Chapter 6

Using Entropy

Learning Outcomes
Explain key concepts related to entropy
and the second law, including entropy
transfer, entropy production, and the
increase in entropy principle.
Evaluate entropy, evaluate entropy
change between two states, and analyze
isentropic processes, using appropriate
property data.

Learning Outcomes, cont.

Represent heat transfer in an internally
reversible process as an area on a
temperature-entropy diagram.
Analyze closed systems and control
volumes, including applying entropy
balances.
Use isentropic efficiencies for turbines,
nozzles, compressors, and pumps for
second law analysis.

Introducing Entropy Change and the

Entropy Balance
Mass and energy are familiar extensive
properties of systems. Entropy is another
important extensive property.
Just as mass and energy are accounted
for by mass and energy balances, entropy
is accounted for by an entropy balance.
Like mass and energy, entropy can be
transferred across the system boundary.

Introducing Entropy Change and the

Entropy Balance
The entropy change and entropy balance
concepts are developed using the Clausius
inequality expressed as:

cycle

(Eq. 5.13)

where

cycle = 0 no irreversibilities present within the system

cycle > 0 irreversibilities present within the system
cycle < 0 impossible

Eq.
5.14

Defining Entropy Change

Consider two cycles, each composed
of two internally reversible processes,
process A plus process C and
process B plus process C, as shown
in the figure.
Applying Eq. 5.13 to these cycles gives,

where cycle is zero because the cycles are composed of

internally reversible processes.

Defining Entropy Change

Subtracting these equations:
Since A and B are arbitrary internally reversible
processes linking states 1 and 2, it follows that the
value of the integral is independent of the
particular internally reversible process and
depends on the end states only.

Defining Entropy Change

Recalling (from Sec. 1.3.3) that a quantity is a property if,
and only if, its change in value between two states is
independent of the process linking the two states, we
conclude that the integral represents the change in some
property of the system.
We call this property entropy and represent it by S. The
change in entropy is

(Eq. 6.2a)
where the subscript int rev signals that the integral is
carried out for any internally reversible process linking
states 1 and 2.

Defining Entropy Change

Equation 6.2a allows the change in entropy between
two states to be determined by thinking of an internally
reversible process between the two states. But since
entropy is a property, that value of entropy change
applies to any process between the states internally
reversible or not.
Entropy change is introduced by the integral of Eq. 6.2a
for which no accompanying physical picture is given.
Still, the aim of Chapter 6 is to demonstrate that entropy
not only has physical significance but also is essential for
thermodynamic analysis.

Entropy Facts
Entropy is an extensive property.
Like any other extensive property, the change in
entropy can be positive, negative, or zero:

By inspection of Eq. 6.2a, units for entropy S are

kJ/K and Btu/oR.
Units for specific entropy s are kJ/kgK and
Btu/lboR.

Entropy Facts
For problem solving, specific entropy values are provided in
Tables A-2 through A-18. Values for specific entropy are
obtained from these tables using the same procedures as
for specific volume, internal energy, and enthalpy, including
use of

(Eq. 6.4)
for two-phase liquid-vapor mixtures, and

(Eq. 6.5)
for liquid water, each of which is similar in form to expressions
introduced in Chap. 3 for evaluating v, u, and h.

Entropy Facts
For problem solving, states often are shown on
property diagrams having specific entropy as a
coordinate: the temperature-entropy and
enthalpy-entropy (Mollier) diagrams shown here

Entropy and Heat Transfer

By inspection of Eq. 6.2a, the defining equation for
entropy change on a differential basis is

(Eq. 6.2b)
Equation 6.2b 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
by heat transfer, the entropy of the system decreases.
From these considerations, we say that entropy transfer
accompanies heat transfer. The direction of the entropy
transfer is the same as the heat transfer.

Entropy and Heat Transfer

In an internally reversible, adiabatic process (no heat
transfer), entropy remains constant. Such a constantentropy process is called an isentropic process.
On rearrangement, Eq. 6.2b gives

Integrating from state 1 to state 2,

(Eq. 6.23)

Entropy and Heat Transfer

From this it follows that
an energy transfer by
heat to a closed system
during an internally
reversible process is
represented by an area
on a temperature-entropy
diagram:

Entropy Balance for Closed Systems

The entropy balance for closed systems can be
developed using the Clausius inequality expressed as Eq.
5.13 and the defining equation for entropy change, Eq.
6.2a. The result is
where the subscript b
indicates the integral
(Eq. 6.24) is evaluated at the
system boundary.

In accord with the interpretation of cycle in the Clausius

inequality, Eq. 5.14, the value of in Eq. 6.24 adheres to
the following interpretation

= 0 (no irreversibilities present within the system)

> 0 (irreversibilities present within the system)
< 0 (impossible)

Entropy Balance for Closed Systems

That has a value of zero when there are no internal
irreversibilities and is positive when irreversibilities are
present within the system leads to the interpretation that
accounts for entropy produced (or generated) within
the system by action of irreversibilities.
Expressed in words, the entropy balance is
change in the amount
of entropy contained
within the system
during some
time interval

net amount of
amount of
entropy transferred in
entropy produced
across the system boundary + within the system
accompanying heat transfer
during some
during some time interval
time interval

Entropy Balance for Closed Systems

Example: One kg of water vapor contained
within a piston-cylinder assembly, initially at
5 bar, 400oC, undergoes an adiabatic
expansion to a state where pressure is 1 bar
and the temperature is (a) 200oC, (b) 100oC.
Using the entropy balance, determine the
nature of the process in each case.

Boundary

Since the expansion occurs adiabatically, Eq. 6.24 reduces to give

0

S 2 S1

T b

m(s2 s1) =

(1)

where m = 1 kg and Table A-4 gives s1 = 7.7938 kJ/kgK.

Entropy Balance for Closed Systems

(a) Table A-4 gives, s2 = 7.8343 kJ/kgK. Thus
Eq. (1) gives
= (1 kg)(7.8343 7.7938) kJ/kgK = 0.0405 kJ/K
Since is positive, irreversibilities are present within
the system during expansion (a).

(b) Table A-4 gives, s2 = 7.3614 kJ/kgK. Thus

Eq. (1) gives
= (1 kg)(7.3614 7.7938) kJ/kgK = 0.4324 kJ/K
Since is negative, expansion (b) is impossible: it
cannot occur adiabatically.

Entropy Balance for Closed Systems

More about expansion (b): Considering Eq. 6.24

<0 = <0 + 0
Since cannot be negative and
For expansion (b) S is negative, then
By inspection the integral must be negative and so heat
transfer from the system must occur in expansion (b).

Entropy Rate Balance for Closed Systems

On a time rate basis, the closed system entropy
rate balance is
(Eq. 6.28)
where

dS
the time rate of change of the entropy of the
dt system
Q j
Tj

the time rate of entropy transfer through the

portion of the boundary whose temperature is Tj

time rate of entropy production due to

irreversibilities within the system

Entropy Rate Balance for Closed Systems

Example: An inventor claims that the device shown
generates electricity at a rate of 100 kJ/s while receiving a
heat transfer of energy at a rate of 250 kJ/s at a temperature
of 500 K, receiving a second heat transfer at a rate of 350
kJ/s at 700 K, and discharging energy by heat transfer at a
rate of 500 kJ/s at a temperature of 1000 K. Each heat
transfer is positive in the direction of the accompanying
arrow. For operation at steady state, evaluate this claim.

Entropy Rate Balance for Closed Systems

Applying an energy rate balance at steady state

dE
0 Q 1 Q 2 Q 3 W e
dt

Solving W e 250 kJ/s 350 kJ/s 500 kJ/s 100 kJ/s

The claim is in accord with the first law of thermodynamics.
Applying an entropy rate balance at steady state

Solving

dS
0
dt

Q 1 Q 2 Q 3

T1 T2 T3

250 kJ/s 350 kJ/s 500 kJ/s

700 K
1000 K
500 K
kJ/s
kJ/s
0.5 0.5 0.5
0.5
K
K

Since is negative, the claim is not in accord with the

second law of thermodynamics and is therefore denied.

Entropy Rate Balance for Control Volumes

Like mass and energy, entropy can be transferred into or
out of a control volume by streams of matter.
Since this is the principal difference between the closed
system and control volume entropy rate balances, the
control volume form can be obtained by modifying the
closed system form to account for such entropy transfer.
The result is

(Eq. 6.34)
i si and m e se account, respectively, for rates of entropy
where m
transfer accompanying mass flow at inlets i and exits e.

Entropy Rate Balance for Control Volumes

For control volumes at steady state, Eq. 6.34 reduces to
give

(Eq. 6.36)
For a one-inlet, one-exit control volume at steady state,
Eq. 6.36 reduces to give

(Eq. 6.37)
where 1 and 2 denote the inlet and exit, respectively, and
is the common mass flow rate at these locations.

Entropy Rate Balance for Control Volumes

Example: Water vapor enters a valve at 0.7
bar, 280oC and exits at 0.35 bar. (a) If the
water vapor undergoes a throttling process,
determine the rate of entropy production
within the valve, in kJ/K per kg of water
vapor flowing. (b) What is the source of
entropy production in this case?
(a) For a throttling process, there is no significant
heat transfer. Thus, Eq. 6.37 reduces to
0
Q j
s1 s 2 cv
0
m s1 s 2 cv 0 m
Tj

Entropy Rate Balance for Control Volumes

Solving

cv
s2 s1
m

From Table A-4, h1 = 3035.0 kJ/kg, s1 = 8.3162 kJ/kgK.

For a throttling process, h2 = h1 (Eq. 4.22). Interpolating
in Table A-4 at 0.35 bar and h2 = 3035.0 kJ/kg,
s2 = 8.6295 kJ/kgK.
cv
(8.6295 8.3162) kJ/kgK = 0.3133 kJ/kgK
Finally
m
(b) Selecting from the list of irreversibilities provided in
Sec. 5.3.1, the source of the entropy production here is
the unrestrained expansion to a lower pressure undergone
by the water vapor.

Entropy Rate Balance for Control Volumes

Comment: The value of the entropy production for a single
component such as the throttling valve considered here often
does not have much significance by itself. The significance of
the entropy production of any component is normally
determined through comparison with the entropy production
values of other components combined with that component to
form an integrated system. Reducing irreversibilities of
components with the highest entropy production rates may
lead to improved thermodynamic performance of the
integrated system.

Calculating Entropy Change

The property data provided in Tables A-2 through A18, similar compilations for other substances, and
numerous important relations among such properties
are established using the TdS equations. When
expressed on a unit mass basis, these equations are

(Eq. 6.10a)
(Eq. 6.10b)

Calculating Entropy Change

As an application, consider a change in
phase from saturated liquid to saturated
vapor at constant pressure.
Since pressure is constant, Eq. 6.10b
reduces to give

dh
ds
T
Then, because temperature is also constant during the
phase change

(Eq. 6.12)
This relationship is applied in property tables for
tabulating (sg sf) from known values of (hg hf).

Calculating Entropy Change

For example, consider water vapor at 100oC
(373.15 K). From Table A-2, (hg hf) = 2257.1 kJ/kg.
Thus
(sg sf) = (2257.1 kJ/kg)/373.15 K = 6.049 kJ/kgK
which agrees with the value from Table A-2, as
expected.
Next, the TdS equations are applied to two additional cases:
substances modeled as incompressible and gases modeled as ideal
gases.

Calculating Entropy Change of an

Incompressible Substance
The incompressible substance model assumes the specific
volume is constant and specific internal energy depends
solely on temperature: u = u(T). Thus, du = c(T)dT, where
c denotes specific heat.
With these relations, Eq. 6.10a reduces to give

On integration, the change in specific entropy is

When the specific heat is constant

(Eq. 6.13)

Calculating Entropy Change of an Ideal Gas

The ideal gas model assumes pressure, specific volume
and temperature are related by pv = RT. Also, specific
internal energy and specific enthalpy each depend solely
on temperature: u = u(T), h = h(T), giving du = cvdT and
dh = cpdT, respectively.
Using these relations and integrating, the TdS equations
give, respectively

(Eq. 6.17)

(Eq. 6.18)

Calculating Entropy Change of an Ideal Gas

Since these particular equations give entropy change on a
unit of mass basis, the constant R is determined from
R R / M.
Since cv and cp are functions of temperature for ideal gases, such functional
relations are required to perform the integration of the first term on the right of
Eqs. 6.17 and 6.18.
For several gases modeled as ideal gases, including air, CO 2, CO, O2, N2, and
water vapor, the evaluation of entropy change can be reduced to a convenient
tabular approach using the variable so defined by

(Eq. 6.19)
where T ' is an arbitrary reference temperature.

Calculating Entropy Change of an Ideal Gas

Using so, the integral term of Eq. 6.18 can be expressed as

Accordingly, Eq. 6.18 becomes

(Eq. 6.20a)
or on a per mole basis as

(Eq. 6.20b)
For air, Tables A-22 and A-22E provide so in units of
kJ/kgK and Btu/lboR, respectively. For the other gases
mentioned, Tables A-23 and A-23E provide s o in units of
kJ/kmolK and Btu/lbmoloR, respectively.

Calculating Entropy Change of an Ideal Gas

Example: Determine the change in specific entropy, in
kJ/kgK, of air as an ideal gas undergoing a process from
T1 = 300 K, p1 = 1 bar to T2 = 1420 K, p2 = 5 bar.
From Table A-22, we get so1 = 1.70203 and so2 = 3.37901, each in kJ/kgK.
Substituting into Eq. 6.20a

s2 s1 (3.37901 1.70203)

Table A-22

kJ
kg K

8.314

28
.
97

kJ 5 bar
kJ
ln

1
.
215

kg

K
1
bar
kg K

Calculating Entropy Change of an Ideal Gas

Tables A-22 and A-22E provide
additional data for air modeled
as an ideal gas. These values,
denoted by pr and vr, refer only
to two states having the same
specific entropy. This case has
important applications, and is
shown in the figure.

Calculating Entropy Change of an Ideal Gas

When s2 = s1, the following equation relates T1, T2, p1, and p2

p2 pr (T2 )

p1
pr (T1 )

(s1 = s2, air only)

(Eq. 6.41)

where pr(T ) is read from Table A-22 or A-22E, as

appropriate.
Table A-22

Calculating Entropy Change of an Ideal Gas

When s2 = s1, the following equation relates T1, T2, v1, and v2

v2 vr (T2 )

v1 vr (T1 )

(s1 = s2, air only)

(Eq. 6.42)

where vr(T ) is read from Table A-22 or A-22E, as

appropriate.
Table A-22

Entropy Change of an Ideal Gas

Assuming Constant Specific Heats
When the specific heats cv and cp are assumed constant,
Eqs. 6.17 and 6.18 reduce, respectively, to
(Eq. 6.17)

(Eq. 6.18)

(Eq. 6.21)

(Eq. 6.22)

These expressions have many applications.

In particular, they can be applied to develop
relations among T, p, and v at two states
having the same specific entropy as shown in
the figure.

Entropy Change of an Ideal Gas

Assuming Constant Specific Heats
Since s2 = s1, Eqs. 6.21 and 6.22 become

With the ideal gas relations

where k is the specific ratio
These equations can be solved,
respectively, to give

(Eq. 6.43)
(Eq. 6.44)

Eliminating the temperature ratio gives

(Eq. 6.45)

Calculating Entropy Change of an Ideal Gas

Example: Air undergoes a process from T1 = 620 K, p1 = 12 bar
to a final state where s2 = s1, p2 = 1.4 bar. Employing the ideal
gas model, determine the final temperature T2, in K. Solve using
(a) pr data from Table A-22 and (b) a constant specific heat ratio
k evaluated at 620 K from Table A-20: k = 1.374. Comment.
(a) With Eq. 6.41 and pr(T1) = 18.36 from Table A-22
p2
1.4 bar

pr T2 pr T1
18.36
2.142

12 bar
p1

Interpolating in Table A-22, T2 = 339.7 K

Table A-22

Calculating Entropy Change of an Ideal Gas

(b) With Eq. 6.43
p2

T2 T1
p1

k 1 / k

1.4 bar
620 K

12 bar

0.374 / 1.374

T2 = 345.5 K

Comment: The approach of (a) accounts for

variation of specific heat with temperature but
the approach of (b) does not. With a k value
more representative of the temperature interval,
the value obtained in (b) using Eq. 6.43 would be
in better agreement with that obtained in (a) with
Eq. 6.41.

Isentropic Turbine Efficiency

For a turbine, the energy rate
balance reduces to

0 Q cv W cv m

(V12 V22 )
(h1 h2 )
g ( z1 z2 )
2

If the change in kinetic energy of flowing matter is negligible,

(V12 V22) drops out.
If the change in potential energy of flowing matter is
negligible, g(z1 z2) drops out.
If the heat transfer with surroundings is negligible, Q cv drops
out.

W cv
h1 h2
m

where
the left side is work developed per unit of mass flowing.

Isentropic Turbine Efficiency

For a turbine, the entropy rate
balance reduces to

If the heat transfer with surroundings is negligible, Q j

drops out.

cv
s 2 s1 0
m

Isentropic Turbine Efficiency

Since the rate of entropy production
cannot be negative, the only turbine exit
states that can be attained in an adiabatic
expansion are those with s2 s1. This is
shown on the Mollier diagram to the right.
The state labeled 2s on the figure would be attained only in an
isentropic expansion from the inlet state to the specified exit
pressure that is, 2s would be attained only in the absence of
internal irreversibilities. By inspection of the figure, the
maximum theoretical value for the turbine work per unit of mass
flowing is developed in such an internally reversible, adiabatic
expansion:
W cv

m h1 h2s

Isentropic Turbine Efficiency

The isentropic turbine efficiency is
the ratio of the actual turbine work
to the maximum theoretical work,
each per unit of mass flowing:

(Eq. 6.46)

Isentropic Turbine Efficiency

Example: Water vapor enters a turbine
at p1 = 5 bar, T1 = 320oC and exits at p2 = 1
1 bar. The work developed is
measured as 271 kJ per kg of water
vapor flowing. Applying Eq. 6.46,
determine the isentropic turbine
efficiency.

From Table A-4, h1 = 3105.6 kJ/kg, s1 = 7.5308 kJ/kg. With s2s = s1, interpolation in Table A-4
at a pressure of 1 bar gives h2s = 2743.0 kJ/kg. Substituting values into Eq. 6.46

W cv / m
271 kJ/kg
t

0.75 (75%)
h1 h2s 3105.6 2743.0 kJ/kg

Isentropic Compressor and Pump Efficiencies

For a compressor the energy rate
balance reduces to

0 Q cv W cv m

1
2

(V12 V22 )
(h1 h2 )
g ( z1 z2 )
2

If the change in kinetic energy of flowing matter is negligible,

(V12 V22) drops out.
If the change in potential energy of flowing matter is
negligible, g(z1 z2) drops out.
If the heat transfer with surroundings is negligible, Q cv drops
out.

W cv

h2 h1

where
the left side is work input per unit of mass flowing.

Isentropic Compressor and Pump Efficiencies

For a compressor the entropy
rate balance reduces to

If the heat transfer with surroundings is negligible, Q j

drops out.

cv
s 2 s1 0
m

Isentropic Compressor and Pump Efficiencies

Since the rate of entropy production
cannot be negative, the only compressor
exit states that can be attained in an
adiabatic compression are those with s2
s1. This is shown on the Mollier
diagram to the right.
The state labeled 2s on the figure would be attained only in an
isentropic compression from the inlet state to the specified exit
pressure that is, state 2s would be attained only in the
absence of internal irreversibilities. By inspection of the figure,
the minimum theoretical value for the compressor work input
per unit of mass flowing is for such an internally reversible,
adiabatic compression:

Wcv
m

h2s h1

Isentropic Compressor and Pump Efficiencies

The isentropic compressor
efficiency is the ratio of the
minimum theoretical work input to
the actual work input, each per unit
of mass flowing:

(Eq. 6.48)
An isentropic pump efficiency is defined similarly.

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
Consider a one-inlet, oneexit control volume at
steady state:
Compressors, pumps, and
other devices commonly
encountered in engineering
practice are included in this
class of control volumes.
The objective is to introduce expressions for the heat
transfer rate Q cv / m and work rate W cv / m in the absence of
internal irreversibilities. The resulting expressions have
important applications.

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
In agreement with the discussion of energy transfer by
heat to a closed system during an internally reversible
process (Sec. 6.6.1), in the present application we have

(Eq. 6.49)
where the subscript int rev signals that the expression applies
only in the absence of internal irreversibilities.
As shown by the figure, when the states visited by a
unit mass passing from inlet to exit without internal
irreversibilities are described by a curve on a T-s
diagram, the heat transfer per unit of mass flowing is
represented by the area under the curve.

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
Neglecting kinetic and potential energy effects, an energy
rate balance for the control volume reduces to
V12 V22
Q cv
W cv

g z1 z 2

m int m int h1 h2

rev

rev

With Eq. 6.49, this becomes

(1)

Since internal irreversibilities are assumed absent, each unit

of mass visits a sequence of equilibrium states as it passes
from inlet to exit. Entropy, enthalpy, and pressure changes
are therefore related by the TdS equation, Eq. 6.10b:

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
Integrating from inlet to exit:
With this relation Eq. (1) becomes
(Eq. 6.51b)
If the specific volume remains approximately constant,
as in many applications with liquids, Eq. 6.51b becomes
(Eq. 6.51c)
This is applied in the discussion of vapor power cycles
in Chapter 8.

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
As shown by the figure, when the states visited
by a unit mass passing from inlet to exit without
internal irreversibilities are described by a curve
on a p-v diagram, the magnitude of vdp is
shown by the area behind the curve.

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
Example: A compressor operates at
steady state with natural gas entering at
at p1, v1. The gas undergoes a polytropic
process described by pv = constant and
exits at a higher pressure, p2.

(a) Ignoring kinetic and potential energy effects, evaluate

the work per unit of mass flowing.
(b) If internal irreversibilities were present, would the
magnitude of the work per unit of mass flowing be less
than, the same as, or greater than determined in part (a)?

Heat Transfer and Work in Internally Reversible

Steady-State Flow Processes
(a) With pv = constant, Eq. 6.51b gives

The minus sign indicates that the compressor

requires a work input.

(b) Left for class discussion.