2 (7.29)
p1

 Assuming Constant Specific Heats

When the specific heats cv and cp are taken as constants, reduce, respectively, to:
T v
s(T2 , v2 )  s(T1 , v1 )  cv ln 2  R ln 2 (7.30)
T1 v1

T2 p
s (T2 , p 2 )  s (T1 , p1 )  c p ln  R ln 2 (7.31)
T1 p1

 Entropy Change of an Incompressible Substance

The incompressible substance model assumes that the specific volume(density)  is

constant and the specific heat depends solely on temperature. cv = c(T) dan du = c(T) dT.
Accordingly, T.ds = du + p.dv, therefore:
c ( T ) dT pdv c ( T ) dT (7.32)
ds   
T T T

On integration, the change in specific entropy is:

T2
c(T )
s2  s1   dT (7.33)
T1
T
When the specific heat is assumed constant, this becomes:
T
s2  s1  c ln 2 (7.34)
T1
Specific heats of some common liquids and solids are given in Table A-19.
7.3 Entropy Change in Internally Reversible Processes

As a closed system undergoes an internally reversible process, its entropy can increase,
decrease, or remain constant. This can be brought out using:
 Q  (7.35)
dS   
 T  int
rev

This indicates that when a closed system undergoing an internally reversible process
receives energy by heat transfer, the system experiences an increase in entropy.
Conversely, when energy is removed from the system by heat transfer, the entropy of the
system is decreasing. This can be interpreted to mean that an entropy transfer
accompanies heat transfer. The direction of the entropy transfer is the same as that of the
heat transfer. On rearrangement, the above expression gives:

 Q intrev  T .dS (7.36)

Integrating from an initial state 1 to a final state 2:
2
Qint   T .dS (7.37)
rev 1

From those equations it can be concluded that an energy transfer

by heat to a closed system during an internally reversible process
can be represented as an area on a temperature–entropy diagram.

Also note that the area interpretation of heat transfer is not valid for irreversible
processes.

To provide an example illustrating both the entropy change that accompanies heat
transfer and the area interpretation of heat transfer:

Carnot Cycle:
For Carnot power cycle:
 Area b-2-3-a: QH = Qin
Represents the heat transfer into the system during the process

 Area b-1-4-a: QL = Qout

Represents the heat transfer out from the system during the
process

 Cycle Works: Wc = Qin – Qout

The net work of any cycle is equal to the net heat transfer, so
enclosed area 1–2–3–4–1 represents the net work of the cycle

The thermal efficiency of the cycle may also be expressed in terms of areas:

W area 1 - 2 - 3 - 4 (T H  T C )( S 3  S 2 ) T
    1 C (7.38)
QH area b - 2 - 3 - a TH ( S 3  S 2 ) TH
7.4 Entropy Balance for Closed Systems (Control Mass)

The cycle consists of process I, during which internal irreversibilities are present,
followed by internally reversible process R :
2 1
Q  Q 
1  T   2  T int   (7.39)
b rev

Second term is the entropy change: S1-S2

Then, the closed system entropy balance results:

2
Q Qj
S 2  S1         (7.40)
1
T b j Tj

or the entropy change of a system = the entropy transfer + entropy production

When applying the entropy balance to a closed system, it is essential to remember the
requirements imposed by the second law on entropy production: The second law requires
that entropy production be positive, or zero, in value. The value of the entropy production
cannot be negative.

Entropy Production ():

  > 0 : irreversibilities present within the system
  = 0: no irreversibilities present within the system

By contrast, the change in entropy of the system may be positive, negative, or zero.

In the other form of the equation,

 On a time rate basis, the closed system entropy rate balance is:
dS Q j
   (7.41)
dt j Tj

 The entropy balance expressed in differential form:

 Q 
dS      (7.42)
 T b

Example:
The entropy balance for the system:
Q
S 2  S1   (7.43)
Tb
The entropy balance for the reservoir:
Q res Q Q (7.44)
 S | res    res  res  
Tb Tb Tb
The second law requires that entropy production be
positive, or zero, in value. The value of the entropy
production cannot be negative. The change in entropy of
the system may be positive, negative, or zero.
 Increase of Entropy Principle

Since energy is an extensive property, its value for the isolated system is the sum of its
values for the system and surroundings.

Values for the system + Surroundings = the isolated system

 First Law of Isolated System:

E system  E surrounding  E isolated  0 (7.45)

In either of these forms, the conservation of energy principle places a constraint on the
processes that can occur. For a process to take place, it is necessary for the energy of the
system plus the surroundings to remain constant.

 Second Law of Isolated System:

2
Q 
S system
 S surroundin g
 S isol
      isol   isol (7.46)
1
T b
Since entropy is produced in all actual processes, the only processes that can occur are
those for which the entropy of the isolated system increases. This is known as the
increase of entropy principle.

7.5 Entropy Rate Balance for Control Volumes

Since this is the principal difference between the closed system and control volume
forms, the control volume entropy rate balance can be obtained by modifying the closed
system entropy rate balance to account for these entropy transfers. The result is:

dSCV Q j
   m i .si   m e .se   CV (7.47)
dt j Tj i e

Rate of change of entropy = Rate of entropy transfer + Rate of entropy production

The term Scv(t), representing the total entropy associated with the control volume at time
t, can be written as a volume integral:

*    
d q *

  .s.dV     dA     s. .Vn .dA      s. .Vn .dA    CV (7.48)

dt V A
T i A i e  A e
 b
7.6 Isentropic Processes

The term isentropic means constant entropy (Adiabatic reversible). Temperature–Entropy

and Enthalpy–Entropy diagrams are particularly convenient for determining properties at
states having the same value of specific entropy. All states on a vertical line passing
through a given state have the same entropy.

Using the Ideal Gas Model:

For two states having the same specific entropy,

p2
s 2  s1  0  s 0 (T2 )  s 0 (T1 )  R ln (7.49)
p1

The value of s0(T) are given in Table A-22 or A-23.

These equation involves four property values: p1, T1, p2, and T2. If any three are known,
the fourth can be determined.

 If T1 and p2/p1 are known, then:

p2
s 0 (T2 )  s 0 (T1 )  R ln (7.50)
p1

The value of s0 (T2) would be calculated, and temperature T2 would then be determined
by interpolation from Table A-22 and A-23.

 if p1, T1 and T2 are known, then p2 can be solved by:

 s 0 (T2 )  s 0 (T1 ) 
p2  p1 exp   (7.51)
 R 
 For the special case of air modeled as an ideal gas, for isentropic process:



p2 exp s 0 (T2 ) R p
 r2
 (7.52)
0

p1 exp s (T1 ) R pr 1 
where: pr1 = pr(T1) = exp [s0(T1)/R] = relative pressure, which its value is provided in
Table A-22.
A relation between specific volumes and temperatures for two states of air having the
same specific entropy can also be developed. With the ideal gas equation of state,
v = RT/p, the ratio of the specific volumes is:

v2  RT2  p1   RT2   pr T1   vr 2

     (7.53)
v1  p2  RT1   pr T2    RT1  vr1
where vr1 = vr(T1) and vr2 = vr(T2) = relative volume, which its value is provided in Table
A-22.

Despite the name given to it, vr(T ) is not truly a volume. Also, be careful not to confuse it
with the pseudoreduced specific volume of the compressibility diagram.

 Assuming Constant Specific Heats

Let us consider next how properties are related for isentropic processes of an ideal gas
when the specific heats are constants:
T2 p
0  c p ln  R ln 2
T1 p1
(7.54 a,b)
T v
0  c v ln 2  R ln 2
T1 v1
For isentropic processes of an ideal gas when the specific heats (cp and cv ) also k are
constants:
k 1
k 1
T2  p2  k v  (7.55)
    2 
T1  p1   v1 
Therefore: p.vk = constant, For isentropic processes of an ideal gas when the k is
constants.
k
p2  v1  (7.56)
 
p1  v2 
Note:
A polytropic process pvn = constant of an ideal gas which :
 If n = 1: isothermal (constant-temperature) process.
 If n = 0: isobaric (constant-pressure) process
 If n =  : isometric (constant-volume) process.
 If n = k: isentropic process.
7.7 Isentropic Efficiencies of Turbines, Nozzles, Compressors, and Pumps

Isentropic efficiencies involve a comparison between the actual performance of a device

and the performance that would be achieved under idealized circumstances for the same
inlet state and the same exit pressure.

Example:

1. Isentropic Turbine Efficiency

Assumption:
Steady state
PE = 0, KE = 0, Q = 0

the work developed through the turbine:


Wcv (7.57)

 h1  h2
m
Since there is no heat transfer, the allowed
exit states are constrained by:

 cv

 s2  s1  0,
m (7.58)
or ... s2   s1

The maximum value for the turbine work is:

  
 Wcv   h  h (7.59)
   1 2s

 m s
The isentropic turbine efficiency defined by :
 
W m h h (7.60)
 t   cv   1 2  70  90%
  h1  h2 s
Wcv m  s
 

2. Isentropic Nozzle Efficiency

A similar approach to that for turbines can be used to introduce the isentropic efficiency
of nozzles operating at steady state. The isentropic nozzle efficiency is defined as the
ratio of the actual specific kinetic energy of the gas leaving the nozzle, to the kinetic
energy at the exit that would be achieved in an isentropic expansion between the same
inlet state and the same exhaust pressure:

V22 2
 nozzel   95% (7.61)
 
V22 2 s
3. Isentropic Compressor Efficiencies

Assumption:
PE = 0, KE = 0, Q = 0

the work input through the compressor is:


Wcv (7.62)

 h2  h1
m
The minimum work input through the compressor is:
  
 Wcv   h  h (7.63)
   2s 1

 m s

Therefore, the isentropic compressor efficiency defined by:

  
Wcv m 
 s h2 s  h1 (7.64)
c   
  75  85%
Wcv m h2  h1

4. Isentropic Pump Efficiencies

Similarly for pump , isentropic pump efficiency is defined by:
  
Wcv m 
 s h2 s  h1 (7.65)
p   

Wcv m h2  h1

7.8 Heat Transfer and Work in Internally Reversible, Steady-State Flow

Processes

This section concerns one-inlet, one-exit control volumes at steady state.

Heat Transfer:
For a control volume at steady state in which the flow is both isothermal and internally
reversible, the appropriate form of the entropy rate balance is:
Q cv
0   m .( s 1  s 2 )   cv (7.66)
T

Then, the heat transfer per unit of mass passing through the control volume is:
Q cv
 T ( s2  s1 ) (7.67)
m
Generally, if the temperatur would vary:
 Q cv  2
    T .ds (7.68)
 m  int
rev 1

The magnitude of the heat transfer per unit of mass flowing can be represented as the area
under the temperature – entropy curve.
 Work
The work per unit of mass passing through the control volume can be found from an
energy rate balance, which reduces at steady state to give :
 
Wcv Qcv  V 2  V22 

 
 (h2  h1 )   1   g ( z1  z2 ) (7.69)
m m  2 

By Clausius Equations (for internal reversible process) and Gibbs Equations:

T.ds = dh v.dp, then:
Q cv
2 2 2
  T .ds   (dh  v.dp)  ( h2  h1 )   v.dp (7.70)
m 1 1 1
Therefore:
   2
 V12  V22 
 Wcv     g ( z1  z 2 ) (7.71)
      v.dp 
 2 
 m  int
rev
1

Applied to reversible control volume devices such as turbines, compressors, and pumps.
In many of these cases, there is no significant change in kinetic or potential energy from
inlet to exit, so :
   2
 Wcv  (7.72)
     1 v.dp
 m  int
rev

The magnitude of the integral ∫v.dp is represented by the

shaded area behind the curve.

 If the specific volume remains approximately constant, as in many applications with

liquids such pumps and there is no significant change in kinetic or potential energy
from inlet to exit, so the equation becomes :

  
 Wcv  (7.73)
    v( p 2  p1 )
 m  int
rev

 The performance of control volumes at steady state in which Wcv = 0 as in the case of
nozzles and diffusers, equation becomes Bernoulli equation:

2
 V22  V12 
1 v.dp     g ( z2  z1 )  0 (7.74)
 2 
 Work In Polytropic Processes

When each unit of mass undergoes a polytropic process p.vn = constant as it passes
through the control volume, then the equations as follows:
   2 2
 Wcv  1n dp n
(7.75)
     1 v.dp   ( cons tan t ) 1 p1 n   n  1 ( p 2 .v2  p1 .v1 ).........n  1
 m  int
rev

when n = 1, then p.v = constant, and work is:

   2 2
 Wcv  1n dp  p2  (7.76)
      v.dp  (cons tan t )  p 1 n   p1 .v1 ln  p .........n  1
 m  int 1 1  1
rev

 For Ideal Gas, the equations becomes:

n 1
    
W
 cv  nR nRT 1 
 p  n

     n  1 T2  T1    n  1  p   1.........n  1
2
(7.77)
 m  int  1
rev  
when n = 1, then p.v = RT = constant (isothermal process), and the work is:

    p2 
 Wcv  (7.78)
     RT  p .........n  1
 m  int  1
rev