222 C H A P T E R 7: Second Law of Thermodynamics and Entropy Transport and Production Mechanisms

For a stationary differential closed system at a uniform temperature T containing a pure substance that is
subjected to only a mechanical moving boundary work mode, Eq. (7.29) becomes
T dS = dU + p dV
and on dividing through by the system mass m and the absolute temperature T,
du p
ds = + dv (7.30)
T T
Since u = h − pv, this equation can also be written as
dh v
ds = − dp (7.31)
T T
In Chapter 3, we define the constant volume and constant pressure specific heats for an incompressible
substance as

du
cv = cp = c =
dT
Since v = constant and dv = 0 for an incompressible material, then Eq. (7.30) becomes
dT
ðdsÞincomp: = c
T
or
Z T2
dT
ðs2 − s1Þincomp: = c (7.32)
T1 T
If the specific heat c is constant over the temperature range from T1 to T2, then this equation can be integrated
to give

ðs2 − s1Þincompressible material = c lnðT2 /T1 Þ (7.33)

with a constant c

In Chapter 3, we also define the constant volume and constant pressure specific heats for an ideal gas as

du
cv = (3.37)
dT
and

cp = dh (3.40)
dT
Consequently, we can now write Eqs. (7.30) and (7.31) as
dT p dT v
ðdsÞ ideal = cv + dv = cp − dp
gas T T T T

Further, for an ideal gas, p/T = R/v and v/T = R/p, so this equation can be integrated to give
Z 2
dT v
ðs2 − s1 Þ ideal = cv + R ln 2 (7.34)
gas 1 T v1

Z 2
= dT − R ln p2
cp (7.35)
1 T p1
and if the specific heats are constant over the temperature range from T1 to T2, then these equations become

T2 v
ðs2 − s1 Þ ideal gas = cv ln + R ln 2 (7.36)
T1 v1
constant
cp and cv

T2 p2
= cp ln − R ln (7.37)
T1 p1
 7.8 Numerical Values for Entropy 223

DO ALL ELASTIC MATERIALS HAVE ENTROPIC ELASTICITY?

No, most elastic solids do not have entropic elasticity, but the elasticity present in rubber and polymers is largely entropic. When
work is done adiabatically on a material with entropic elasticity, the temperature of the material increases. You can demonstrate
this by stretching a rubber band rapidly then immediately touching it to your lips (which are very sensitive to temperature). The
rubber band is warmer than it was before it was stretched. Then, if you hold the stretched rubber band long enough for it to
return to room temperature and suddenly release it and touch it to your lips, it is colder than it was before it was stretched.

When an elastic deformation produces a decrease in the specific entropy of a material, it is said to have entropic
elasticity. In the case of an ideal gas, Eq. (7.36) shows that an isothermal (T2 = T1 ) compression (v 2 < v1 )
produces a decrease in the specific entropy of the gas. Consequently, ideal gases have entropic elasticity.
Any process in which entropy remains constant is called an isentropic process. The term isentropic comes from the
Greek words for “constant entropy.”
If an ideal gas with constant specific heats undergoes an isentropic process, then s2 − s1 and Eqs. (7.36) and
(7.37) give
T2 R v R p2
ln = − ln 2 = ln
T1 cv v1 cp p1
or
For an isentropic process with an ideal gas,
1−k ðk−1Þ/k
T2 v2 p2
= = (7.38)
T1 v1 p1

and
p1 v1k = p2 v2k = constant (7.39)
where
k = cp /cv and R = cp − cv (7.40)
Consequently, from Eq. (4.27), we see that, in the case of an ideal gas with constant specific heats, an isentropic
process is the same as a polytropic process with n = k.
These equations for the specific entropy of an incompressible substance and an ideal gas are the only such for-
mulae to be introduced at this point. Specific entropy equations for more complex substances are introduced
later in the text as they are needed.

EXAMPLE 7.4
An insulated apparatus contains 1.5 kg of saturated liquid water at 20.°C. Determine the change in specific entropy of the
water as it is pressurized from 0.10 MPa to 10. MPa. Assume the liquid water is an incompressible material.

Solution
First, draw a sketch of the system (Figure 7.12).

The unknown is the change in specific entropy, s2 − s1, for the system. The material is liquid water.

An energy balance for this process gives

1Q2 − 1W2 = mðu2 − u1 Þ

Z
and since the apparatus is insulated 1Q2 = 0. The only possible work mode here is moving boundary work, so 1W2 = pdV.
But the water is to taken as incompressible, so V = constant and dV = 0. Also, Eq. (3.33) gives the specific internal energy
change of an incompressible material as u2 − u1 = cðT2 − T1 Þ, where c is the specific heat of the material. Then, the energy
balance equation gives for this process
0 − 0 = mcðT2 − T1 Þ

(Continued )
224 C H A P T E R 7: Second Law of Thermodynamics and Entropy Transport and Production Mechanisms

EXAMPLE 7.4 (Continued )

Insulation

m = 1.5 kg
x1 = 0 m = 1.5 kg
T1 = 20.°C p2 = 0.10 MPa
p1 = 0.10 MPa ∀2 =∀1
s1 = ? s2 = ?
State 1 State 2
Constant volume process
s2 − s 1 = ?

FIGURE 7.12
Example 7.4.
or, T2 = T1. Therefore, the process must also be isothermal, and Eq. (7.33) gives the specific entropy change as
s2 − s1 = c lnðT2 =T1 Þ = c lnð1Þ = 0
Consequently, the entropy of an incompressible material is not altered by changing its pressure.

EXAMPLE 7.5
An apparatus contains 0.035 kg of air (an ideal gas). The apparatus is used to compress the air isentropically (i.e., at
constant entropy) from a pressure of 0.100 MPa to a pressure of 5.00 MPa. If the initial temperature of the air is 20.0°C,
determine the final temperature and specific volume of the air.

Solution
First, draw a sketch of the system (Figure 7.13).

Air Air
m = 0.035 kg m = 0.035 kg
p1 = 0.100 MPa p2 = 5.00 MPa
T1 = 20.0°C T2 = ?
v2 = ?
State 1 State 2
Isentropic process

FIGURE 7.13
Example 7.5.
The unknowns are the final temperature, T 2 , and specific volume, v 2 , of the air in the system. Since p 1 = 0.100 MPa,
T1 = 20.0°C, and p2 = 5.00 MPa, then Eq. (7.38) can be used to find T2 and v2 as follows. From Thermodynamic Tables to
accompany Modern Engineering Thermodynamics, Table C.13b, we find for air that k = 1.4; and solving Eq. (7.38) for T2 gives
k−1 0:4
p
T2 = T1 2 k = ð20:0 + 273:15 KÞ 5:00 MPa 1:4 = 896 K = 623°C
p1 0:100 MPa
Using the ideal gas equation of state and Table C.13b for the gas constant of air (Rair = 0.286 kJ/kg · K), we find the initial
specific volume of the air to be
v1 = mRT1 /p1
= ð0:035 kgÞð0:286 kJ=kg . KÞð20:0 + 273:15 KÞ/ð0:100 × 103 kN=m2 Þ
= 0:02934 m3 =kg
Then, solving Eq. (7.38) for v2 gives
1 1
−
= ð0:02934 m3 =kgÞ 623 + 273:15
T2 1−k 0:4 = 0:00180 m3 =kg
v2 = v1
T1 20:0 + 273:15

Exercises
7. Determine the change in specific entropy as a 1.00 kg block of solid incompressible iron is heated from 20.0°C to 100.°C.
(See Table 3.6 for specific heat values.) Answer: (s2 − s1)iron = 0.108 kJ/kg · K.
8. Determine the change in specific entropy of air as it is heated from 20.0°C to 100.°C in a constant pressure (isobaric)
process. Assume air behaves as an ideal gas. Answer: (s2 − s1)isobaric air = 0.242 kJ/kg · K.
9. Determine the change in specific entropy of air as it is heated from 20.0°C to 100.°C in a constant volume (isochoric)
process. Assume air behaves as an ideal gas. Answer: (s2 − s1)isochoric air = 0.173 kJ/kg · K.
 7.8 Numerical Values for Entropy 225

The tables and charts in Thermodynamic Tables to accompany Modern Engineering Thermodynamics list specific
entropy along with the specific properties v, u, and h. Specific entropy values are obtained from these sources in
the same way that any of the other specific properties are obtained. In particular, the quality x of a liquid-vapor
mixture is computed using the same type of lever rule relation as was used with v, u, and h; that is,
v − vf u − uf h − hf s − sf
x= = = = (7.41)
vfg ufg hfg sfg

EXAMPLE 7.6
Determine the change in total entropy of 3.00 lbm of steam at 100.°F and 80.0% quality when it is heated in an unknown
process to 200. psia and 800.°F.

Solution
First, draw a sketch of the system (Figure 7.14).

Steam m = 3.00 lbm

m = 3.00 lbm
p2 = 200. psia
T1 = 100.°F
T2 = 800.°F
x1 = 80.0%
State 1 State 2
Unknown process
s2 − s1 = ?

FIGURE 7.14
Example 7.6.
The unknown is the change in total entropy of the steam. Since we are given two independent properties in each state in
this problem, we do not need to know how the heating process (i.e., the path) took place. We have a closed system consist-
ing of 3.0 lbm of water, for which

State 1 Unknown process path State 2

!
T1 = 100:°F p2 = 200: psia
x1 = 0:800 T2 = 800:°F
s1 = sf ð100:°FÞ + x1 sfg ð100:°FÞ s2 = 1:7662 Btu/lbm . R
= 0:1296 + 0:800ð1:8528Þ
= 1:6118 Btu/lbm . R

where the specific entropy values have been found in Tables C.1a and C.3a. Then,
S2 − S1 = mðs2 − s1 Þ
= ð3:00 lbmÞ½ð1:7662 − 1:6118Þ Btu/ðlbm . R Þ
= 0:463 Btu/R

Exercises
10. Determine the change in specific entropy of steam as it is cools from a saturated vapor (x = 100.%) at 100.°F to a
saturated liquid (x = 0%) at 100.°F. Answer: s2 − s1 = sf (100.°F) − sg (100.°F) = −sfg(100.°F) = −1.8528 Btu/lbm· R.
11. Saturated liquid ammonia at 0.00°C is heated in a constant pressure process until it has a quality of 50.0%. Determine
the change in specific entropy of the ammonia. Answer: s2 − s1 = 2.311 kJ/kg · K.
12. Determine the magnitude of the change in specific entropy of a water liquid-vapor mixture at 100.°C as its quality
decreases from 1.000 by (a) 1.00%, (b) 10.0%, (c) 50.0%. Answers: (a) |s2 − s1| = 0.0605 kJ/kg · K, (b) |s2 − s1| =
0.605 kJ/kg · K, and (c) |s2 − s1| = 3.024 kJ/kg · K.

Figure 7.15 is an h-s plot for water. It is called a Mollier diagram after the German engineer Richard Mollier
(1863–1935), who developed it in 1904. States 1 and 2 of Example 7.6 are shown on this chart to illustrate its
use. Small charts like this are usually inaccurate for engineering problem solving. Professional engineers used
much larger charts like this before thermodynamic property software became available.
At this point, we must expand the classical concepts presented thus far so that they fit into the more general
balance equations introduced at the beginning of this chapter. We must now look for a set of general entropy
transport mechanisms, valid for both open and closed systems, that are consistent with Eq. (7.28) when applied
to closed systems.
226 C H A P T E R 7: Second Law of Thermodynamics and Entropy Transport and Production Mechanisms

State 2 of
Example 7.6

1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2

1600

1550

1500

1450

1400

1350

1300
/lbm
tu

1250
h, B
,
alpy
enth

1200
cific
Spe

1150

1100

2.2
1050

2.1
1000

2.0
950
Critical
state
1.9
State 1 of
900 Example 7.6

1.8
850

1.7
800
1.0 1.1 1.2 1.3 1.4 1.5 1.6
Specific entropy, s, Btu/(lbm . R)

FIGURE 7.15
The Mollier diagram for water. (Source: Keenan, J. H., Keyes, J., 1936. Thermodynamic Properties of Steam. Wiley, New York. Reprinted
by permission of John Wiley & Sons.)
 7.10 Differential Entropy Balance 227

7.9 ENTROPY TRANSPORT MECHANISMS

Several conceptual problems occur when Eq. (7.22) is used to define the entropy of a system. First of all, this
equation is limited to closed systems, and at this point, we do not know how it must be altered to accommo-
date open systems. Second, it does not indicate how system entropy may be influenced by the work transport of
energy; third, it deals only with hypothetical “reversible” processes. The third point is particularly bothersome,
since all of our auxiliary formulae for heat transfer have been developed from an empirical basis and therefore
always give the actual rather than the reversible heat transport of energy (see Chapter 4).
From the work of Carnot, Thomson, and Clausius discussed earlier in this chapter, it seems clear that energy and
entropy are related in some way. In this chapter, we investigate the possibility that the energy transport mechan-
isms of heat transfer and work modes are also mechanisms for entropy transport. In Chapter 9, we expand this
investigation to include mass flow transport of entropy.
First, we investigate heat and work transports of entropy by again restricting our analysis to closed systems. In
Chapter 4, we note a modern definition of heat transfer: It is an energy transport mechanism that is neither a
work mechanism nor a mass flow mechanism. It is often conveniently viewed as a nonwork, nonmass flow
mechanism for transporting internal energy.

7.10 DIFFERENTIAL ENTROPY BALANCE

In a reversible process, the production of entropy is always zero, by definition. Therefore, if Eq. (7.22) is viewed
as a differential entropy balance for a closed system undergoing a reversible heat transport of energy, then from
a differential form of Eq. (7.2), it is clear that the heat transport of entropy is given by

dQ
ðdSG ÞQ = ðdSÞQ = ðdST Þrev + ðdSP Þrev =
Q Q T rev

So, the differential entropy transport due to a hypothetical reversible heat transfer is simply

dQ
ðdST Þrev = (7.42)
Q T rev

Unfortunately, the two sides of Eq. (7.42) do not have the same differential form. The left side is the total differ-
ential of ST, whereas the right side is a differential divided by an absolute temperature. To integrate this equation
over the surface area of the system, we need to know the exact mathematical relationship between Q and the
temperature of the boundary Tb at the point where this heat transfer occurs. For a reversible Carnot cycle, this
relation is very simple, since a reversible heat transfer occurs only during an isothermal process; so Tb must be a
constant. In this case, Eq. (7.42) can be integrated to give

1Q2
=
1ðST Þ2 rev Q and
Tb (7.43)
rev Q and
isothermal isothermal

However, Eq. (7.42) cannot be as easily integrated for common nonisothermal heat transfer processes. This pro-
blem can be solved by changing the form of Eq. (7.42) by introducing the following mathematical identity

dQ Q Q
=d + 2 dT (7.44)
T T T
Then, Eq. (7.42) becomes

Q Q
ðdST Þrev = d + dT
Q T rev T2 rev

Recall that heat transfer irreversibility is simply due to the heat transport of energy through a finite temperature
difference, so that for all reversible heat transfers, we must have dT = 0, or

Q
dT =0
T2 rev