Chapter 5

The Second Law of

Thermodynamics

Thermodynamics treats the principles of energy transformations, and the laws of thermodynamics
establish the bounds within which these transformations are observed to occur. The first law
states the principle of energy conservation, leading to energy balances in which work and heat are
included as simple additive terms. Yet work and heat are otherwise quite different. Work is directly
useful in ways that heat is not, e.g., for the elevation of a weight or for the acceleration of a mass.
Evidently, work is a form of energy intrinsically more valuable than an equal quantity of heat. This
difference is reflected in a second fundamental law which, together with the first law, makes up the
foundation upon which the edifice of thermodynamics is built. The purpose of this chapter is to:

∙ Introduce the concept of entropy, an essential thermodynamic property

∙ Present the second law of thermodynamics, which reflects the observation that limits
exist to what can be accomplished even by reversible processes
∙ Apply the second law to some familiar processes
∙ Relate changes in entropy to T and P for substances in the ideal-gas state
∙ Present entropy balances for open systems
∙ Demonstrate the calculation of ideal work and lost work for flow processes
∙ Relate entropy to the microscopic world of molecules

5.1 AXIOMATIC STATEMENTS OF THE SECOND LAW

The two axioms presented in Chapter 2 in relation to the first law have counterparts with
respect to the second law. They are:
Axiom 4: There exists a property called entropy1 S, which for systems
at internal equilibrium is an intrinsic property, functionally related to the
1Pronounced en’-tro-py to distinguish it clearly from en-thal’-py.

173
 measurable state variables that characterize the system. Differential
changes in this property are given by the equation:

​​ ​dS​​  t​= ​dQ​ rev​​ / T ​​ (5.1)

where St is the system (rather than the molar) entropy.

Axiom 5: (The Second Law of Thermodynamics) The entropy change

of any system and its surroundings, considered together, and resulting
from any real process, is positive, approaching zero when the process
approaches reversibility. Mathematically,

​​ Δ​S​ total​​ ≥ 0 ​​ (5.2)

The second law affirms that every process proceeds in such a direction that the total
entropy change associated with it is positive, the limiting value of zero being attained only by
a reversible process. No process is possible for which the total entropy decreases. The practical
utility of the second law is illustrated by application to two very common processes. The first
shows its consistency with our everyday experience that heat flows from hot to cold. The second
shows how it establishes limits to the conversion of heat to work by any device.

Application of the Second Law to Simple Heat Transfer

First, consider direct heat transfer between two heat reservoirs, bodies imagined capable of absorbing
or rejecting unlimited quantities of heat without temperature change.2 The equation for the
entropy change of a heat reservoir follows from Eq. (5.1). Because T is constant, integration gives:
Q
ΔS = __
​ ​   ​​
T
A quantity of heat Q is transferred to or from a reservoir at temperature T. From the res-
ervoir’s point of view the transfer is reversible, because its effect on the reservoir is the same
regardless of source or sink of the heat.
Let the temperatures of the reservoirs be TH and TC with TH > TC. Heat quantity Q,
transferred from one reservoir to the other, is the same for both reservoirs. However, QH and
QC have opposite signs: positive for the heat added to one reservoir and negative for the heat
extracted from the other. Therefore QH = −QC, and the entropy changes of the reservoirs at
TH and at TC are:

t ​QH ​  ​​ ​− Q​ C​​ t ​Q​ C​​

Δ​S​  H ​​  = ___
​ ​   ​ = _____​   ​   and  Δ​S​  C ​​  = ___
​   ​​
​T​ H​​ ​T​ H​​ ​T​ C​​

These two entropy changes are added to give:

( ​T​ H​​​T​ C​​ )
t t ​− Q​ C​​ ___ ​Q​ C​​ ​T​ H​​ − ​T​ C​​
Δ​S​ total​​ = Δ​S​  H ​​  + Δ​S​  C ​​  = _____
​ ​   ​ + ​   ​ = ​Q​C​ _______
​   ​ ​​
​T​ H​​ ​T​ C​​

2The firebox of a furnace is in effect a hot reservoir, and the surrounding atmosphere, a cold reservoir.
 Because the heat-transfer process is irreversible, Eq. (5.2) requires a positive value for
ΔStotal, and therefore
​​Q​ C​​​(​T​ H​​ − ​T​ C​​)​ > 0​

With the temperature difference positive, QC must also be positive, which means that
heat flows into the reservoir at TC, i.e., from the higher to the lower temperature. This result
conforms to universal experience that heat flows from higher to lower temperature. A formal
statement conveys this result:
No process is possible which consists solely of the transfer of heat from
one temperature level to a higher one.
Note also that ΔStotal becomes smaller as the temperature difference decreases.
When TH is only infinitesimally higher than TC, the heat transfer is reversible, and ΔStotal
approaches zero.

Application of the Second Law to Heat Engines

Heat can be used far more usefully than by simple transfer from one temperature level to a
lower one. Indeed, useful work is produced by countless engines that employ the flow of heat
as their energy source. The most common examples are the internal-combustion engine and
the steam power plant. Collectively, these are heat engines. They all rely on a high-temperature
source of heat, and all discard heat to the environment.
The second law imposes restrictions on how much of their heat intake can be converted
into work, and our object now is to establish quantitatively this relationship. We imagine that
the engine receives heat from a higher-temperature heat reservoir at TH and discards heat to a
lower-temperature reservoir TC. The engine is taken as the system and the two heat reservoirs
comprise the surroundings. The work and heat quantities in relation to both the engine and the
heat reservoirs are shown in Fig. 5.1(a).
With respect to the engine, the first law as given by Eq. (2.3) becomes:
​
ΔU = Q + W = ​QH
​ ​+ ​Q​C​+ W​

Because the engine inevitably operates in cycles, its properties over a cycle do not
change. Therefore ΔU = 0, and W = −QH − QC.
The entropy change of the surroundings equals the sum of the entropy changes of the
reservoirs. Because the entropy change of the engine over a cycle is zero, the total entropy
change is that of the heat reservoirs. Therefore

​QH ​ ​ ​Q​C​
Δ​S​total​= − ___
​ ​ ​− ___​ ​​
​T​H​ ​T​C​

Note that QC with respect to the engine is a negative number, whereas QH is positive. Combining
this equation with the equation for W to eliminate QH yields:

( ​T​C​ )
​T​H​− ​T​C​
W = ​T​H​Δ​S​total​+ ​Q​C​ ______
​ ​ ​ ​​
 Hot Reservoir Hot Reservoir

QH QH

W W

QC QC

Cold Reservoir Cold Reservoir

(a) (b)

Figure 5.1: Schematic diagrams: (a) Carnot engine; (b) Carnot heat pump or refrigerator.

This result gives the work output of a heat engine within two limits. If the engine is
totally ineffective, W = 0; the equation then reduces to the result obtained for simple heat
transfer between the two heat reservoirs, i.e.:

( ​T​H​​T​C​ )
​T​H​− ​T​C​
Δ​S​total​= − ​Q​C​ ______
​ ​ ​ ​​

The difference in sign here simply reflects the fact that QC is with respect to the engine,
whereas previously it was with respect to the lower-temperature reservoir.
If the process is reversible in all respects, then ΔStotal = 0, and the equation reduces to:

( ​T​ C​​ )
​T​ H​​
W = ​Q​C​ ___
​ ​   ​ − 1 ​​ (5.3)

A heat engine operating as described in a completely reversible manner is very special

and is called a Carnot engine. The characteristics of such an ideal engine were first described
by N. L. S. Carnot3 in 1824.
Note again that QC is a negative number, as it represents heat transferred from the engine.
This makes W negative, in accord with the fact that work is not added to, but is produced by,
the engine. Clearly, for any finite value of W, QC is also finite. This means that a portion of
the heat transferred from the higher-temperature reservoir must inevitably be exhausted to the
lower-temperature reservoir. This observation can be given formal statement:
It is impossible to construct an engine that, operating in a cycle, produces
no effect (in system and surroundings) other than the extraction of heat
from a reservoir and the performance of an equivalent amount of work.
3Nicolas Leonard Sadi Carnot (1796−1832), French engineer. See http://en.wikipedia.org/wiki/Nicolas_Leonard_
Sadi_Carnot.
 The second law does not prohibit the continuous production of work from heat, but it does
place a limit on how much of the heat taken into a cyclic process can be converted into work.
Combining this equation with W = −QH − QC to eliminate first W and then QC leads to
Carnot’s equations:
− ​Q​C​ ___
____ ​QH ​​
​
​ ​= ​ ​​ (5.4)
​T​C​ ​T​H​
W
___ ​T​C​
​ ​= ___
​ ​ ​− 1​ (5.5)
​QH
​ ​ ​T​H​
Note that in application to a Carnot engine QH, representing heat transferred to the
engine, is a positive number, making the work produced (W) negative. In Eq. (5.4) the small-
est possible value of QC is zero; the corresponding value of TC is absolute zero on the Kelvin
scale, which corresponds to −273.15°C.
The thermal efficiency of a heat engine is defined as the ratio of the work produced to
the heat supplied to the engine. With respect to the engine, the work W is negative. Thus,
−W
η ≡ ___
​ ​ ​​ (5.6)
​QH
​​
In view of Eq. (5.5) the thermal efficiency of a Carnot engine is:
​T​C​
​​η​  Carnot​​ = 1 − ___
​ ​​ (5.7)
​T​H​
Although a Carnot engine operates reversibly in all respects, and cannot be improved,
its efficiency approaches unity only when TH approaches infinity or TC approaches zero.
Neither condition exists on earth; all terrestrial heat engines therefore operate with thermal
efficiencies less than unity. The cold reservoirs available on earth are the atmosphere, lakes,
rivers, and oceans, for which TC ≃ 300 K. Hot reservoirs are objects such as furnaces where the
temperature is maintained by combustion of fossil fuels or by fission of radioactive elements,
and for which TH ≃ 600 K. With these values, η = 1 − 300/600 = 0.5, an approximate realistic
limit for the thermal efficiency of a Carnot engine. Actual heat engines are irreversible, and
η rarely exceeds 0.35.

Example 5.1
A central power plant, rated at 800,000 kW, generates steam at 585 K and discards
heat to a river at 295 K. If the thermal efficiency of the plant is 70% of the maximum
possible value, how much heat is discarded to the river at rated power?

Solution 5.1
The maximum possible thermal efficiency is given by Eq. (5.7). With TH as the
steam-generation temperature and TC as the river temperature:
295
​​η​  Carnot​​ = 1 − ____
​ ​= 0.4957  and  η = (0.7)(0.4957) = 0.3470​
585
 where η is the actual thermal efficiency. Combining Eq. (5.6) with the first law,
written W = −QH − QC, to eliminate QH, yields:

( η ) ( 0.347 )
1−η 1 − 0.347
​Q​C​= ​ ___
​ ​ ​ ​W = ​ _______
​ ​ ​(− 800,000) = −1,505,475 kW​

This rate of heat transfer to a modest river would cause a temperature rise of several °C.

5.2 HEAT ENGINES AND HEAT PUMPS

The following steps make up the cycle of any Carnot engine:

∙ Step 1: A system at an initial temperature of a cold reservoir at TC undergoes a reversible

adiabatic process that causes its temperature to rise to that of a hot reservoir at TH.
∙ Step 2: The system maintains contact with the hot reservoir at TH and undergoes a
reversible isothermal process during which heat QH is absorbed from the hot reservoir.
∙ Step 3: The system undergoes a reversible adiabatic process in the opposite direction of
Step 1 that brings its temperature back to that of the cold reservoir at TC.
∙ Step 4: The system maintains contact with the reservoir at TC, and undergoes a reversible
isothermal process in the opposite direction of Step 2 that returns it to its initial state
with rejection of heat QC to the cold reservoir.

This set of processes can in principle be performed on any kind of system, but only a
few, yet to be described, are of practical interest.
A Carnot engine operates between two heat reservoirs in such a way that all heat
absorbed is transferred at the constant temperature of the hot reservoir and all heat rejected is
transferred at the constant temperature of the cold reservoir. Any reversible engine operating
between two heat reservoirs is a Carnot engine; an engine operating on a different cycle must
necessarily transfer heat across finite temperature differences and therefore cannot be reversi-
ble. Two important conclusions inevitably follow from the nature of the Carnot engine:

∙ Its efficiency depends only on the temperature levels and not upon the
working substance of the engine.
∙ For two given heat reservoirs no engine can have a thermal efficiency
higher than that of a Carnot engine.

We provide further treatment of practical heat engines in Chapter 8.

Because a Carnot engine is reversible, it may be operated in reverse; the Carnot cycle
is then traversed in the opposite direction, and it becomes a reversible heat pump operating
between the same temperature levels and with the same quantities QH, QC, and W as for the
engine but reversed in direction, as illustrated in Fig. 5.1(b). Here, work is required, and it is
used to “pump” heat from the lower-temperature heat reservoir to the higher-temperature heat
reservoir. Refrigerators are heat pumps with the “cold box” as the lower-temperature reservoir
and some portion of the environment as the higher-temperature reservoir. The usual measure
of quality of a heat pump is the coefficient of performance, defined as the heat extracted at
the lower temperature divided by the work required, both of which are positive quantities with
respect to the heat pump:
​Q​C​
ω ≡ ___
​ ​ ​​ (5.8)
W
For a Carnot heat pump this coefficient can be obtained by combining Eq. (5.4) and
Eq. (5.5) to eliminate QH:
​T​C​
​ω​Carnot​≡ ______
​ ​ ​​ (5.9)
​T​H​− ​T​C​
For a refrigerator at 4°C and heat transfer to an environment at 24°C, Eq. (5.9) yields:
4 + 273.15
​ω​Carnot​= ________
​ ​ ​= 13.86​
24 − 4
Any actual refrigerator would operate irreversibly with a lower value of ​ω​. The practical
aspects of refrigeration are treated in Chapter 9.

5.3 CARNOT ENGINE WITH IDEAL-GAS-STATE WORKING FLUID

The cycle traversed by a working fluid in its ideal-gas state in a Carnot engine is shown on
a PV diagram in Fig. 5.2. It consists of four reversible processes corresponding to Steps 1
through 4 of the general Carnot cycle described in the preceding section:

∙ a → b Adiabatic compression with temperature rising from TC to TH.

∙ b → c Isothermal expansion to arbitrary point c with absorption of heat QH.
∙ c → d Adiabatic expansion with temperature decreasing to TC.
∙ d → a Isothermal compression to the initial state with rejection of heat QC.

In this analysis the ideal-gas-state working fluid is regarded as the system. For the iso-
thermal steps b → c and d → a, Eq. (3.20) yields:
ig ig
​V​  c​  ​ ​V​  a​  ​
​​Q​ H​​ = ​RT​ H​​ ln ___ Q​ C​​ = ​RT​ C​​ ln ___
​  ig ​  and  ​ ​  ig ​​
​V​  b​  ​ ​V​  d​  ​
Dividing the first equation by the second gives:
​QH ​T​H​ln (​ ​V​cig​ ​/ ​V​big​)​ ​
​ ​ ____________
___
​
​ ​ =   
​ ​​
​Q​C​ ​T​C​ln (​ ​V​aig​​/ ​V​ig​)​ ​
d

For an adiabatic process Eq. (3.16) with dQ = 0 becomes,

ig
​C​  ​  ​dT d​V​ ​ ig
− ____
​ ​  V ​___ ​ ​ = ____
​ ​​
R T ​V​ig​
 TH

QH

Figure 5.2: PV diagram showing a

P Carnot cycle for a working fluid in the
ideal-gas state.
c
TC

TH
a
d
QC TC

For steps a → b and c → d, integration gives:

​T​ H​​ ​T​ H​​ ig
​C​  ig​  ​ dT ​V​  aig​  ​ ​C​  ​  ​ dT ​V​  ig​  ​
∫ ​T​ C​​ R T ∫ ​T​ C​​ R T
​​ ​  ___
​​  V ​ ​ ___ ​ ​= ln ___
​  ig ​  and  ​ ​  ___ ​​  V ​ ​ ___ ​ ​= ln ___
​  dig ​​
​V​  b​  ​ ​V​  c​  ​
Because the left sides of these two equations are the same, the adiabatic steps are related by:
​V​ig​​ ​V​aig​​ ig
​V​c​ ​ ​V​a​​ ig
ln ___
​ ​ dig ​ = ln ___
​ ig ​  or  ln ___
​ ​ = − ln ___
​ ​​
​V​c​ ​ ​V​b​​ ​V​big​​ ​V​dig​​
Combining the second expression with the equation relating the two isothermal steps gives:
​QH
___​​ ​T​H​ − ​Q​C​ ​​
​QH
​ ​ = − ___
​ ​ ​  or  ​____​ = ___
​ ​​
​Q​C​ ​T​C​ ​T​C​ ​T​H​

This last equation is identical with Eq. (5.4).

5.4 ENTROPY

Points A and B on the PVt diagram of Fig. 5.3 represent two equilibrium states of a particular
fluid, and paths ACB and ADB represent two arbitrary reversible processes connecting these
points. Integration of Eq. (5.1) for each path gives:
​ ​ ​ ​
∫ ACB T
d​Qrev
∫ ADB T
_____ d​Qrev
_____
​
Δ​S​t​= ​  ​ ​ ​ ​   and  Δ​S​t​= ​  ​ ​ ​ ​​
 Rev. Confirming Pages

5.4. Entropy 181

P Figure 5.3: Two reversible paths

A joining equilibrium states A and B.

Vt

t t
Because ΔSt is a property change, it is independent of path and is given by ​S​B​− ​S​A​.​
If the fluid is changed from state A to state B by an irreversible process, the entropy
t t
change is again ​Δ​S​t​ = ​S​B​ − ​S​A​​, but experiment shows that this result is not given by
​∫dQ / T​evaluated for the irreversible process itself, because the calculation of entropy changes by this
integral must, in general, be along reversible paths.
The entropy change of a heat reservoir, however, is always given by Q/T, where Q is the
quantity of heat transferred to or from the reservoir at temperature T, whether the transfer is
reversible or irreversible. As noted earlier, the effect of heat transfer on a heat reservoir is the
same regardless of the temperature of the source or sink of the heat.
If a process is reversible and adiabatic, dQrev = 0; then by Eq. (5.1), dSt = 0. Thus the
entropy of a system is constant during a reversible adiabatic process, and the process is said
to be isentropic.
The characteristics of entropy may be summarized as follows:

∙ Entropy relates to the second law in much the same way that internal energy relates to
the first law. Equation (5.1) is the ultimate source of all equations that connect entropy
to measurable quantities. It does not represent a definition of entropy; there is none in
the context of classical thermodynamics. What it provides is the means for calculating
changes in this property.
∙ The change in entropy of any system undergoing a finite reversible process is given by the
integral form of Eq. (5.1). When a system undergoes an irreversible process between two
equilibrium states, the entropy change of the system Δ ​ ​S​​  t​​is evaluated by application of
Eq. (5.1) to an arbitrarily chosen reversible process that accomplishes the same change
of state as the actual process. Integration is not carried out for the irreversible path.
Because entropy is a state function, the entropy changes of the irreversible and reversible
processes are identical.
∙ In the special case of a mechanically reversible process (Sec. 2.8), the entropy change
of the system is correctly evaluated from ​∫dQ / T​applied to the actual process, even
though the heat transfer between system and surroundings represents an external
irreversibility. The reason is that it is immaterial, as far as the system is concerned,

smi96529_ch05_173-209.indd 181 06/19/17 12:21 PM

 whether the temperature difference causing the heat transfer is infinitesimal (making
the process externally reversible) or finite. The entropy change of a system result-
ing only from the transfer of heat can always be calculated by ∫​ dQ / T,​whether the
heat transfer is accomplished reversibly or irreversibly. However, when a process is
irreversible on account of finite differences in other driving forces, such as pressure,
the entropy change is not caused solely by the heat transfer, and for its calculation
one must devise a mechanically reversible means of accomplishing the same change
of state.

5.5 ENTROPY CHANGES FOR THE IDEAL-GAS STATE

For one mole or a unit mass of fluid undergoing a mechanically reversible process in a closed
system, the first law, Eq. (2.7), becomes:
​
dU = d​Qrev
​ ​− PdV​

Differentiation of the defining equation for enthalpy, H = U + PV, yields:

​
dH = dU + PdV + V dP​
Eliminating dU gives:
​
dH = d​Qrev
​ ​− PdV + PdV + VdP​
or
​
d​Qrev
​ ​= dH − VdP​
For the ideal-gas state, d​​H​ig​ = ​C​Pig​​dT and ​V​ig​ = RT / P​
. With these substitutions and
division by T,
​ ​
d​Qrev
_____ dT dP
​
​ ​= ​C​Pig​​___
​ ​− R ___
​ ​​
T T P
As a result of Eq. (5.1), this becomes:

dT
ig ___ dP
___ ____ ​C​Pig​​___
d​S​ig​ ___ dT
​
d​S​ ​= ​C​P​​​ ​− R ​ ​  or  ​ ​= ​ ​​ ​−
ig d ln P​
T P R R T
where Sig is the molar entropy for the ideal-gas state. Integration from an initial state at condi-
tions T0 and P0 to a final state at conditions T and P gives:

Δ​S​​  ​ ig T ​C​  ig​  ​ dT

∫ ​T​ 0​​ R T
P
​​ ____  ​= ​ ​  ​​   ​ ​   ​ ​ − ln ___
___ P ___
​   ​​ (5.10)
R ​P​ 0​​

Although derived for a mechanically reversible process, this equation

relates properties only, independent of the process causing the change
of state, and is therefore a general equation for the calculation of entropy
changes in the ideal-gas state.
Example 5.2
For the ideal-gas state and constant heat capacities, Eq. (3.23b) for a reversible adia-
batic (and therefore isentropic) process can be written:

( ​P​  1​​ )
(γ−1)/γ
​T​  2​​
___ ​P​  2​​
​   ​ = ​​ ___
​ ​   ​ ​​​  ​​
​T​  1​​
Show that this same equation results from application of Eq. (5.10) with ΔSig = 0.

Solution 5.2
Because ​C​Pig​​is constant, Eq. (5.10) becomes:
​C​ig​​ ​T​2​ ​P​2​ ​T​2​ R ​P​2​
0 = ___
​ ​ P ​ln ___
​ ​− ln ___
​ ​= ln ___
​ ​− ___
​ ig ​ln ___
​ ​​
R ​T​1​ ​P​1​ ​T​1​ ​C​P​​ ​P​1​
By Eq. (3.12) for the ideal-gas state, with ​γ = ​C​Pig​​/ ​C​Vig​​​:
R γ−1
​ ​C​Pig​​= ​C​Vig​​+ R  or  ​___ ​= ___
​ ​​
ig
​C​P​​ γ
Whence,
​T​2​ γ − 1 ___ ​P​2​
​ln ___
​ ​= ____
​ ​ln ​ ​​
​T​1​ γ ​P​1​
Exponentiating both sides of this equation leads to the given equation.

Equation (4.5) for the temperature dependence of the molar heat capacity ​C​Pig​​ allows
integration of the first term on the right of Eq. (5.10). The result can be written as:

​ ​+ ​ B + ​(C + ​ 2 2 ​)​(​ 2 ​)​ ​(​T − ​T​0​)​​

​T​0​ [ ]
T ​C​ig​​dT
T D
_____ T + ​T​0​
_____
​∫ ​ ​​ ​​ ​= A ln ___
​ ___P ___
(5.11)
​T​0​ R T
​T​0​​T​ ​

As with the integral ∫(CP/R)dT of Eq. (4.8), this integral is often evaluated; for computational
purposes we define the right side of Eq. (5.11) as the function ICPS(T0, T; A, B, C, D) and
presume the existence of a computer routine for its evaluation.4 Equation (5.11) then becomes:
T ​C​ig​​dT

∫ ​T​ 0​​ R T
​​ ___P ___
​  ​​ ​​ ​ ​ = ICPS(​T​0​, T; A, B, C, D)​

Also useful is a mean heat capacity, here defined as:

T

∫ ​T​  ​​
​ ​  ​​C​  Pig​  ​dT /T ​
​​​⟨​​C​Pig​​⟩​​  ​​ = __________
​  0  ​​ (5.12)
S ln (T /​T​ 0​​)
In accord with this equation, division of Eq. (5.11) by ln (T/T0) yields:
​⟨​​C​Pig​​⟩​​  ​​
= A + ​ B + ​(C + ​  2 2 ​)​​(​  2 ​ )]​​ln ​(​T / ​T​0​)​​​
[
_____D T + ​T​ 0​​
______ T − ​T​0​
​​ ______  ​ S ​ _______ (5.13)
R ​T​  0​  ​​T​​  ​

4Examples of these defined functions implemented in Microsoft Excel, Matlab, Maple, Mathematica, and Mathcad

are provided in the online learning center at http://highered.mheducation.com:80/sites/1259696529.

 The right side of this equation is defined as another function, MCPS (T0, T; A, B, C, D).
Equation (5.13) is then written:

​⟨​​C​Pig​​⟩​​  ​​
​​ ______  ​ S
= MCPS(​T​0​, T; A, B, C, D)​
R
The subscript S denotes a mean value specific to entropy calculations. Comparison of
this mean value with the mean value specific to enthalpy calculations, as defined by Eq. (4.9),
shows the two means to be quite different. This is inevitable because they are defined for the
purpose of evaluating entirely different integrals.
Solving for the integral in Eq. (5.12) gives:
T
​ ​ ​ = ​⟨​C​Pig​​⟩​ ​ln ___
∫ ​T​ 0​​ P T
dT T
​​ ​  ​C​ig​___ ​ ​​
S ​
T ​0​

and Eq. (5.10) becomes:

ig​ ​⟨​C​P​​⟩​​  ​​
ig
Δ​
S ​ T P
​​ ​_​= ​ ______  ​ S
ln _
​ ​− ln _
​ ​ ​​ (5.14)
R R ​T​0​ ​P​0​
This form of the equation for entropy changes for the ideal-gas state is often useful in iterative
calculations where the final temperature is unknown.

Example 5.3
Methane gas at 550 K and 5 bar undergoes a reversible adiabatic expansion to 1 bar.
Assuming ideal-gas-state methane at these conditions, find its final temperature.

Solution 5.3
For this process ΔSig = 0, and Eq. (5.14) becomes:

⟨ P ⟩S ​T​2​ ​ ​2​
P 1 ​ ​C​ig​​ ​​  ​​
​​ ______
 ​ ln ___
​ ​= ln ___
​ ​= ln __
​ ​= − 1.6094​
R ​ ​1​
T ​P​1​ 5
Because ​⟨​C​Pig​​⟩​ ​​ depends on T2, we rearrange this equation for iterative solution:
S
− 1.6094
( )
​T​2​ − 1.6094 ________
ln ___
​ ​= ________  ​  or  ​T​2​= ​T​1​exp ​ ​  ig  ​ ​​
⟨ ⟩
​ ​  ig
​T​1​ ⟨ ​ ​C​P​⟩
​ ​​  ​​ / R ​ ​
C ​
P ​​ ​  ​​​ / R
S S

With constants from Table C.1 of App. C, ​​​⟨​C​Pig​​⟩​​  ​​ / R​is evaluated by Eq. (5.13)
S
written in its functional form:
​⟨​C​Pig​​⟩​​  ​​
​​ ______  ​ S
= 𝖬𝖢𝖯𝖲​​(​550, ​T​2​; 1.702, 9.081 × ​10​​−3​, − 2.164 × ​10​​−6​, 0.0​)​​
R
 For an initial value of T2 < 550, compute a value of ​⟨
​​ ​C​Pig​​⟩​​  ​​ / R​for substitution into
the equation for T2. This new value of T2 allows recalculation of ​⟨ ​​ ​C​Pig​​⟩​​  ​​ / R​, and the
S

process continues to convergence on a final value of T2 = 411.34 K. S

As with Ex. 4.3 a trial procedure is an alternative approach, with Microsoft
Excel’s Goal Seek providing a prototypical automated version.

Example 5.4
A 40 kg steel casting (CP = 0.5 kJ⋅kg−1⋅K−1) at a temperature of 450°C is quenched
in 150 kg of oil (CP = 2.5 kJ⋅kg−1⋅K−1) at 25°C. If there are no heat losses, what is the
change in entropy of (a) the casting, (b) the oil, and (c) both considered together?

Solution 5.4
The final temperature t of the oil and the steel casting is found by an energy bal-
ance. Because the change in energy of the oil and steel together must be zero,
​
(40)(0.5)(t− 450) + (150)(2.5)(t − 25) = 0​
Solution yields t = 46.52°C.
(a) Change in entropy of the casting:
​C​ P​​ dT ​T​ 2​​
∫
Δ​S​​  t​ = m​ ​  _____
​​   ​  ​= m​C​ P​​ ln ___
​   ​
T ​T​ 1​​
​​​     ​  ​ ​​
273.15 + 46.52
_____________ −1
​ = (40)(0.5) ln ​       ​ = −16.33 kJ⋅​K​​  ​
273.15 + 450
(b) Change in entropy of the oil:
273.15 + 46.52
____________
​   ​= 26.13 kJ⋅​K​−1​​
Δ​S​t​= ​(​150​)​(​2.5​)​ln   
​
273.15 + 25
(c) Total entropy change:
Δ​S​total​= −16.33 + 26.13 = 9.80 kJ⋅​K​−1​​
​
Note that although the total entropy change is positive, the entropy of the casting
has decreased.

5.6 ENTROPY BALANCE FOR OPEN SYSTEMS

Just as an energy balance is written for processes in which fluid enters, exits, or flows
through a control volume (Sec. 2.9), so too may an entropy balance be written. There is,
however, an important difference: Entropy is not conserved. The second law states that the
total entropy change associated with any process must be positive, with a limiting value of
zero for a reversible process. This requirement is taken into account by writing the entropy
balance for both the system and its surroundings, considered together, and by including an
entropy-­generation term to account for the irreversibilities of the process. This term is the sum
of three others: one for the difference in entropy between exit and entrance streams, one for
entropy change within the control volume, and one for entropy change in the surroundings.
If the process is reversible, these three terms sum to zero, making ΔStotal = 0. If the process is
irreversible, they sum to a positive quantity, the entropy-generation term.
The statement of balance, expressed as rates, is therefore:
⎧Time rate of⎫
⎧ Net rate of ⎫ ⎧ Time rate of ⎫
⎪ change of ⎪ ⎪ change in ⎪ ⎪ change of ⎪ Total rate
entropy of ⎪ ⎪ entropy in ⎪ {
generation}
​​⎨​ entropy ​
​​ ⎬
​ ​+ ⎨
​   
​  ​​ ⎬
​ ​+ ⎨
​ ​  ​ ​⎬
​ ​= ​ ​  of entropy​​ ​​
⎪ in control ⎪ ⎪ ⎩flowing streams⎭ ⎩surroundings⎭
⎩ volume ⎭
The equivalent equation of entropy balance is
t
d​​(​mS​)​cv​
_______ d​S​surr​ ∙
​ ​+ Δ​(​S​m​​)​​  fs​​ + _____
∙
​
​ ​ ​= ​​S​​  G​​ ≥ 0​ (5.15)
dt dt
∙
where ​​​S​​  G​​​ is the rate of entropy generation. This equation is the general rate form of the entropy
balance, applicable at any instant. Each term can vary with time. The first term is the time rate
of change of the total entropy of the fluid contained within the control volume. The second
term is the net rate of gain in entropy of the flowing streams, i.e., the difference between the
total entropy transported out by exit streams and the total entropy transported in by entrance
streams. The third term is the time rate of change of the entropy of the surroundings, resulting
from heat transfer between system ∙
and surroundings.
Let rate of heat transfer ​​​Q​​ ​​  j​​​with respect to a particular part of the control surface be
associated with Tσ,j where subscript σ,j denotes a temperature in the surroundings. ∙
The rate
of entropy change ∙
in the surroundings as a result of this transfer is then −​ ​​​​Q​​  j​​ / ​T​ σ, j​​​. The minus
sign converts ​​​Q​​  j​​​, defined with respect to the system, to a heat transfer rate with respect to the
surroundings. The third term in Eq. (5.15) is therefore the sum of all such quantities:
∙
t
d​S​surr​
_____
​​Q​​  j​​
​​   ​ = −​∑​ ​​​ ____ ​​
dt j ​T​ σ, j​​

Equation (5.15) is now written:

∙
​d(mS)​  cv​​ j ∙ ​​ ​​  ​​
Q
​​ _______
 ​ + Δ​(S​m∙ ​)​​  ​  fs​​ – ​∑​ ____
​​   ​​ = ​​S​​  G​​ ≥ 0​ (5.16)
dt j ​T​ σ, j​​
∙
The final term, representing the rate of entropy generation S​​ ​​​ ​​  G​​​, reflects the second-law
requirement that it be positive for irreversible processes. There are two sources of irreversibility:
(a) those within the control volume, i.e., internal irreversibilities, and (b) those resulting
from heat transfer across finite temperature differences between system ∙
and surroundings,
i.e., external thermal irreversibilities. The limiting case for which ​​​S​​  G​​ = 0​ applies when the
process is completely reversible, implying:

∙ The process is internally reversible within the control volume

∙ Heat transfer between the control volume and its surroundings is reversible
 Rev. Confirming Pages

5.6. Entropy Balance for Open Systems 187

The second item means either that heat reservoirs are included in the surroundings with
temperatures equal to those of the control surface or that work-producing Carnot engines are
interposed in the surroundings between the control-surface temperatures and the heat-reservoir
temperatures.
For a steady-state flow process the mass and entropy of the fluid in the control volume
are constant, and d(mS)cv/dt is zero. Equation (5.16) then becomes:
∙
j ∙ ∙ ​​ ​​  ​​
Q
​​  )​  fs​​ – ​∑​ ​​​ ____ ​ = ​​S​​  G​​ ≥ 0​ ​​
​​ ​Δ​(​S​m (5.17)
j ​T​ σ, j​​

If in addition there is but one entrance and one exit, ​​m​​ ∙ ​​is the same for both streams, and divid-
ing through by ​​m​​ ∙ ​​ yields:
∙
j ​​  ​​ ​​  ​​
Q
​ΔS − ​∑​ ​_
​ ​ ​= ​S​ ​≥ 0 ​​ G (5.18)
j ​T​σ, j​

Each term in Eq. (5.18) is based on a unit mass of fluid flowing through the control volume.

Example 5.5
In a steady-state flow process carried out at atmospheric pressure, 1 mol⋅s−1 of air at
600 K is continuously mixed with 2 mol⋅s−1 of air at 450 K. The product stream is at 400 K
and 1 atm. A schematic representation of the process is shown in Fig. 5.4. Determine
the rate of heat transfer and the rate of entropy generation for the process. Assume
the ideal-gas state for air with ​C​ig
P​​= (7/ 2)R​, that the surroundings are at 300 K, and that
kinetic- and potential-energy changes of the streams are negligible.

n
. 3 mol s 1

T 400 K

Figure 5.4:
. 1 . 1
Process
nA 1 mol s nB 2 mol s
Control Volume described in
TA 600 K TB 450 K Ex. 5.5.

.
Q

smi96529_ch05_173-209.indd 187 06/19/17 12:54 PM

 Solution 5.5
We start by applying an energy balance to determine the rate of heat transfer,
which we will need to know in order to compute the rate of entropy generation.
Writing the energy balance, Eq. (2.29), with ​​m​​ ∙ ​​replaced by ​​n​​ ∙ ​​, and then replacing ​​
∙
n​​ ∙ ​​ with ​​n∙ ​​​​ A + ​​n​​B,

​​  ​ig​− ​​n∙ ​​  A​​​H​Aig​​− ​​n​​  B​​ ​H​Big​​= ​​n​​  A​​​(​H​ig​− ​H​Aig​​)​+ ​​n​​  B​​​(​H​ig​− ​H​Big​​)​​
∙ ∙ ∙ ∙
​​Q​​ ​ = ​n∙ ​H
∙
​ ​= ​​n​​  A​​​C​  Pig​  ​(T − ​T​ A​​) + ​​n​​  B​​​C​  Pig​  ​(T − ​T​ B​​) = ​C​  Pig​  ​  [​​n​​  A​​  (T − ​T​ A​​) + ​​n​​  B​​  (T − ​T​ B​​)]
∙ ∙ ∙ ∙
Q
​​      
​  ​  ​   ​​​
= (7 / 2)(8.314)[(1)(400 − 600) + (2)(400 − 450)] = − 8729.7 J⋅​s​​  −1​
∙
The steady-state entropy balance, Eq. (5.17), with ​​m​​ ∙ ​​again replaced by ​​n​​, can
­similarly be written as
∙ ∙
​Q​ ​ ​
Q
n​​ ​​  A​​​( ​S​​  ig​− ​S​  Aig​  ​)​+ ​​n​​  B​​​( ​S​​  ig​− ​S​  Big​  )​ ​− ___
∙
​​S ​​  G​​ = ​n​​S​​  ig​− ​​n​​  A​​​S​  Aig​  ​− ​​n​​  B​​​S​  Big​  ​− ___
∙ ∙ ∙ ∙ ∙
​   ​ = ​   ​ 
​Tσ​  ​​ ​Tσ​  ​​

( ​T​ B​​ ) ​Tσ​  ​​
∙ ∙
T T ​Q​ T T ​Q​
​​​​ ​  =​  ​​n​​  A​​​C​  Pig​  ​ln  ___
      
       ∙
​   ​ + ​​n​​  B​​​C​  Pig​  ​ln ___
∙
​   ​ − ___
​   ​ = ​C​  pig​  ​​  ​​n∙ ​​  A​​ ln ___ ​   ​  ​− ​___
​   ​ + ​​n​​  B​​ ln ___
∙
​   ​  ​ ​​
​T​ A​​ ​T​ B​​ ​Tσ​  ​​ ​T​ A​​

[ 450 ]
400 400 8729.7
= (7 / 2)(8.314)​ (1) ln ____
​   ​ + (2) ln ____
​   ​  ​+ ______
​   ​ = 10.446 J⋅​K​​  −1​⋅​s​​  −1​
600 300
The rate of entropy generation is positive, as it must be for any real process.

Example 5.6
An inventor claims to have devised a process which takes in only saturated steam at
100°C and which by a complicated series of steps makes heat continuously available
at a temperature level of 200°C, with 2000 kJ of energy available at 200°C for every
kilogram of steam taken into the process. Show whether or not this process is possible.
To give this process the most favorable conditions, assume cooling water available
in unlimited quantity at a temperature of 0°C.

Solution 5.6
For any process to be even theoretically possible, it must meet the requirements of the
first and second laws of thermodynamics. The detailed mechanism need not be known
to determine whether this is true; only the overall result is required. If the claims of
the inventor satisfy the laws of thermodynamics, fulfilling the claims is theoretically
possible. The determination of a mechanism is then a matter of ingenuity. Otherwise,
the process is impossible, and no mechanism for carrying it out can be devised.
In the present instance, a continuous process takes in saturated steam at 100°C,
and makes heat Q continuously available at a temperature level of 200°C. Because
cooling water is available at 0°C, the maximum possible use is made of the steam if
it is condensed and cooled (without freezing) to this exit temperature and discharged
 at atmospheric pressure. This is a limiting case (most favorable to the inventor), and
requires a heat-exchange surface of infinite area.
It is not possible in this process for heat to be liberated only at the 200°C tem-
perature level, because as we have shown no process is possible that does nothing
except transfer heat from one temperature level to a higher one. We must therefore
suppose that some heat Qσ is transferred to the cooling water at 0°C. Moreover,
the process must satisfy the first law; thus by Eq. (2.32):
​
ΔH = Q + ​Qσ​ ​+ ​Ws​​​
where ΔH is the enthalpy change of the steam as it flows through the system.
Because no shaft work accompanies the process, Ws = 0. The surroundings con-
sist of cooling water, which acts as a heat reservoir at the constant temperature of
Tσ = 273.15 K, and a heat reservoir at T = 473.15 K to which heat in the amount of
2000 kJ is transferred for each kilogram of steam entering the system. The diagram
of Fig. 5.5 indicates overall results of the process based on the inventor’s claim.

Heat reservoir
at 200° C

Q 2000 kJ

Saturated steam
at 100° C Liquid water at 0° C Figure 5.5: Process
Apparatus
H1 2676.0 kJ kg 1 H2 0.0 described in Ex. 5.6.
S1 7.3554 kJ kg 1 K 1 S2 0.0
Q

Heat reservoir
at 0 ° C
(cooling water)

The values of H and S shown on Fig. 5.5 for liquid water at 0°C and for satu-
rated steam at 100°C are taken from the steam tables (App. E). Note that the val-
ues for liquid water at 0°C are for saturated liquid (Psat = 0.61 kPa), but the effect
of an increase in pressure to atmospheric pressure is insignificant. On the basis of
1 kg of entering steam, the first law becomes:
​
ΔH = ​H​2​− ​H​1​= 0.0 − 2676.0 = −2000 + ​Qσ​ ​  and  ​Qσ​ ​= −676.0 kJ​
The negative value for Qσ indicates heat transfer is from the system to the
­cooling water.
We now examine this result in the light of the second law to determine whether
the entropy generation is greater than or less than zero for the process. Equation
(5.18) is here written:
​Qσ​ ​ Q
​ ΔS − ___
​ ​− ______
​ ​= ​S​G​​
​Tσ​ ​ 473.15
 For 1 kg of steam,
ΔS = ​S​2​− ​S​1​= 0.0000 − 7.3554 = −7.3554 kJ⋅​K​−1​​
​
The entropy generation is then:
−676.0 ______ − 2000
S​ ​ G​​ = − 7.3554 −  ______
​   ​ − ​   ​​
​​   
​  ​  ​  273.15 473.15 ​ ​​
= − 7.3554 + 4.2270 + 2.4748 = − 0.6536 kJ⋅​K​​  −1​
This negative result means that the process as described is impossible; the second
law in the form of Eq. (5.18) requires SG ≥ 0.

The negative result of the preceding example does not mean that all processes of this general
nature are impossible; only that the inventor claimed too much. Indeed, the maximum amount
of heat which can be transferred to the hot reservoir at 200°C is readily calculated. The energy
balance is:
​
Q + ​Qσ​ ​= ΔH​ (A)
The maximum heat transfer to the hot reservoir occurs when the process is completely revers-
ible, in which case SG = 0, and Eq. (5.18) becomes
Q ​Qσ​ ​
__
​ ​+ ___
​ ​ ​= ΔS​ (B)
T ​Tσ​ ​
Combination of Eqs. (A) and (B) and solution for Q yields:
T
Q = ____
​ ​ ​(ΔH − ​Tσ​ ​ΔS)​
T − ​Tσ​ ​
With respect to the preceding example,

​[ ]​ = − 1577.7 kJ⋅ ​kg​​−1​​

473.15 − 2676.0 − ​(​273.15​)​(​− 7.3554​)​
Q = ______
​ ​
200
​ 2000 kJ⋅ ​kg​​−1​​claimed.
This value is smaller in magnitude than the −

5.7 CALCULATION OF IDEAL WORK

In any steady-state flow process requiring work, an absolute minimum amount of work is
required to produce the desired change of state in the fluid flowing through the control vol-
ume. In a process producing work, an absolute maximum amount of work can be realized from
a given change of state of the fluid flowing through the control volume. In either case, the
limiting value results when the change of state associated with the process is accomplished
completely reversibly. For such a process, the entropy generation is zero, and Eq. (5.17), writ-
ten for a uniform surroundings temperature Tσ, becomes:
∙
​Q​​​  ∙
Δ​(S​m ​)​​  ​  fs​​ − ___
​ ​   ​ = 0  or  ​
∙
Q​​​  = ​Tσ​ ​Δ​(S​m∙ ​)​​  ​  fs​​​
​Tσ​  ​​
 ∙
Substituting this expression for ​​Q​​ ​​in the energy balance, Eq. (2.29):

Δ​​[ ​(H + _​  12 ​​u​​  2​ + zg)​​m∙ ​ ​​  ] ​​  ​​ = ​Tσ​  ​​Δ​(S​m∙ ​)​​  ​  fs​​ + ​​W​​  s​​(rev)​
∙
​
fs
∙ ∙
The shaft work, ​​​W ​​ s​​  ​​​(rev),
∙
is here the work of a completely reversible process. If ​​​W ​​ s​​  ​​​(rev) is given
the name ideal work, ​​​W ​​ ​​  ideal​​​, the preceding equation may be rewritten:

​​​W​​ ​​  ideal​​ = Δ​​[ ​(H + _​  12 ​​u​​  2​ + zg)​​m∙ ​ ​​  ] ​​  ​​ − ​Tσ​  ​​Δ​(S​m∙ ​)​​  ​  fs​​​
∙
(5.19)
fs

In most applications to chemical processes, the kinetic- and potential-energy terms are
­negligible compared with the others; in this event Eq. (5.19) reduces to:
∙ ∙
​​ ​​W​​  ideal​​  = Δ​(H​m∙ ​)​​  ​  fs​​ − ​Tσ​ ​Δ​(S​m​)f​  s​​ ​​ (5.20)

For the special case of a single stream flowing through the control volume, ​​m​​ ∙ ​​may be factored.
The resulting equation may then be divided by ​​m​​ ∙ ​​to express it on the basis of a unit amount of
fluid flowing through the control volume. Thus,

∙
​W
​​ ​​  ideal​​ = ​m∙ ​(​​  ΔH − ​Tσ​ ​ΔS)​​ (5.21) ​W​ideal​= ΔH − ​Tσ​ ​ΔS​ (5.22)

A completely reversible process is hypothetical, devised here solely for determination of the
ideal work associated with a given change of state.

The sole connection between an actual process and an imagined hypothetical

reversible process employed for determining ideal work is that they both
apply to the same changes of state.
∙
Our objective is to compare the actual work of a process W ​​​ s​​  ​​​ (or Ws) as given by an energy
balance to the ideal work as given by Eqs. (5.19) through (5.22) for a hypothetical reversible
process that produces the same property changes. No description of the hypothetical process is
required, as it ∙may always be imagined (see Ex. 5.7).
When ​​​W ​​ ​​  ideal​​​ (or Wideal) is positive, it is the minimum work required to ∙
bring about a
given change in the properties of the flowing streams, and is smaller than ​​​Ws​​  ​​​. In this case a
thermodynamic efficiency ηt is defined as the ratio of the ideal work to the actual work:
∙
​​W​​  ideal​​
​η​​(work required) = _____
​ ​  ∙  ​​ t (5.23)
​​Ws​​  ​​

| |
∙ ∙
When ​​​W​​  ideal​​​ (or Wideal) is negative, ​​  ​​W​​  ideal​​  ​​ is the maximum work∙ obtainable from a
given change in the properties of the flowing streams, and is larger than ​​  ​W​s ​​. In this case, the | |
thermodynamic efficiency is defined as the ratio of the actual work to the ideal work:
∙
​​Ws​​  ​​
​η​​(work produced) = _____
​ ​  ∙  ​​ t (5.24)
​​W​​  ideal​​
Example 5.7
What is the maximum work that can be obtained in a steady-state flow process from
1 mol of nitrogen in its ideal-gas state at 800 K and 50 bar? Take the temperature and
pressure of the surroundings as 300 K and 1.0133 bar.

Solution 5.7
The maximum possible work is obtained from any completely reversible process
that reduces the nitrogen to the temperature and pressure of the surroundings, i.e.,
to 300 K and 1.0133 bar. Required here is the calculation of Wideal by Eq. (5.22),
in which ΔS and ΔH are the molar entropy and enthalpy changes of the nitrogen
as its state changes from 800 K and 50 bar to 300 K and 1.0133 bar. For the
ideal-gas state, enthalpy is independent of pressure, and its change is given by:
​T​ 2​​

∫ ​T​ 1​​
Δ​H​ig​= ​ ​  ​​C​Pig​​dT ​​
​

The value of this integral is found from Eq. (4.8), and is represented by:
8.314 × ICPH(800, 300; 3.280, 0.593 ×𝟣𝟢−3, 0.0, 0.040 × 𝟣𝟢−5) = −15,060 J⋅​mol​​−1​
where the parameters for nitrogen come from Table C.1 of App. C.
Similarly, the entropy change is found from Eq. (5.10), here written:
​T​ 2​​
​P​2​
∫ ​T​ 1​​
dT
Δ​S​ig​= ​ ​  ​C​Pig​​___
​ ​ ​ ​− R ln ___
​ ​​
T ​P​1​

The value of the integral, found from Eq. (5.11), is represented by:
​8.314 × ICPS(800, 300; 3.280, 0.593 ×𝟣𝟢−3, 0.0, 0.040 × 𝟣𝟢−5) = −29.373 J⋅​mol​​−1​⋅​K​−1​​
1.0133
Δ​S​ig​= −29.373 − 8.314 ln ______
Whence, ​ ​ ​= 3.042 J⋅​mol​​−1​⋅​K​−1​​
50
With these values of ΔHig and ΔSig, Eq. (5.22) becomes:
​W​ideal​= −15,060 − (300)(3.042) = −15,973 J⋅​mol​​−1​​
​

One can easily devise a specific reversible process to bring about the given change of state
of the preceding example. Suppose the nitrogen is continuously changed to its final state at
1.0133 bar and T2 = Tσ = 300 K by the following two-step steady-flow process:

∙ Step 1: Reversible, adiabatic expansion (as in a turbine) from initial state P1, T1, H1 to
1.0133 bar. Let T′ denote the discharge temperature.
∙ Step 2: Cooling (or heating, if T′ is less than T2) to the final temperature T2 at a constant
pressure of 1.0133 bar.

For step 1, with Q = 0, the energy balance is Ws = ΔH = (H′ − H1), where H′ is the
enthalpy at the intermediate state of T′ and 1.0133 bar.
 For maximum work production, step 2 must also be reversible, with heat exchanged
reversibly with the surroundings at Tσ. This requirement is satisfied when Carnot engines
take heat from the nitrogen, produce work WCarnot, and reject heat to the surroundings at Tσ.
Because the temperature of the nitrogen decreases from T′ to T2, Eq. (5.5) for the work of a
Carnot engine is written in differential form:

(T ) ( T)
​Tσ​ ​ ​Tσ​ ​
d​W​Carnot​= ​ __
​ ​ ​− 1 ​(​−dQ​)​= ​ 1 − __
​ ​ ​dQ​

Here dQ refers to the nitrogen, which is taken as the system, rather than to the engine.
­Integration yields:
​T​ 2​​

∫ T’ T
dQ
​W​Carnot​= Q − ​Tσ​ ​ ​  ​___
​ ​ ​ ​​

The first term on the right is the heat transferred with respect to the nitrogen, given by
Q = H2 − H′. The integral is the change in entropy of the nitrogen as it is cooled by the Carnot engines.
Because step 1 occurs at constant entropy, the integral also represents ΔS for both steps. Hence,
​W​Carnot​= ​(​H​2​− ​H​′​)​− ​Tσ​ ​ΔS​​
​

The sum of Ws and WCarnot gives the ideal work; thus,

​W​ideal​=​(​H​′​− ​H​1​)​+ ​(​H​2​− ​H​′​)​− ​Tσ​ ​ΔS = ​(​H​2​− ​H​1​)​− ​Tσ​ ​ΔS​​
​
or
​
​W​ideal​= ΔH − ​Tσ​ ​ΔS​
which is the same as Eq. (5.22).
This derivation makes clear the difference between Ws, the reversible adiabatic shaft
work of the turbine, and Wideal. The ideal work includes not only Ws, but also all work obtain-
able from Carnot engines for the reversible exchange of heat with the surroundings at Tσ. In
practice, work produced by a turbine can be as much as 80% of the reversible adiabatic work,
but usually no mechanism is present for extraction of WCarnot.5

Example 5.8
Rework Ex. 5.6, making use of the equation for ideal work.

Solution 5.8
The procedure here is to calculate the maximum possible work Wideal which can
be obtained from 1 kg of steam in a flow process as it undergoes a change in state
from saturated steam at 100°C to liquid water at 0°C. The problem then reduces
to the question of whether this amount of work is sufficient to operate a Carnot

5Acogeneration plant produces power both from a gas turbine and from a steam turbine operating on steam gen-
erated by heat from the gas-turbine exhaust.
 refrigerator rejecting 2000 kJ as heat at 200°C and taking heat from the unlimited
supply of cooling water at 0°C. From Ex. 5.6, we have
ΔH = −2676.0 kJ⋅​kg​​−1​  and  ΔS = −7.3554 kJ⋅​K​−1​⋅​kg​​−1​​
​
With negligible kinetic- and potential-energy terms, Eq. (5.22) yields:
​W​ideal​= ΔH − ​Tσ​ ​ΔS = −2676.0 − (273.15)(−7.3554) = −666.9 kJ⋅k​g​−1​​
​
If this amount of work, numerically the maximum obtainable from the steam, is
used to drive the Carnot refrigerator operating between the temperatures of 0°C
and 200°C, the heat rejected is found from Eq. (5.5), solved for QH:

( ​Tσ​ ​− T ) ( 200 − 0 )
T 200 + 273.15
​Q​H​= ​W​ideal​ ____
​ ​ ​ ​= 666.9​ __________
​   ​ ​= 1577.7 kJ​

As calculated in Ex. 5.6, this is the maximum possible heat release at 200°C; it is
less than the claimed value of 2000 kJ. As in Ex. 5.6, we conclude that the process
as described is not possible.

5.8 LOST WORK

Work that is wasted as the result of irreversibilities in a process is called lost work, Wlost, and
is defined as the difference between the actual work of a change of state and the ideal work for
the same change of state. Thus by definition,
​W​lost​≡ ​Ws​​− ​W​ideal​​
​ (5.25)
In terms of rates,
∙ ∙ ∙
​​​W​​  lost​​ ≡ ​​W​​  s​​ − ​​W​​  ideal​​​ (5.26)
The actual work rate comes from the energy balance, Eq. (2.29), and the ideal work rate is
obtained using Eq. (5.19):

[( ) ]
∙ 1 ∙
​​W​​  s​​ = Δ​​ ​ H + __ ​   ​​u​​  2​+ zg ​​m​  ​​  ​​ − ​Q​
∙

2
fs
​​     ​  ​  ​  ​ ​​

[( ) ]
∙ 1 2
__ ∙ ∙
​​W​​  ideal​​ = Δ​​ ​ H + ​   ​​u​​  ​+ zg ​​m​  ​​  ​​ − ​Tσ​  ​​Δ​(S​m​)​  fs​​
2
fs
By difference, as given by Eq. (5.26),
∙ ∙
​​ ​​W​​  lost​​ = ​Tσ​ ​Δ​(​S​m​​)​​  fs​​ − ​Q​ ​​
∙
(5.27)

For the case of a single surroundings temperature Tσ, the steady-state entropy balance, Eq.
(5.17), becomes:
∙
​Q​ ∙
​​​S​​  G​​ = Δ​​(​S​m​)​ ​​  fs​​ − ___
∙
​   ​​ (5.28)
​Tσ​  ​​
 ∙ ∙
Multiplication by Tσ gives: ​​Tσ​ ​​​S​​  G​​ = ​Tσ​ ​Δ​(​S​m​​)​​  fs​​ − ​Q​​
∙

The right sides of this equation and Eq. (5.27) are identical; therefore,
∙ ∙
​​ ​​W​​  lost​​ = ​Tσ​ ​​​S​​  G​​ ​​ (5.29)
∙ ∙
As a consequence of the second law, ​​​S​​  G​​ ≥∙ 0;​it follows that ​​​W​​  lost​​ ≥ 0.​When a process is
completely reversible,
∙
the equality holds, and W
​​​ ​​  lost​​ = 0.​For irreversible processes the inequal-
ity holds, and ​​​W​​  lost​​,​i.e., the energy that becomes unavailable for work, is positive.
The engineering significance of this result is clear: The greater the irre-
versibility of a process, the greater the rate of entropy production and
the greater the amount of energy made unavailable for work. Thus every
irreversibility carries with it a price. Minimizing entropy production is
essential for conservation of the earth’s resources.
∙
For the special case of a single stream flowing through the control volume, ​​m​​factors and
∙
becomes a multiplier of the entropy difference in Eqs. (5.27) and (5.28). Division by m ​​ ​​ con-
verts all terms to the basis of a unit amount of fluid flowing through the control volume. Thus,

∙ ∙ ∙
​​​W​​  lost​​ = ​m​​Tσ​ ​ΔS − ​Q​​ (5.30) ​W​lost​= ​Tσ​ ​ΔS − Q​ (5.31)

Q (5.32) Q
​​​S∙ ​​  G​​ = ​m∙ ​ΔS − ___
​   ​​ ​ ​ (5.33)
​S​G​= ΔS − ___
​Tσ​  ​​ ​Tσ​ ​
∙
Recall here that Q​​ ​​ and Q represent heat exchange with the surroundings, but with the sign
referred to the system. Equations (5.31) and (5.33) combine for a unit amount of fluid to give:
​
​W​lost​= ​Tσ​ ​S​G​​ (5.34)
Again, because SG ≥ 0, it follows that Wlost ≥ 0.

Example 5.9
The two basic types of steady-flow heat exchanger are characterized by their flow pat-
terns: cocurrent and countercurrent. Temperature profiles for the two types are indi-
cated in Fig. 5.6. In cocurrent flow, heat is transferred from a hot stream, flowing from
left to right, to a cold stream flowing in the same direction, as indicated by arrows. In
countercurrent flow, the cold stream, again flowing from left to right, receives heat
from the hot stream flowing in the opposite direction.
The lines ∙
relate the temperatures of the hot and cold streams, TH and TC respec-
tively, to ​​​Q​​  C​​​, the accumulated rate of heat addition to the cold stream as it progresses
through the exchanger from the left end to an arbitrary downstream location. The fol-
lowing specifications apply to both cases:
∙
​T​​H​1​​= 400 K  ​T​​H​2​​= 350 K  ​T​​C​1​​= 300 K  ​​n​​  H​​ = 1 mol⋅​s​−1​​
​
 TH1 400 K 400 K TH1

390 K TC2

TH TH
TC
T 350 K TH2 350 K
T
340 K

TC

TC1 300 K TC1 300 K

0 . 0 .
QC QC

(a) (b)

Figure 5.6: Heat exchangers. (a) Case I, cocurrent. (b) Case II, countercurrent.

The minimum temperature difference between the flowing streams is 10 K. Assume

the ideal-gas state for both streams with CP = (7/2)R. Find the lost work for both cases.
Take Tσ = 300 K.

Solution 5.9
With∙
the assumption ∙
of negligible kinetic- and potential-energy changes, with
​​​Ws​​​ = 0,​and with ​​Q​ = 0​(there is no heat exchange with the surroundings) the
energy balance [Eq. (2.29)] can be written:
​​​n​​  H​​​(​Δ​H​ig​)​H​+ ​​n​​  C​​​(​Δ​H​ig​)​C​= 0​
∙ ∙

With constant molar heat capacity, this becomes:

​​​​n​​  H​​ ​C​Pig​​(​​T​​H​2​​ − ​T​​H​1​)​ ​+ ​​n​​  C​​​C​Pig​​(​T​​C​2​​ − ​T​​C​1​)​ ​= 0​​
∙ ∙
(A)
The total rate of entropy change for the flowing streams is:
Δ ​(​​S​ig​n​​)​​  fs​​ = ​​n​​  H​​​(​Δ​S​ig​)​H​+ ​​n​​  C​​​(​Δ​S​ig​)​C​​
∙ ∙ ∙
​

By Eq. (5.10), with the assumption of negligible pressure change in the flowing
streams,

( ​T​​H​1​​ ​​n∙ ​​  H​​ ​T​​C​1​​)

​T​​H​ ​​ ​​n​​  C​​ ∙
​T​​C​ ​​
Δ(​ ​S​ig​n)​​ ​​  fs​​ = ​​n​​  H​​​C​Pig​​ ln ___
​ 2 ​+ ___ ln ___
​ 2 ​ ​​
∙ ∙
​ ​   ​ (B)
 ∙
Finally, by Eq. (5.27), with ​​Q​​ = 0,
​​​W​​  lost​​ = ​Tσ​ ​Δ ​(​​S​ig​n​​)​​  fs​​​
∙ ∙
(C)
These equations apply to both cases.
∙ Case I: Cocurrent flow. By Eqs. (A), (B), and (C), respectively:
∙
​​n​​  C​​ 400 − 350
___
​  ∙  ​ = ________
​ ​= 1.25
​​n​​  H​​ 340 − 300

( 400 300 )
   
​​         ​  ​  ​ 350 340 ​​​
Δ​(​S​​  ig​​n​)f​  s​​ = (​ 1)(​ 7 / 2)​(8.314)​ ln ____
​ ​+ 1.25 ln ____
​ ​ ​= 0.667 J​·K​​−1​·s​​−1​
∙

∙
​​W​​  lost​​ = ​(300)​(0.667)​= 200.1 J⋅​s​−1​
∙ Case II: Countercurrent flow. By Eqs. (A), (B), and (C), respectively:
∙
​​n​​  C​​ 400 − 350
___
​  ∙  ​ = ________
​ ​= 0.5556
​​n​​  H​​ 390 − 300

( 400 300 )
   
​​         ​  ​  350
​ 390 ​​​
Δ ​(​S​ig​n​)f​  s​​ = (​ 1)(​ 7 / 2)(​ 8.314)​ ln ____
​ ​ + 0.5556 ln ____
​ ​ ​= 0.356 J​·K​​−1​·s​​−1​
∙

∙
​​W​​  lost​​ = (300)(0.356) = 106.7 J⋅​s​−1​
Although the total rate of heat transfer is the same for both exchangers, the
temperature rise of the cold stream in countercurrent flow is more than
twice that for cocurrent flow. Thus, its entropy increase per unit mass is larger
than for the cocurrent case. However, its flow rate is less than half that of
the cold stream in cocurrent flow, so that the total entropy increase of the cold
stream is less for countercurrent flow. From a thermodynamic point ∙
of view, the
∙
countercurrent case is much more efficient. Because Δ(​​S​​  ​​​​n​​)fs = ​​SG
ig ​​ , both the rate
of entropy generation and the lost work for the countercurrent case are only about
half the value for the cocurrent case. Greater efficiency in the countercurrent case
would be anticipated based on Fig. 5.6, which shows that heat is transferred across
a smaller temperature difference (less irreversibly) in the countercurrent case.

5.9 THE THIRD LAW OF THERMODYNAMICS

Measurements of heat capacities at very low temperatures provide data for the calculation from
Eq. (5.1) of entropy changes down to 0 K. When these calculations are made for different crystal-
line forms of the same chemical species, the entropy at 0 K appears to be the same for all forms.
When the form is noncrystalline, e.g., amorphous or glassy, calculations show that the entropy of
the disordered form is greater than that of the crystalline form. Such calculations, which are sum-
marized elsewhere,6 lead to the postulate that the absolute entropy is zero for all perfect crystalline
substances at absolute zero temperature. While this essential idea was advanced by Nernst and

6K. S. Pitzer, Thermodynamics, 3d ed., chap. 6, McGraw-Hill, New York, 1995.

 Rev. Confirming Pages

198 CHAPTER 5. The Second Law of Thermodynamics

Planck at the beginning of the twentieth century, more recent studies at very low temperatures have
increased confidence in this postulate, which is now accepted as the third law of thermodynamics.
If the entropy is zero at T = 0 K, then Eq. (5.1) lends itself to the calculation of absolute
entropies. With T = 0 as the lower limit of integration, the absolute entropy of a gas at temper-
ature T based on calorimetric data is:
​T​ f​​ Δ​H​f​ ​Tυ​  ​​ T ​(​C​ ​)​ ​
​(​CP​ ​)​s​ ​(​CP​ ​)​l​ Δ​Hυ​ ​
∫0 ∫ ∫
P g
S = ​ ​  ​_____
​ ​ ​ ​dT + ____
​ ​+ ​ ​  ​____ ​ ​ ​dT + ____
​ ​+ ​ ​  ​_____​ ​ ​dT​ (5.35)
T ​T​f​ ​T​ f​​ T ​Tυ​ ​ ​Tυ​  ​​ T

This equation7 is based on the supposition that no solid-state transitions take place and thus no
heats of transition need appear. The only constant-temperature heat effects are those of melt-
ing at Tf and vaporization at Tυ. When a solid-phase transition occurs, a term ΔHt /Tt is added.
Note that although the third law implies that absolute values of entropy are obtainable,
for most thermodynamic analyses, only relative values are needed. As a result, reference states
other than the perfect crystal at 0 K are commonly used. For example, in the steam tables of
App. E, ­saturated liquid water at 273.16 K is taken as the reference state and assigned zero
entropy. However, the absolute or “third law” entropy of saturated liquid water at 273.16 K is
3.515 kJ⋅kg−1⋅K−1.

5.10 ENTROPY FROM THE MICROSCOPIC VIEWPOINT

Because molecules in the ideal-gas state do not interact, their internal energy resides with
individual molecules. This is not true of the entropy, which is inherently a collective property
of a large number of molecules or other entities. The microscopic interpretation of entropy is
suggested by the following example.
Suppose an insulated container, partitioned into two equal volumes, contains Avoga-
dro’s number NA of molecules in one section and no molecules in the other. When the partition
is withdrawn, the molecules quickly distribute themselves uniformly throughout the total vol-
ume. The process is an adiabatic expansion that accomplishes no work. Therefore,
ig
ΔU = ​C​V​Δ
​ ​ T = 0​
and the temperature does not change. However, the pressure of the gas decreases by half, and
the entropy change, as given by Eq. (5.10), is:
​P​2​
​ Δ​S​ig​= −R ln ___
​ ​= R ln 2​
​P​1​
Because this is the total entropy change, the process is clearly irreversible.
At the instant when the partition is removed, the molecules occupy only half the space
available to them. In this momentary initial state, the molecules are not randomly distributed
over the total volume to which they have access but are crowded into just half the total vol-
ume. In this sense they are more ordered than they are in the final state of uniform distribution
throughout the entire volume. Thus, the final state can be regarded as a more random, or more
disordered, state than the initial state. Generalizing from this example, and from many other
7Evaluation of the first term on the right is not a problem for crystalline substances, because ​​C​ P​​/T​ remains finite
as T → 0.

smi96529_ch05_173-209.indd 198 06/19/17 12:32 PM

similar observations, one is led to the notion that increasing disorder (or decreasing structure)
at the molecular level corresponds to increasing entropy.
The means for expressing disorder in a quantitative way was developed by L. Boltzmann
and J. W. Gibbs through a quantity Ω, defined as the number of different ways that micro-
scopic particles can be distributed among the “states” accessible to them. It is given by the
general formula:
N!
​Ω = _____________
​  ​​ (5.36)
​(​N​1​!​)​(​N​2​!​)​(​N​3​!​)​. . .

where N is the total number of particles, and N1, N2, N3, etc., represent the numbers of parti-
cles in “states” 1, 2, 3, etc. The term “state” denotes a condition of the microscopic particles,
and the quotation marks distinguish this idea of state from the usual thermodynamic meaning
as applied to a macroscopic system.
With respect to our example there are but two “states” for each molecule, representing
location of the given molecule in one half or the other of the container. The total number of
particles is NA molecules, and initially they are all in a single “state.” Thus
​N​A​!
​Ω​1​= _______
​ ​ ​= 1​
​(​N​A​!​)​(​0!​)​

This result confirms that initially the molecules can be distributed between the two accessible
“states” in just one way. They are all in a given “state,” all in just one half of the container. For
an assumed final condition of uniform distribution of the molecules between the two halves of
the container, N1 = N2 = NA/2, and
​N​A​!
​Ω​2​= ________
​ ​ ​​
[​ ​(​N​A​/ 2​)​!]​ ​
2

This expression gives a very large number for Ω2, indicating that the molecules can be dis-
tributed uniformly between the two “states” in many different ways. Many other values of Ω2
are possible, each one of which is associated with a particular nonuniform distribution of the
molecules between the two halves of the container. The ratio of a particular Ω2 to the sum of
all possible values is the probability of that particular distribution.
The connection established by Boltzmann between entropy S and Ω is given by the equation:

​
S = k ln Ω​ (5.37)

Boltzmann’s constant k equals R/NA. The entropy difference between states 1 and 2 is:
​Ω​2​
​S​2​− ​S​1​= k ln ___
​ ​ ​​
​Ω​1​

Substituting values for Ω1 and Ω2 from our example into this expression gives:
​N​A​!
​S​2​− ​S​1​= k ln ________
​ ​ ​= k[ln ​N​A​! − 2 ln (​N​A​/ 2)!]​
[​ A ]​ ​
2
(
​ ​
N ​ /
​ )
2​ !
​
 Because NA is very large, we take advantage of Stirling’s formula for the logarithms of
factorials of large numbers:
​
ln X ! = X ln X − X​
Whence,

[ (2 2 )]
​N​A​ ​N​A​ ___
​N​A​
S​ ​2​− ​S​1​= k​ ​N​ A​​ ln ​N​A​− ​N​A​− 2​ ___​ ​ln ___
​ ​− ​ ​ ​ ​​
2
​​​      ​  ​   ​​ ​
​N​A​
​ = k​N​A​ln _____
​ ​= k​N​A​ln 2 = R ln 2
​N​A​/ 2

This value for the entropy change of the expansion process is the same as that given by
Eq. (5.10), the classical thermodynamic formula for the ideal-gas state.
Equations (5.36) and (5.37) provide a basis for relating macroscopic thermodynamic
properties to the microscopic configurations of molecules. Here we have applied them to a
very simple, and somewhat contrived, situation involving molecules in the ideal gas state, in
order to provide a simple illustration of this connection between molecular configurations and
macroscopic properties. The field of science and engineering devoted to studying and exploit-
ing this connection is called statistical thermodynamics or statistical mechanics. The methods
of statistical thermodynamics are well developed, and are now routinely applied, in combina-
tion with computational simulation of the behavior of molecules, to make useful predictions of
thermodynamic properties of real substances without recourse to experiment.8

5.11 SYNOPSIS

After studying this chapter, including the end-of-chapter problems, one should be able to:

∙ Comprehend the existence of entropy as a state function, related to observable proper-

ties of a system, for which changes are computed from:
​ d​S​t​ = d​Qrev
​ ​/ T​ (5.1)
∙ State the second law of thermodynamics in words and as an inequality in terms of entropy.
∙ Define and distinguish between thermal efficiency and thermodynamic efficiency.
∙ Compute the thermal efficiency of a reversible heat engine.
∙ Compute entropy changes for the ideal-gas state with heat capacity expressed as a poly-
nomial in temperature.
∙ Construct and apply entropy balances for open systems.
∙ Determine whether a specified process violates the second law.
∙ Compute ideal work, lost work, and thermodynamic efficiencies of processes.
8Many introductory texts on statistical thermodynamics are available. The interested reader is referred to
­ olecular Driving Forces: Statistical Thermodynamics in Chemistry & Biology, by K.A. Dill and S. Bromberg,
M
Garland ­Science, 2010, and many books referenced therein.
5.12 PROBLEMS

5.1. Prove that it is impossible for two lines representing reversible, adiabatic processes
on a PV diagram to intersect. (Hint: Assume that they do intersect, and complete the
cycle with a line representing a reversible, isothermal process. Show that performance
of this cycle violates the second law.)

5.2. A Carnot engine receives 250 kJ·s−1 of heat from a heat-source reservoir at 525°C and
rejects heat to a heat-sink reservoir at 50°C. What are the power developed and the
heat rejected?

5.3. The following heat engines produce power of 95,000 kW. Determine in each case
the rates at which heat is absorbed from the hot reservoir and discarded to the cold
reservoir.

(a) A Carnot engine operates between heat reservoirs at 750 K and 300 K.
(b) A practical engine operates between the same heat reservoirs but with a thermal
efficiency η = 0.35.

5.4. A particular power plant operates with a heat-source reservoir at 350°C and a heat-
sink reservoir at 30°C. It has a thermal efficiency equal to 55% of the Carnot-engine
thermal efficiency for the same temperatures.
(a) What is the thermal efficiency of the plant?
(b) To what temperature must the heat-source reservoir be raised to increase the ther-
mal efficiency of the plant to 35%? Again η is 55% of the Carnot-engine value.

5.5. An egg, initially at rest, is dropped onto a concrete surface; it breaks. Prove that
the process is irreversible. In modeling this process treat the egg as the s­ ystem, and
assume the passage of sufficient time for the egg to return to its initial temperature.

5.6. Which is the more effective way to increase the thermal efficiency of a Carnot engine:
to increase TH with TC constant, or to decrease TC with TH constant? For a real engine,
which would be the more practical way?

5.7. Large quantities of liquefied natural gas (LNG) are shipped by ocean tanker. At the
unloading port, provision is made for vaporization of the LNG so that it may be deliv-
ered to pipelines as gas. The LNG arrives in the tanker at atmospheric pressure and
113.7 K, and represents a possible heat sink for use as the cold reservoir of a heat
engine. For unloading of LNG as a vapor at the rate of 9000 m3·s−1, as measured
at 25°C and 1.0133 bar, and assuming the availability of an adequate heat source at
30°C, what is the maximum possible power obtainable and what is the rate of heat
transfer from the heat source? Assume that LNG at 25°C and 1.0133 bar is an ideal
gas with the molar mass of 17. Also assume that the LNG vaporizes only, absorbing
only its latent heat of 512 kJ·kg−1 at 113.7 K.
 5.8. With respect to 1 kg of liquid water:

(a) Initially at 0°C, it is heated to 100°C by contact with a heat reservoir at 100°C.
What is the entropy change of the water? Of the heat reservoir? What is ΔStotal?
(b) Initially at 0°C, it is first heated to 50°C by contact with a heat reservoir at 50°C
and then to 100°C by contact with a reservoir at 100°C. What is ΔStotal?
(c) Explain how the water might be heated from 0°C to 100°C so that ΔStotal = 0.

5.9. A rigid vessel of 0.06 m3 volume contains an ideal gas, CV = (5/2)R, at 500 K and
1 bar.

(a) If heat in the amount of 15,000 J is transferred to the gas, determine its entropy
change.
(b) If the vessel is fitted with a stirrer that is rotated by a shaft so that work in the
amount of 15,000 J is done on the gas, what is the entropy change of the gas if the
process is adiabatic? What is ΔStotal? What is the irreversible feature of the process?

5.10. An ideal gas, CP = (7/2)R, is heated in a steady-flow heat exchanger from 70°C to
190°C by another stream of the same ideal gas which enters at 320°C. The flow rates
of the two streams are the same, and heat losses from the exchanger are negligible.

(a) Calculate the molar entropy changes of the two gas streams for both parallel and
countercurrent flow in the exchanger.
(b) What is ΔStotal in each case?
(c) Repeat parts (a) and (b) for countercurrent flow if the heating stream enters
at 200°C.

5.11. For an ideal gas with constant heat capacities, show that:
(a) For a temperature change from T1 to T2, ΔS of the gas is greater when the change
occurs at constant pressure than when it occurs at constant volume.
(b) For a pressure change from P1 to P2, the sign of ΔS for an isothermal change is
opposite that for a constant-volume change.

5.12. For an ideal gas prove that:

ΔS T ​C​ig​​dT

∫ ​T​ 0​​ R T
___ V
​ ​= ​ ​  ​___
​ ​ V ​___
​ ​ ​+ ln ___
​ ​​
R ​V​0​

5.13. A Carnot engine operates between two finite heat reservoirs of total heat capacity
t t
​​C​  H ​​​  and ​C​C​​.
(a) Develop an expression relating TC to TH at any time.
​ ​Ct ​,​  ​T​H​ ​,​ and
​​ Ht ​,​  C
(b) Determine an expression for the work obtained as a function of C​
the initial temperatures ​T​​H​0​​and ​T​​C​0​​​.
(c) What is the maximum work obtainable? This corresponds to infinite time, when
the reservoirs attain the same temperature.
 In approaching this problem, use the differential form of Carnot’s equation,
d​Q​H​
____ ​T​H​
​ ​ ​= − ___
​ ​​
d​Q​C​ ​T​C​
and a differential energy balance for the engine,

​
dW − d​Q​C​− d​QH
​ ​= 0​

Here, QC and QH refer to the reservoirs.

5.14. A Carnot engine operates between an infinite hot reservoir and a finite cold reservoir
t
of total heat capacity ​C​C​​.
t
(a) Determine an expression for the work obtained as a function of ​C ​​C​, ​T​H​ ​​
(= constant), TC , and the initial cold-reservoir temperature ​T​​C​0​.​
(b) What is the maximum work obtainable? This corresponds to infinite time, when
TC becomes equal to TH.

The approach to this problem is the same as for Prob. 5.13.

5.15. A heat engine operating in outer space may be assumed equivalent to a Carnot engine
operating between reservoirs at temperatures TH and TC . The only way heat can be dis-
carded from the engine is by radiation, the rate of which is given (approximately) by:

| |
∙
​​ ​​Q​​  C​​  ​ = kA​T​C4 ​​

where k ∙is a constant and A is the area of the radiator. Prove that, for fixed power
output |​​W​​| and for fixed temperature TH, the radiator area A is a minimum when the
temperature ratio TC ​/​TH is 0.75.

5.16. Imagine that a stream of fluid in steady-state flow serves as a heat source for an infinite
set of Carnot engines, each of which absorbs a differential amount of heat from the
fluid, causing its temperature to decrease by a differential amount, and each of which
rejects a differential amount of heat to a heat reservoir at temperature Tσ. As a result of
the operation of the Carnot engines, the temperature of the fluid decreases from T1 to T2.
Equation (5.8) applies here in differential form, wherein η is defined as:

η ≡ dW / dQ​
​

where Q is heat transfer with respect to the flowing fluid. Show that the total work of
the Carnot engines is given by:

​
W = Q − ​Tσ​ ​ΔS​

where ΔS and Q both refer to the fluid. In a particular case, the fluid is an ideal gas,
with CP = (7/2)R, and the operating temperatures are T1 = 600 K and T2 = 400 K.
If Tσ = 300 K, what is the value of W in J·mol−1? How much heat is discarded to the
heat reservoir at Tσ? What is the entropy change of the heat reservoir? What is ΔStotal?
 5.17. A Carnot engine operates between temperature levels of 600 K and 300 K. It drives
a Carnot refrigerator, which provides cooling at 250 K and discards heat at 300 K.
Determine a numerical value for the ratio of heat extracted by the refrigerator (“cooling
load”) to the heat delivered to the engine (“heating load”).

5.18. An ideal gas with constant heat capacity undergoes a change of state from conditions
T1, P1 to conditions T2, P2. Determine ΔH (J·mol−1) and ΔS (J·mol−1·K−1) for one of
the following cases.

(a) T1 = 300 K, P1 = 1.2 bar, T2 = 450 K, P2 = 6 bar, CP/R = 7/2.

(b) T1 = 300 K, P1 = 1.2 bar, T2 = 500 K, P2 = 6 bar, CP/R = 7/2.
(c) T1 = 450 K, P1 = 10 bar, T2 = 300 K, P2 = 2 bar, CP/R = 5/2.
(d ) T1 = 400 K, P1 = 6 bar, T2 = 300 K, P2 = 1.2 bar, CP/R = 9/2.
(e) T1 = 500 K, P1 = 6 bar, T2 = 300 K, P2 = 1.2 bar, CP/R = 4.

5.19. An ideal gas, CP = (7/2)R and CV = (5/2)R, undergoes a cycle consisting of the follow-
ing mechanically reversible steps:

∙ An adiabatic compression from P1, V1, T1 to P2, V2, T2.

∙ An isobaric expansion from P2, V2, T2 to P3 = P2, V3, T3.
∙ An adiabatic expansion from P3, V3, T3 to P4, V4, T4.
∙ A constant-volume process from P4, V4, T4 to P1, V1 = V4, T1.
Sketch this cycle on a PV diagram and determine its thermal efficiency if T1 = 200°C,
T2 = 1000°C, and T3 = 1700°C.

5.20. The infinite heat reservoir is an abstraction, often approximated in engineering appli-
cations by large bodies of air or water. Apply the closed-system form of the energy
balance [Eq. (2.3)] to such a reservoir, treating it as a constant-volume system. How is
it that heat transfer to or from the reservoir can be nonzero, yet the temperature of the
reservoir remains constant?

5.21. One mole of an ideal gas, CP = (7/2)R and CV = (5/2)R, is compressed adiabatically in
a piston/cylinder device from 2 bar and 25°C to 7 bar. The process is irreversible and
requires 35% more work than a reversible, adiabatic compression from the same initial
state to the same final pressure. What is the entropy change of the gas?

5.22. A mass m of liquid water at temperature T1 is mixed adiabatically and isobarically

with an equal mass of liquid water at temperature T2. Assuming constant CP, show

​(​T​1​+ ​T​2​)​/ 2
Δ​S​t​= Δ​S​total​= ​S​G​= 2m​CP​ ​ln ________
​ ​ ​​
​(​T​1​​T​2​)​1/2​

and prove that this is positive. What would be the result if the masses of the water were
different, say, m1 and m2?
 5.23. Reversible adiabatic processes are isentropic. Are isentropic processes necessarily
reversible and adiabatic? If so, explain why; if not, give an illustrative example.

5.24. Prove that the mean heat capacities ⟨CP⟩H and ⟨CP⟩S are inherently positive, whether
T > T0 or T < T0. Explain why they are well defined for T = T0.

5.25. A reversible cycle executed by 1 mol of an ideal gas for which CP = (5/2)R and
CV = (3/2)R consists of the following:
∙ Starting at T1 = 700 K and P1 = 1.5 bar, the gas is cooled at constant pressure to
T2 = 350 K.
∙ From 350 K and 1.5 bar, the gas is compressed isothermally to pressure P2.
∙ The gas returns to its initial state along a path for which PT = constant.

What is the thermal efficiency of the cycle?

5.26. One mole of an ideal gas is compressed isothermally but irreversibly at 130°C from
2.5 bar to 6.5 bar in a piston/cylinder device. The work required is 30% greater than
the work of reversible, isothermal compression. The heat transferred from the gas
during compression flows to a heat reservoir at 25°C. Calculate the entropy changes
of the gas, the heat reservoir, and ΔStotal.

5.27. For a steady-flow process at approximately atmospheric pressure, what is the entropy
change of the gas:
(a) When 10 mol of SO2 is heated from 200 to 1100°C?
(b) When 12 mol of propane is heated from 250 to 1200°C?
(c) When 20 kg of methane is heated from 100 to 800°C?
(d) When 10 mol of n-butane is heated from 150 to 1150°C?
(e) When 1000 kg of air is heated from 25 to 1000°C?
( f) When 20 mol of ammonia is heated from 100 to 800°C?
(g) When 10 mol of water is heated from 150 to 300°C?
(h) When 5 mol of chlorine is heated from 200 to 500°C?
(i) When 10 kg of ethylbenzene is heated from 300 to 700°C?

5.28. What is the entropy change of the gas, heated in a steady-flow process at approxi-
mately atmospheric pressure,

(a) When 800 kJ is added to 10 mol of ethylene initially at 200°C?

(b) When 2500 kJ is added to 15 mol of 1-butene initially at 260°C?
(c) When 106(Btu) is added to 40(lb mol) of ethylene initially at 500(°F)?

5.29. A device with no moving parts provides a steady stream of chilled air at −25°C and
1 bar. The feed to the device is compressed air at 25°C and 5 bar. In addition to the
stream of chilled air, a second stream of warm air flows from the device at 75°C and
1 bar. Assuming adiabatic operation, what is the ratio of chilled air to warm air that the
device produces? Assume that air is an ideal gas for which CP = (7/2)R.
 5.30. An inventor has devised a complicated nonflow process in which 1 mol of air is the
working fluid. The net effects of the process are claimed to be:
∙ A change in state of the air from 250°C and 3 bar to 80°C and 1 bar.
∙ The production of 1800 J of work.
∙ The transfer of an undisclosed amount of heat to a heat reservoir at 30°C.
Determine whether the claimed performance of the process is consistent with the sec-
ond law. Assume that air is an ideal gas for which CP = (7/2)R.

5.31. Consider the heating of a house by a furnace, which serves as a heat-source reservoir at a
high temperature TF. The house acts as a heat-sink reservoir at temperature T, and heat |Q|
must be added to the house during a particular time interval to maintain this temperature.
Heat |Q| can of course be transferred directly from the furnace to the house, as is the usual
practice. However, a third heat reservoir is readily available, namely, the surroundings at
temperature Tσ, which can serve as another heat source, thus reducing the amount of heat
required from the furnace. Given that TF = 810 K, T = 295 K, Tσ = 265 K, and |Q| = 1000 kJ,
determine the minimum amount of heat |QF| which must be extracted from the heat-source
reservoir (furnace) at TF. No other sources of energy are available.

5.32. Consider the air conditioning of a house through use of solar energy. At a particular
location, experiment has shown that solar radiation allows a large tank of pressurized
water to be maintained at 175°C. During a particular time interval, heat in the amount
of 1500 kJ must be extracted from the house to maintain its temperature at 24°C when
the surroundings temperature is 33°C. Treating the tank of water, the house, and the
surroundings as heat reservoirs, determine the minimum amount of heat that must be
extracted from the tank of water by any device built to accomplish the required cool-
ing of the house. No other sources of energy are available.

5.33. A refrigeration system cools a brine from 25°C to −15°C at a rate of 20 kg·s−1. Heat is
discarded to the atmosphere at a temperature of 30°C. What is the power requirement
if the thermodynamic efficiency of the system is 0.27? The specific heat of the brine
is 3.5 kJ·kg−1·°C−1.

5.34. An electric motor under steady load draws 9.7 amperes at 110 volts; it delivers
1.25(hp) of mechanical energy. The temperature of the surroundings is 300 K. What is
the total rate of entropy generation in W·K−1?

5.35. A 25-ohm resistor at steady state draws a current of 10 amperes. Its temperature is
310 K; the temperature
∙
of the surroundings is 300 K. What is the total rate of entropy
generation S​​​ ​​  G​​​? What is its origin?

5.36. Show how the general rate form of the entropy balance, Eq. (5.16), reduces to
Eq. (5.2) for the case of a closed system.
 Rev. Confirming Pages

5.12. Problems 207

5.37. A list of common unit operations follows:

(a) Single-pipe heat exchanger;

(b) Double-pipe heat exchanger;
(c) Pump;
(d) Gas compressor;
(e) Gas turbine (expander);
( f) Throttle valve;
(g) Nozzle.

Develop a simplified form of the general steady-state entropy balance appropriate to

each operation. State carefully, and justify, any assumptions you make.

5.38. Ten kmol per hour of air is throttled from upstream conditions of 25°C and 10 bar to a
downstream pressure of 1.2 bar. Assume air to be an ideal gas with CP = (7/2)R.

(a) What is the downstream temperature?

(b) What is the entropy change of the air in J·mol−1·K−1 ?
(c) What is the rate of entropy generation in W·K−1 ?
(d) If the surroundings are at 20°C, what is the lost work?

5.39. A steady-flow adiabatic turbine (expander) accepts gas at conditions T1, P1, and
discharges at conditions T2, P2. Assuming ideal gases, determine (per mole of gas)
W, Wideal, Wlost, and SG for one of the following cases. Take Tσ = 300 K.

(a) T1 = 500 K, P1 = 6 bar, T2 = 371 K, P2 = 1.2 bar, CP/R = 7/2.

(b) T1 = 450 K, P1 = 5 bar, T2 = 376 K, P2 = 2 bar, CP/R = 4.
(c) T1 = 525 K, P1 = 10 bar, T2 = 458 K, P2 = 3 bar, CP/R = 11/2.
(d) T1 = 475 K, P1 = 7 bar, T2 = 372 K, P2 = 1.5 bar, CP/R = 9/2.
(e) T1 = 550 K, P1 = 4 bar, T2 = 403 K, P2 = 1.2 bar, CP/R = 5/2.

5.40. Consider the direct heat transfer from a heat reservoir at T1 to another heat reservoir at
temperature T2, where T1 > T2 > Tσ. It is not obvious why the lost work of this process
should depend on Tσ, the temperature of the surroundings, because the surroundings
are not involved in the actual heat-transfer process. Through appropriate use of the
Carnot-engine formula, show for the transfer of an amount of heat equal to |Q| that
​T​ 1​​−​T​ 2​​
​​W​ lost​​ = ​T​  σ​​​| Q |______
​​   ​= ​T​  σ​​​S​ G​​​
​T​ 1​​​T​ 2​​

5.41. An ideal gas∙ at 2500∙ kPa is throttled adiabatically to 150 kPa at the rate of 20 mol·s–1.
Determine S​​​ ​​  G​​​ and ​​​W​​  lost​​​ if Tσ = 300 K.

5.42. An inventor claims to have devised a cyclic engine which exchanges heat with res-
ervoirs at 25°C and 250°C, and which produces 0.45 kJ of work for each kJ of heat
extracted from the hot reservoir. Is the claim believable?

smi96529_ch05_173-209.indd 207 06/19/17 12:34 PM

 5.43. Heat in the amount of 150 kJ is transferred directly from a hot reservoir at TH = 550 K
to two cooler reservoirs at T1 = 350 K and T2 = 250 K. The surroundings temperature
is Tσ = 300 K. If the heat transferred to the reservoir at T1 is half that transferred to the
reservoir at T2, calculate:
(a) The entropy generation in kJ·K–1.
(b) The lost work.

How could the process be made reversible?

5.44. A nuclear power plant generates 750 MW; the reactor temperature is 315°C and a river
with water temperature of 20°C is available.
(a) What is the maximum possible thermal efficiency of the plant, and what is the
minimum rate at which heat must be discarded to the river?
(b) If the actual thermal efficiency of the plant is 60% of the maximum, at what rate
must heat be discarded to the river, and what is the temperature rise of the river if
it has a flow rate of 165 m3·s–1 ?

5.45. A single gas stream enters a process at conditions T1, P1, and leaves at pressure P2.
The process is adiabatic. Prove that the outlet temperature T2 for the actual (irrevers-
ible) adiabatic process is greater than that for a reversible adiabatic process. Assume
the gas is ideal with constant heat capacities.

5.46. A Hilsch vortex tube operates with no moving mechanical parts and splits a gas stream
into two streams: one warmer and the other cooler than the entering stream. One such
tube is reported to operate with air entering at 5 bar and 20°C, and air streams leaving
at 27°C and –22°C, both at 1(atm). The mass flow rate of warm air leaving is six times
that of the cool air. Are these results possible? Assume air to be an ideal gas at the
conditions given.

5.47. (a) Air at 70(°F) and 1(atm) is cooled at the rate of 100,000(ft)3(hr)–1 to 20(°F) by
refrigeration. For a surroundings temperature of 70(°F), what is the minimum
power requirement in (hp)?
(b) Air at 25°C and 1(atm) is cooled at the rate of 3000 m3·hr–1 to –8°C by refrig-
eration. For a surroundings temperature of 25°C, what is the minimum power
requirement in kW?

5.48. A flue gas is cooled from 2000 to 300(°F), and the heat is used to generate saturated
steam at 212(°F) in a boiler. The flue gas has a heat capacity given by:
​C​P​
___
​ ​ ​= 3.83 + 0.000306 T / (R )​
R
Water enters the boiler at 212(°F) and is vaporized at this temperature; its latent heat
of vaporization is 970.3(Btu)(lbm)–1.
 (a) With reference to a surroundings temperature of 70(°F), what is the lost work of
this process in (Btu)(lb mole)–1 of flue gas?
(b) With reference to a surroundings temperature of 70(°F), what is the maximum
work, in (Btu)(lb mole)–1 of flue gas, that can be accomplished by the saturated
steam at 212(°F) if it condenses only, and does not subcool?
(c) How does the answer to part (b) compare with the maximum work theoretically
obtainable from the flue gas itself as it is cooled from 2000 to 300(°F)?

5.49. A flue gas is cooled from 1100 to 150°C, and the heat is used to generate saturated
steam at 100°C in a boiler. The flue gas has a heat capacity given by:
​C​P​
___
​ ​ ​= 3.83 + 0.000551 T / K​
R
Water enters the boiler at 100°C and is vaporized at this temperature; its latent heat of
vaporization is 2256.9 kJ·kg–1.
(a) With reference to a surroundings temperature of 25°C, what is the lost work of
this process in kJ·mol–1 of flue gas?
(b) With reference to a surroundings temperature of 25°C, what is the maximum
work, in kJ·mol–1 of flue gas, that can be accomplished by the saturated steam at
100°C if it condenses only, and does not subcool?
(c) How does the answer to part (b) compare with the maximum work theoretically
obtainable from the flue gas itself as it is cooled from 1100 to 150°C?

5.50. Ethylene vapor is cooled at atmospheric pressure from 830 to 35°C by direct heat
transfer to the surroundings at a temperature of 25°C. With respect to this surround-
ings temperature, what is the lost work of the process in kJ·mol–1? Show that the
same result is obtained as the work which can be derived from reversible heat engines
­operating with the ethylene vapor as heat source and the surroundings as sink. The
heat capacity of ethylene is given in Table C.1 of App. C.