Chapter 6

Entropy
6.1 Clausius Inequality and Definitionof Entropy
The Clausius inequality states that for any thermodynamic cycle

δQ
≤0 (6.1-1)
T b

In this expression δQ is the heat transfer and T is the temperature at the system boundary.
The equality applies when there are no (internal) irreversibilities as the system excecute the
cycle. Consider two cycles executed by a closed system shown in Figure 6.1. One cycle
follows a reversible path A from state 1 to state 2, followed by a reversible path C from state
2 to state 1. The other cycle follows a reversible path B from state 1 to state 2, followed by
the same reversible path C from state 2 to state 1 as in the first cycle.

C
B
A

1
Figure 6.1-1 Two reversible cycles.

Applying Clausius inequality to the first cycle 1A2C1 gives

2 δQ 1 δQ
+ =0 (6.1-2a)
1 T A
2 T C

The right hand side of Clausius inequality is set to zero since the cycle is composed of
reversible processes. Similarly for the second cycle 1B2C1 we have

2 δQ 1 δQ
+ =0 (6.1-2b)
1 T B
2 T C

Comparing Eq. (6.1-2a) and Eq. (6.1-2b) we obtain

2 δQ 2 δQ
=
1 T A
1 T B

Since the paths A and B are arbitrary, the value of the integral depends only on the end states.
6-1
The integral therefore represents the change in some property of the system. We call this
property entropy, and the change in entropy is given by

2 δQ
∆S = S2 − S1 = (6.1-3)
1 T rev

On differential form, the definition of entropy is given by

δ Qrev
dS = (6.1-4)
T

Since entropy is a property, the change in entropy of a system in going from one state to
another state is independent of the processes, reversible or irreversible. The entropy value
might be obtained from software, table, or chart as shown in Table 6.1-1 and Figure 6.1-1.

Table 6.1-1 Entropy values for water at 212oF

Specific Internal Specific Specific
Temp Pressure Volume Energy Enthalpy Entropy Quality Phase
F psia ft3/lbm Btu/lbm Btu/lbm Btu/lbm/R
1 212 14.7 0.01672 180.1 180.1 0.3121 0 Saturated Liquid
2 212 14.7 26.8 1078 1150 1.757 1 Saturated Vapor
3 212 14.7 10.73 539.1 568.3 0.8899 0.4 Liquid Vapor Mixture

Figure 6.1-1 Temperature-entropy diagram for water.

6-2
6.2 Fundamental Property Relations
The first law for a closed system undergoing reversible process with only PV work is given
by

dU = δQrev + δWrev

From the second law, δQrev = TdS, the first law can be written as

d U = Td S − p d V (6.2-1)

We can write the change in internal energy in terms of two independent variables S and V,
that is, U = U(S, V):

∂U ∂U
dU = dS + dV (6.2-2)
∂S V ∂V S

Comparing equations (6.2-1) and (6.2-2) we have

∂U ∂U
T= and p = − (6.2-3)
∂S V ∂V S

The four functions U, H, A, and G are collectively called thermodynamic potentials. The
expression represented by U = U(S, V) results in the partial derivatives of the thermodynamic
potentials corresponding to thermodynamic properties T and p as defined in Eq. (6.2-3).
While U can be a function of any two properties, no other grouping of independent properties
x and y, U = U(x, y), allows us to write partial derivatives in terms of thermodynamic
properties as given by Eq. (6.2-3). The three properties {U, S, V} form a fundamental
grouping.

Similarly, the change in enthalpy (H = U + pV) is given by

dH = dU + d(pV) = TdS − pdV + pdV +Vdp

d H = Td S + V d p (6.2-4)

The change in enthalpy in terms of two independent variables S and p is

∂H ∂H
dH = dS + dp (6.2-5)
∂S P ∂p S

Comparing equations (6.2-4) and (6.2-5) we have

∂H ∂H
T= and V = (6.2-6)
∂S P ∂p S

6-3
We have two more relations for the change in Helmholtz free energy, dA, and the change in
Gibbs free energy, dG,

dA = − S dT − p dV (6.2-7)

dG = − SdT + VdpP (6.2-8)

The fundamental groupings {A, T, V} and {G, T, p} result in

∂A ∂A
S=− and p = − (6.2-9)
∂T V ∂V T

∂G ∂G
S=− and V = (6.2-10)
∂T P ∂p T

The grouping can be obtained from the following diagram where there properties at a corner
form a fundamental grouping, for example {A, T, V} and {G, T, p}.

G p H Great physicists Have Study

Under Very Able Teachers
T S

A V U

Thermodynamic properties can then be obtained from the partial derivative of the
thermodynamics potentials. Temperature can be obtained from the derivative of H or U. In
both cases, the variable opposite T in the diagram will be in the denominator of the derivative
and the remaining variable belong to the grouping will be the variable keeping constant.

G p H G p H

T S T S

A V U A V U

Using this rule, we have

∂U ∂H
T= and T =
∂S V ∂S P

6-4
Similarly, p can be expressed in terms of the partial derivative of thermodynamic potentials
using the following diagram. Note the minus sign since V is in the negative direction of P.

G p H G p H

T S T S

A V U A V U

∂U ∂A
p=− and p = −
∂V S ∂V T

Similarly, we have

G p H G p H

T S T S

A V U A V U

∂A ∂G
S=− and S = −
∂T V ∂T P

and
G p H G p H

T S T S

A V U A V U

∂H ∂G
V= and V =
∂p S
∂p T

When we study phase equilibrium, the Gibbs free energy will be use frequently to obtain the
relations between the measured properties.

6-5
6.3 Entropy Balance for Closed Systems

The entropy balance for a closed system can be written as

2 δQ
S2 − S1 = +σ (6.3-1)
1 T b

In this equation, S2 − S1 is the change in the amount of entropy contained within the system,
2 δQ
is the net amount of entropy transferred in across the system boundary, and σ is
1 T
b

the amount of entropy produced within the system all during some time interval ∆t. The
entropy production will be zero if no irreversibilities present within the system. In differential
form, the entropy balance is given by

δQ
dS = + δσ (6.3-2)
T b

Example 6.3-11. ----------------------------------------------------------------------------------

Water initially a saturated liquid at 150°C is contained within a piston–cylinder assembly.
The water undergoes a process to the corresponding saturated vapor state, during which the
piston moves freely in the cylinder. There is no heat transfer with the surroundings. If the
change of state is brought about by the action of a paddle wheel, determine the net work per
unit mass, in kJ/kg, and the amount of entropy produced per unit mass, in kJ/kg·K.

Solution ------------------------------------------------------------------------------------------

Specific Internal Specific Specific

Temp Pressure Volume Energy Enthalpy Entropy Quality Phase
C MPa m3/kg kJ/kg kJ/kg kJ/kg/K
1 150 0.4759 0.00109 631.7 632.2 1.842 0 Saturated Liquid
2 150 0.4759 0.3928 2560 2746 6.838 1 Saturated Vapor

From the energy balance with negligible change in kinetic and potential energies:

1 Moran, M. J. and Shapiro H. N., Fundamentals of Engineering Thermodynamics, Wiley, 2008, pg. 272
6-6
 ∆U = Q + W

W
Since Q = 0, = u2 − u1 = 2560 − 631.7 = 1928.3 kJ/kg
m

2 δQ
S2 − S1 = +σ=σ
1 T b

σ
= s2 − s1 = 6.838 − 1.842 = 4.996 kJ/kg⋅K
m

Example 6.3-22. ----------------------------------------------------------------------------------

During steady state operation, a gearbox receives 60 kW through the input shaft and delivers
power through the output shaft. For the gearbox as the system, the rate of energy transfer by
convection is

Q = − hA(Tb − Tf), where h = 0.171 kW/m2⋅K, A = 1.0 m2.

Evaluate the rate of entropy production σ , in kW/K, for (a) the gearbox as the system and
(b) an enlarge system consisting of the gearbox and enough of its surroundings that heat
transfer occurs at the temperature of the surroundings away from the immediate vicinity of
the gearbox, Tf = 293 K.

Solution ------------------------------------------------------------------------------------------

(a) The rate of entropy production σ , in kW/K, for the gearbox as the system

The entropy balance is given by

2 δQ
S2 − S1 = +σ
1 T b

2 Moran, M. J. and Shapiro H. N., Fundamentals of Engineering Thermodynamics, Wiley, 2008, pg. 277
6-7
For constant temperature, the entropy rate balance for the closed system is

dS Q
= +σ
dt Tb

For steady state we have

Q
σ=−
Tb

Q = − hA(Tb − Tf) = − (0.171 kW/m2⋅K)(1 m2)(300 − 293)K = − 1.2 kW

Q (−1.2 kW)
σ = =− = 4×10-3 kW/K
Tb 300 K

(b) The rate of entropy production σ , in kW/K, for an enlarge system consisting of the
gearbox and enough of its surroundings that heat transfer occurs at the temperature of
the surroundings.

dS Q
= +σ
dt Tf

For steady state we have

Q (−1.2 kW)
σ=− = − = 4.1×10-3 kW/K
Tf 293 K

------------------------------------------------------------------------------------------

The entropy balance for an isolated system is given by

2 δQ
∆Siso = + σiso
1 T b

2 δQ
Since = 0 for an isolated system, we have
1 T b

∆Siso = ∆Ssys + ∆Ssurr = σiso ≥ 0

The only processes that can occur are those for which the production of entropy for isolated
systems is positive.

6-8