CHAPTER 6

Entropy

6.1 INTRODUCTION
To allow us to apply the second law of thermodynamics to a process we will identify a property
called entropy. This will parallel our discussion of the first law; first we stated the first law for a cycle and
then derived a relationship for a process.

6.2 DEFINITION
Consider the reversible
H Carnot engine operating on a cycle consisting of the processes described in
Sec. 5.5. The quantity Q=T is the cyclic integral of the heat transfer divided by the absolute tem-
perature at which the heat transfer occurs. Since the temperature TH is constant during the heat transfer
QH , and TL is constant during heat transfer QL , the integral is given by
I
Q Q Q
= H − L ð6:1Þ
T TH TL
where the heat QL leaving the Carnot engine is considered to be positive. Using (5.4) and (5.9) we see
that, for the Carnot cycle,
QL T QH Q
= L or = L ð6:2Þ
QH TH TH TL
Substituting this into (6.1), we find the interesting result
I
Q
=0 ð6:3Þ
T
Thus, the quantity Q=T is a perfect differential, since its cyclic integral is zero. We let this perfect
differential be denoted by dS, where S represents a scalar function that depends only on the state of the
system. This, in fact, was our definition of a property of a system. We shall call this extensive property
entropy; its differential is given by

Q
dS = ð6:4Þ
T rev

133
134 ENTROPY [CHAP. 6

Fig. 6-1 The Carnot cycle.

where the subscript ‘‘rev’’ emphasizes the reversibility of the process. This can be integrated for a process
to give
Z 2
Q
S = ð6:5Þ
1 T rev

From the above equation we see that the entropy change for a reversible process can be either positive or
negative depending on whether energy is added to or extracted from the system during the heat transfer
process. For a reversible adiabatic process the entropy change is zero.
We often sketch a temperature-entropy diagram for cycles or processes of interest. The Carnot cycle
provides a simple display when plotting temperature vs. entropy. It is shown in Fig. 6-1. The change in
entropy for the first process from state 1 to state 2 is
Z 2
Q Q
S2 − S1 = =− L ð6:6Þ
1 T TL
The entropy change for the reversible adiabatic process from state 2 to state 3 is zero. For the process
from state 3 to state 4 the entropy change is numerically equal to that of the first process; the process
from state 4 to state 1 is also a reversible adiabatic process and is accompanied with a zero entropy
change.
The heat transfer during a reversible process can be expressed in differential form [see (6.4)] as
Q = T dS ð6:7Þ
Hence, the area under the curve in the T -S diagram represents the heat transfer during any reversible
process. The rectangular area in Fig. 6-1 thus represents the net heat transfer during the Carnot cycle.
Since the heat transfer is equal to the work done for a cycle, the area also represents the net work
accomplished by the system during the cycle. Here, Qnet = Wnet = T S.
The first law of thermodynamics, for a reversible infinitesimal change, becomes, using (6.7),
T dS − P dV = dU ð6:8Þ
This is an important relationship in our study of simple systems. We arrived at it assuming a reversible
process. However, since it involves only properties of the system, it holds for an irreversible process also.
If we have an irreversible process, in general, W 6¼ P dV and Q 6¼ T dS but (6.8) still holds as a
relationship between the properties. Dividing by the mass, we have
T ds − P dv = du ð6:9Þ
where the specific entropy is defined to be
S
s= ð6:10Þ
m
CHAP. 6] ENTROPY 135

To relate the entropy change to the enthalpy change we differentiate (4.12) and obtain
dh = du + P dv + v dP ð6:11Þ
Substituting into (6.9) for du, we have
T ds = dh − v dP ð6:12Þ
Equations (6.9) and (6.12) will be used in subsequent sections of our study of thermodynamics for
various reversible and irreversible processes.

6.3 ENTROPY FOR AN IDEAL GAS WITH CONSTANT SPECIFIC HEATS

Assuming an ideal gas, (6.9) becomes
du P dv dT dv
ds = + = Cv +R ð6:13Þ
T T T v
where we have used
du = Cv dT Pv = RT ð6:14Þ
(6.13) is integrated, assuming constant specific heat, to yield
T2 v
s2 − s1 = Cv ln + R ln 2 ð6:15Þ
T1 v1
Similarly, (6.12) is rearranged and integrated to give
T2 P
s2 − s1 = Cp ln − R ln 2 ð6:16Þ
T1 P1
Note again that the above equations were developed assuming a reversible process; however, they relate
the change in entropy to other thermodynamic properties at the two end states. Since the change of a
property is independent of the process used in going from one state to another, the above relationships
hold for any process, reversible or irreversible, providing the working substance can be approximated by
an ideal gas with constant specific heats.
If the entropy change is zero, i.e., an isentropic process, (6.15) and (6.16) can be used to obtain
k−1 ðk−1Þ=k
T2 v1 T2 P2
= = ð6:17Þ
T1 v2 T1 P1
These two equations are combined to give
k
P2 v1
= ð6:18Þ
P1 v2

These are, of course, identical to the equations obtained in Chap. 4 when an ideal gas undergoes a
quasiequilibrium adiabatic process.

EXAMPLE 6.1 Air is contained in an insulated, rigid volume at 20 C and 200 kPa. A paddle wheel, inserted in
the volume, does 720 kJ of work on the air. If the volume is 2 m3 , calculate the entropy increase assuming
constant specific heats.
Solution: To determine the final state of the process we use the energy equation, assuming zero heat
transfer. We have − W = U = mCv T . The mass m is found from the ideal-gas equation to be
PV ð200Þð2Þ
m= = = 4:76 kg
RT ð0:287Þð293Þ
136 ENTROPY [CHAP. 6

The first law, taking the paddle-wheel work as negative, is then

720 = ð4:76Þð0:717ÞðT2 − 293Þ ∴ T2 = 504:0 K
Using (6.15) for this constant-volume process there results
T2 504
S = mCv ln = ð4:76Þð0:717Þ ln = 1:851 kJ=K
T1 293

EXAMPLE 6.2 After a combustion process in a cylinder the pressure is 1200 kPa and the temperature is
350 C. The gases are expanded to 140 kPa with a reversible adiabatic process. Calculate the work done by the
gases, assuming they can be approximated by air with constant specific heats.
Solution: The first law can be used, with zero heat transfer, to give − w = u = Cv ðT2 − T1 Þ. The
temperature T2 is found from (6.17) to be
ðk − 1Þ=k
P 140 ð1:4 −1Þ=1:4
T2 = T1 2 = ð623Þ = 337 K
P1 1200
This allows the specific work to be calculated: w = Cv ðT1 − T2 Þ = ð0:717Þð623 − 337Þ = 205 kJ/kg.

6.4 ENTROPY FOR AN IDEAL GAS WITH VARIABLE SPECIFIC HEATS

If the specific heats for an ideal gas cannot be assumed constant over a particular temperature range
we return to (6.12) and write
dh v dP Cp R
ds = − = dT − dP ð6:19Þ
T T T P
The gas constant R can be removed from the integral, but Cp = Cp ðT Þ cannot. Hence, we integrate (6.19)
and obtain
Z T2
Cp P
s2 − s 1 = dT − R ln 2 ð6:20Þ
T1 T P1
The integral in the above equation depends only on temperature, and we can evaluate its magnitude
from the gas tables. It is found, using the tabulated function so ; to be
Z T2
Cp
s2 − s1 =
o o
dT ð6:21Þ
T1 T

Thus, the entropy change is (in some textbooks is used rather than so )
P2
s2 − s1 = so2 − so1 − R ln ð6:22Þ
P1
This more exact expression for the entropy change is used only when improved accuracy is desired.
For an isentropic process we cannot use (6.17) and (6.18) if the specific heats are not constant.
However, we can use (6.22) and obtain, for an isentropic process,
o
P2 s − so1 expðso2 =RÞ f ðT2 Þ
= exp 2 = = ð6:23Þ
P1 R expðso1 =RÞ f ðT1 Þ
Thus, we define a relative pressure Pr , which depends only on the temperature, as
o
=R
Pr = e s ð6:24Þ
CHAP. 6] ENTROPY 137

It is included as an entry in the gas table E-1. The pressure ratio for an isentropic process is then
P2 P
= r2 ð6:25Þ
P1 Pr1
The volume ratio can be found using the ideal-gas equation of state. It is
v2 P T
= 2 2 ð6:26Þ
v1 P1 T1
where we would assume an isentropic process when using the relative pressure ratio. Consequently, we
define a relative specific volume vr , dependent solely on the temperature, as
T
vr = const: ð6:27Þ
Pr
Using its value from the gas tables we find the specific volume ratio for an isentropic process; it is
v2 v
= r2 ð6:28Þ
v1 vr1
With the entries from the gas tables we can perform the calculations required in working problems
involving an ideal gas with variable specific heats.

EXAMPLE 6.3 Repeat Example 6.1 assuming variable specific heats.

Solution: Using the gas tables, we write the first law as − W = U = mðu2 − u1 Þ. The mass is found from
the ideal-gas equation to be
PV ð200Þð2Þ
m= = = 4:76 kg
RT ð0:287Þð293Þ
The first law is then written as
W − 720
u2 = − + u1 = − + 209:1 = 360:4 kJ=kg
m 4:76
where u1 is found at 293 K in the gas tables by interpolation. Now, using this value for u2 , we can interpolate to
find
T2 = 501:2 K so2 = 2:222
The value for so1 is interpolated to be so1 = 1:678. The pressure at state 2 is found using the ideal-gas equation for
our constant-volume process:

P2 P T 501:2
= 1 P2 = P1 2 = ð200Þ = 342:1 kPa
T2 T1 T1 293
Finally, the entropy change is

P 342:1
S = m so2 − so1 − R ln 2 = 4:76 2:222 − 1:678 − 0:287 ln = 1:856 kJ=K
P1 200
The approximate result of Example 6.1 is seen to be less than 0.3% in error because T2 is not very large.

EXAMPLE 6.4 After a combustion process in a cylinder the pressure is 1200 kPa and the temperature is
350 C. The gases are expanded to 140 kPa in a reversible, adiabatic process. Calculate the work done by the
gases, assuming they can be approximated by air with variable specific heats.
Solution: First, at 623 K the relative pressure Pr1 is interpolated to be Pr1 = ð20 3
Þð20:64 − 18:36Þ +
18:36 = 18:70. For an isentropic process,

P 140
Pr2 = Pr1 2 = ð18:70Þ = 2:182
P1 1200