Thermo

CHAPTER
ENTROPY
4
S = k ln W
L. Boltzmann
We have discussed energy balances and the fact that friction and velocity gradients cause the loss of
useful work. It would be desirable to determine maximum work output (or minimum work input)
for a given process. Our concern for accomplishing useful work inevitably leads to a search for
what might cause degradation of our capacity to convert any form of energy into useful work. As an
example, isothermally expanding an ideal gas from V i to 2V i can produce a significant amount of
useful work if carried out reversibly, or possibly zero work if carried out irreversibly. If we could
understand the difference between these two operations, we would be well on our way to under-
standing how to minimize wasted energy in many processes. Inefficiencies are addressed by the
concept of entropy.
Entropy provides a measure of the disorder of a system. As we will see, increased “disorder of
the universe” leads to reduced capability for performing useful work. This is the second law of ther-
modynamics. Conceptually, it seems reasonable, but how can we define “disorder” mathemati-
cally? That is where Boltzmann showed the way:
S = klnW
where S is the entropy, W is the number of ways of arranging the molecules given a specific set of
independent variables, like T and V; k is known as Boltzmann’s constant.
For example, there are more ways of arranging your socks around the entire room than in a
drawer, basically because the volume of the room is larger than that of the drawer. We will see that
ΔS = Nkln(V2/V1) in this situation, where N is the number of socks and Nk = nR, where n is the
number of moles, V is the volume, and R is the gas constant. In Chapter 1, we wrote Uig = 1.5NkT
without thinking much about who Boltzmann was or how his constant became so fundamental to
the molecular perspective. This connection between the molecular and macroscopic scales was
Boltzmann’s major contribution.
129
130 Unit I First and Second Laws
Chapter Objectives: You Should Be Able to...

1. Explain entropy changes in words and with numbers at the microscopic and macroscopic
levels. Typical explanations involve turbines, pumps, heat exchangers, mixers, and power
cycles.
2. Simplify the complete entropy balance to its most appropriate form for a given situation
and solve for the productivity of a reversible process.
3. Sketch and interpret T-S, T-V, H-S, and P-H diagrams for typical processes.
4. Use inlet and outlet conditions and efficiency to determine work associated with turbines/
compressors.
5. Determine optimum work interactions for reversible processes as benchmarks for real sys-
tems.
6. Sketch and interpret T-S, T-V, H-S, and P-H diagrams for typical processes.
4.1 THE CONCEPT OF ENTROPY

Chapters 2 and 3 showed the importance of irreversibility when it comes to efficient energy trans-
formations. We noted that prospective work energy was generally dissipated into thermal energy
(stirring) when processes were conducted irreversibly. If we only had an “irreversibility meter,” we
could measure the irreversibility of a particular process and design it accordingly. Alternatively, we
could be given the efficiency of a process relative to a reversible process and infer the magnitude of
the irreversibility from that. For example, experience might show that the efficiency of a typical
1000 kW turbine is 85%. Then, characterizing the actual turbine would be simple after solving for
the reversible turbine (100% efficient).
In our initial encounters, entropy generation provides this measure of irreversibility. Upon
studying entropy further, however, we begin to appreciate its broader implications. These broader
implications are especially important in the study of multicomponent equilibrium processes, as dis-
cussed in Chapters 8–16. In Chapters 5–7, we learn to appreciate the benefits of entropy being a
state property. Since its value is path independent, we can envision various ways of computing it,
selecting the path that is most convenient in a particular situation.
Entropy may be contemplated microscopically and macroscopically. The microscopic perspec-

! Entropy is a tive favors the intuitive connection between entropy and “disorder.” The macroscopic perspective
useful property for favors the empirical approach of performing systematic experiments, searching for a unifying con-
determining maxi-
mum/minimum
cept like entropy. Entropy was initially conceived macroscopically, in the context of steam engine
work. design. Specifically, the term “entropy” was coined by Rudolf Clausius from the Greek for trans-
formation.1 To offer students connections with the effect of volume (for gases) and temperature,
Rudolf Julius Eman-
uel Clausius (1822–
this text begins with the microscopic perspective, contemplating the detailed meaning of “disorder”
1888), was a Ger- and then demonstrating that the macroscopic definition is consistent.
man physicist and
mathematician To appreciate the distinction between the two perspectives on entropy, it is helpful to define the
credited with formu-
both perspectives first. The macroscopic definition is especially convenient for solving problems
lating the macro-
scopic form of process problems, but the connection between this definition and disorder is not immediately
entropy to interpret apparent.
the Carnot cycle
and developed the
second law of
thermodynamics.
1. Denbigh, K. 1971. The Principles of Chemical Equilibrium. 3rd ed. New York: Cambridge University Press, p.33.
Section 4.1 The Concept of Entropy 131
Macroscopic definition—Intensive entropy is a state property of the system. For a differential

change in state of a closed simple system (no internal temperature gradients or composition gradients
and no internal rigid, adiabatic, or impermeable walls),2 the differential entropy change of the sys-
tem is equal to the heat absorbed by the system along a reversible path divided by the absolute tem-
perature of the system at the surface where heat is transferred.
dQ rev
dS ≡ -------------- 4.1
T sys
where dS is the entropy change of the system. We will later show that this definition is consistent
with the microscopic definition.
Microscopic definition—Entropy is a measure of the molecular disorder of the system. Its

value is related to the number of microscopic states available at a particular macroscopic state. Spe-
cifically, for a system of fixed energy and number of particles, N,
p2
S i ≡ k ln ( p i ) or ΔS ≡ k ln  ----- 4.2
 p 1
where pi is the number of microstates in the ith macrostate, k = R/NA. We define microstates and mac-
rostates in the next section.
The microscopic perspective is directly useful for understanding how entropy changes with
volume (for a gas), temperature, and mixing. It simply states that disorder increases when the num-
ber of possible arrangements increases, like the socks and drawers mentioned in the introduction.
Similarly, molecules redistribute themselves when a valve is opened until the pressures have equil-
ibrated. From the microscopic approach, entropy is a specific mathematical relation related to the
number of possible arrangements of the molecule. Boltzmann showed that this microscopic defini-
tion is entirely consistent with the macroscopic property inferred by Rudolf Clausius. We will dem-
onstrate how the approaches are equivalent.
Entropy is a difficult concept to understand, mainly because its influence on
physical situations is subtle, forcing us to rely heavily on the mathematical defi-
nition. We have ways to try to make some physical connection with entropy, and
we will discuss these to give you every opportunity to develop a sense of how
entropy changes. Ultimately, you must reassure yourself that entropy is defined
mathematically, and like enthalpy, can be used to solve problems even though our
physical connection with the property is occasionally less than satisfying.
In Section 4.2, the microscopic definition of entropy is discussed. On the microscopic scale, S ! The micro-
is influenced primarily by spatial arrangements (affected by volume and mixing), and energetic scopic approach
to entropy is dis-
arrangements (occupation) of energy levels (affected by temperature). We clarify the meaning of cussed first, then
the microscopic definition by analyzing spatial distributions of molecules. To make the connection the macroscopic ap-
between entropy and temperature, we outline how the principles of volumetric distributions extend proach is discussed.
to energetic distributions. In Section 4.3, we introduce the macroscopic definition of entropy and
conclude with the second law of thermodynamics.
The second law is formulated mathematically as the entropy balance in Section 4.4. In this sec-
tion we demonstrate how heat can be converted into work (as in an electrical power plant). How-
2. A simple system is not acted on by external force fields or inertial forces.

ever, the maximum thermal efficiency of the conversion of heat into work is less than 100%, as
indicated by the Carnot efficiency. The thermal efficiency can be easily derived using entropy bal-
ances. This simple but fundamental limitation on the conversion of heat into work has a profound
impact on energy engineering. Section 4.5 is a brief section, but makes the key point that pieces of
an overall process can be reversible, even while the overall process is irreversible.
In Section 4.6 we simplify the entropy balance for common process equipment, and then use
the remaining sections to demonstrate applications of system efficiency with the entropy balance.
Overall, this chapter provides an understanding of entropy which is essential for Chapter 5 where
entropy must be used routinely for process calculations.
4.2 THE MICROSCOPIC VIEW OF ENTROPY

Probability theory is nothing but common sense reduced to calculation.
LaPlace
To begin, we must recognize that the disorder of a system can change in two ways. First, disorder
! Configurational occurs due to the physical arrangement (distribution) of atoms, and we represent this with the con-
entropy is associ- figurational entropy.3 There is also a distribution of kinetic energies of the particles, and we repre-
ated with spatial dis- sent this with the thermal entropy. For an example of kinetic energy distributions, consider that a
tribution. Thermal
entropy is associ- system of two particles, one with a kinetic energy of 3 units and the other of 1 unit, is microscopi-
ated with kinetic en- cally distinct from the same system when they both have 2 units of kinetic energy, even when the
ergy distribution. configurational arrangement of atoms is the same. This second type of entropy is more difficult to
implement on the microscopic scale, so we focus on the configurational entropy in this section.4
Entropy and Spatial Distributions: Configurational Entropy

Given N molecules and M boxes, how can these molecules be distributed among the boxes? Is one
distribution more likely than another? Consideration of these issues will clarify what is meant by
microstates and macrostates and how entropy is related to disorder. Our consideration will focus on
the case of distributing particles between two boxes.
First, let us suppose that we distribute N = 2 ideal gas5 molecules in M = 2 boxes, and let us
suppose that the molecules are labeled so that we can identify which molecule is in a particular box.
We can distribute the labeled molecules in four ways, as shown in Fig. 4.1. These arrangements are
! Distinguishabil- called microstates because the molecules are labeled. For two molecules and two boxes, there are
ity of particles is as- four possible microstates. However, a macroscopic perspective makes no distinction between
sociated with which molecule is in which box. The only macroscopic characteristic that is important is how many
microstates. Indis-
tinguishability is particles are in a box, rather than which particle is in a certain box. For macrostates, we just need to
associated with keep track of how many particles are in a given box, not which particles are in a given box. It might
macrostates. help to think about connecting pressure gauges to the boxes. The pressure gauge could distinguish
3. The term “configurational” is occasionally used in different contexts. We apply the term in the context of Denbigh, K.
1981. The Principles of Chemical Equilibrium, 4th ed. Cambridge University Press, pp. 54–55. Technically, the configura-
tional entropy includes both the combinatorial contribution discussed here for ideal gases, and the entropy departure func-
tion discussed in Unit II. Note that configurational energy is equivalent to the energy departure function of Chapter 7
because the change in energy of spatially rearranging ideal gas particles is zero.
4. The distinctions between these types of entropy are discussed in more detail by Denbigh, K. 1981. The Principles of
Chemical Equilibrium, 4th ed. Cambridge University Press, pg. 353.
5. Ideal gases are non-interacting. Non-interacting particles are oblivious to the presence of other particles and the energy is
independent of the interparticle separations. In other words, potential energies are ignored.
Section 4.2 The Microscopic View of Entropy 133
Box A Box B Box A Box B Box A Box B Box A Box B

1 1 2 1 2
2 2 1
Microstate α Microstate β Microstate γ Microstate δ

Figure 4.1 Illustration of configurational arrangements of two molecules in two boxes, showing the
microstates. Not that β and γ would have the same macroscopic value of pressure.
between zero, one, and two particles in a box, but could not distinguish which particles are present.
Therefore, microstates α and δ are different macrostates because the distribution of particles is dif-
ferent; however, microstates β and γ give the same macrostate. Thus, from our four microstates, we
have only three macrostates.
To find out which arrangement of particles is most likely, we apply the “principle of equal a
priori probabilities.” This “principle” states that all microstates of a given energy are equally likely.
Since all of the states we are considering for our non-interacting particles are at the same energy,
they are all equally likely.6 From a practical standpoint, we are interested in which macrostate is
most likely. The probability of a macrostate is found by dividing the number of microstates in the
given macrostate by the total number of microstates in all macrostates as shown in Table 4.1. For
our example, the probability of the first macrostate is 1/4 = 0.25. The probability of the evenly dis-
tributed state is 2/4 = 0.5. That is, one-third of the macrostates possess 50% of the probability. The
“most probable distribution” is the evenly distributed case.
Table 4.1 Illustration of Macrostates for Two Particles and Two Boxes
Macrostate Probability
# of microstates of
# in box A # in box B macrostate
0 2 1 0.25
1 1 2 0.55
2 0 1 0.25
What happens when we consider more particles? It turns out that the total number of
microstates for N particles in M boxes is MN, so the counting gets tedious. For five particles in two
boxes, the calculations are still manageable. There will be two microstates where all the particles
are in one box or the other. Let us consider the case of one particle in box A and four particles in
box B. Recall that the macrostates are identified by the number of particles in a given box, not by
which particles are in which box. Therefore, the five microstates for this macrostate appear as given
in Table 4.2(a).
6. Note that the number of particles and the energy are constant throughout the discussion presented here and the volume is
specified at each stage. The constant energy for non-interacting particles means that the temperature will be constant; only
the pressure will be reduced at larger volumes because it takes the molecules longer to get around the box and collide with a
particular wall. We can think of this as an N, V, U perspective, and we will demonstrate that entropy is maximized at equilib-
rium within this perspective, but some other quantity might characterize equilibrium if we held other quantities constant.
Table 4.2 Microstates for the Second and Third Macrostates for Five Particles Distributed in Two Boxes
(a) One particle in Box A (b) Two particles in Box A

Box A Box B Box A Box B Box A Box B
1 2,3,4,5 1,2 3,4,5 2,4 1,3,5
2 1,3,4,5 1,3 2,4,5 2,5 1,3,4
3 1,2,4,5 1,4 2,3,5 3,4 1,2,5
4 1,2,3,5 1,5 2,3,4 3,5 1,2,4
5 1,2,3,4 2,3 1,4,5 4,5 1,2,3
The counting of microstates for putting two particles in box A and three in box B is slightly
more tedious, and is shown in Table 4.2(b). It turns out that there are 10 microstates in this mac-
rostate. The distributions for (three particles in A) + (two in B) and for (four in A) + (one in B) are
like the distributions (two in A) + (three in B), and (one in A) + (four in B), respectively. These
three cases are sufficient to determine the overall probabilities. There are M N = 25 = 32 microstates
total summarized in the table below.
Macrostate Probability of
# Microstates
Box A Box B Macrostate
0 5 1 0.0313
1 4 5 0.1563
2 3 10 0.3125
3 2 10 0.3125
4 1 5 0.1563
5 0 1 0.0313
Note now that one-third of the macrostates (two out of six) possess 62.5% of the microstates.
Thus, the distribution is now more peaked toward the most evenly distributed states than it was for
two particles where one-third of the macrostates possessed 50% of the microstates. This is one of the
most important aspects of the microscopic approach. As the number of particles increases, it won’t
be long before 99% of the microstates are in one-third of the macrostates. The trend will continue,
and increasing the number of particles further will quickly yield 99% of the microstates in that one-
tenth of the macrostates. In the limit as N→∞ (the “thermodynamic limit”), virtually all of the
microstates are in just a few of the most evenly distributed macrostates, even though the system has
! With a large a very slight finite possibility that it can be found in a less evenly distributed state. Based on the
number of particles, discussion, and considering the microscopic definition of entropy (Eqn. 4.2), entropy is maximized
the most evenly dis-
tributed configura- at equilibrium for a system of fixed energy and total volume.7
tional state is most
probable, and the
probability of any
other state is small.
7. In an isolated system at constant (U, V), entropy will be generated as equilibrium is approached; S will increase and will
be maximized at equilibrium. If the system is closed but not isolated, the property which is minimized is determined by the
property which is a natural function of the controlled variables: H is minimized for constant (S,P); A for constant (T,V); G
for constant (T,P). A and G will be introduced in future chapters.
Generalized Microstate Formulas

To extend the procedure for counting microstates to large values of N (~1023), we cannot imagine
listing all the possibilities and counting them up. It would require 40 years to simply count to 109 if
we did nothing but count night and day. We must systematically analyze the probabilities as we
consider configurations and develop model equations describing the process.
How do we determine the number of microstates for a given macrostate for large N? For the
first step in the process, it is fairly obvious that there are N ways of moving one particle to box B,
i.e., 1 came first, or 2 came first, and so on, which is what we did to create Table 4.2(a). However,
counting gets more complicated when we have two particles in a box. Since there are N ways of
moving the first particle to box B, and there are (N − 1) particles left, we begin with the same logic
for the (N − 1) remaining particles. For example, with five particles, there would then be five ways ! Factorials are a
of placing the first particle, then four ways of placing the second particle for a total of 20 possible quick tool for count-
ing arrangements.
ways of putting two particles in box B. One way of writing this would be 5·4, which is equivalent to
(5·4·3·2·1)/(3·2·1), which can be generalized to N!/(N − m)!, where m is the number of particles we
have placed in the first box.8 (N! is read “N factorial,” and calculated as N·(N − 1)·(N − 2)......·2·1).
Our formula gives 20 ways, but Table 4.2(b) shows only 10 ways. What are we missing? Answer:
When we count this way, we are implicitly double counting some microstates. Note in Table 4.2(b)
that although there are two ways that we could put the first particle in box B, the order in which we
place them does not matter when we count microstates. Therefore, using N!/(N − m)! implicitly dis-
tinguishes between the order in which particles are placed. For counting microstates, the history of
how a particular microstate was achieved does not interest us. Therefore, we say there are only 10
distinguishable microstates.
It turns out that it is fairly simple to correct for this overcounting. For two particles in a box,
they could have been placed in the order 1-2, or in the order 2-1, which gives two possibilities. For
three particles, they could have been placed 1-2-3, 1-3-2, 2-1-3, 2-3-1, 3-1-2, 3-2-1, for six possibil-
ities. For m particles in a box, without correction of the formula, we overcount by m!. Therefore,
we modify the above formula by dividing by m! to correct for overcounting. Finally, the number of
microstates for arranging N particles in two boxes, with m particles in one of the boxes, is:9
N j!
p j = -------------------------------- 4.3
m j! ( N j – m j )!
The general formula for M boxes is:10
N j!
p j = -------------------- 4.4 ! General for-
mula for number of
M
microstates for N
∏ mij ! particles in M
boxes.
i=1
8. In statistics, this is called the number of permutations.

9. The formula for the particles in boxes is an example of a binomial coefficient, fundamental in the study of probability and
statistics. Detailed development of the binomial distribution and the issue of indistinguishability can be found in any text-
book or handbook on the subject.
10. In statistics this is called the number of combinations.It is also known as the multinomial coefficient.
mij is the number of particles in the ith box at the jth macrostate. We will not derive this general for-
mula, but it is a straightforward extension of the formula for two boxes which was derived above.
Therefore, with 10 particles, and three in the first box, two in the second box and five in the third
box, we have 10!/(3!2!5!) = 3,628,800/(6·2·120) = 2520 microstates for this macrostate.
Recall the microscopic definition of entropy given by Eqn. 4.2. Let us use it to calculate the
entropy change for an ideal gas due to an isothermal change in volume. The statistics we have just
derived will apply since an ideal gas consists of non-interacting particles whose energy is indepen-
dent of their nearest neighbors. During an expansion like that described, the energy is constant
because the system is isolated. Therefore, the temperature is also constant because dU = CV dT for
an ideal gas.
Entropy and Isothermal Volume/Pressure Change for

Ideal Gases
Suppose an insulated container, partitioned into two equal volumes, contains N molecules of an
ideal gas in one section and no molecules in the other. When the partition is withdrawn, the mole-
cules quickly distribute themselves uniformly throughout the total volume. How is the entropy
affected? Let subscript 1 denote the initial state and subscript 2 denote the final state. Here we take
for granted that the final state will be evenly distributed.
We can develop an answer by applying Eqn. 4.4, and noting that 0! = 1:
2
N! ⁄ [ ( N ⁄ 2 )! ]
ln ( p 2 ⁄ p 1 ) = ln  -----------------------------------
N! - = 1 ; N!
p 1 = ---------- p 2 = ------------------------------------ ;
N!0! ( N ⁄ 2 )! ( N ⁄ 2 )!  1 
N 2
Substituting into Eqn. 4.2, and recognizing ln  ---- ! = 2 ln  ---- ! ,
N
 2  2
ΔS = S 2 – S 1 = k ln ( p 2 ⁄ p 1 ) = k { ln ( N! ) – 2 ln [ ( N ⁄ 2 )! ] }
Stirling’s approximation may be used for ln(N!) when N > 100,
! Stirling’s ln ( N! ) ≈ N ln ( N ) – N 4.5
approximation.
The approximation is a mathematical simplification, and not, in itself, related to thermodynamics.
 ΔS = k [ N ln ( N ) – N – 2 ( N ⁄ 2 ) ln ( N ⁄ 2 ) + 2 ( N ⁄ 2 ) ]
= k [ N ln ( N ) – N – N ln ( N ) + N ln ( 2 ) + N ]
= kN ln ( 2 )  ΔS = nR ln ( 2 )
! Therefore, entropy of the system has increased by a factor of ln(2) when the volume has doubled at
Entropy of a
constant tempera- constant T. Suppose the box initially with particles is three times as large as the empty box. In this
ture system in- case the increase in volume will be 33%. Then what is the entropy change? The trick is to imagine
creases when four equal size boxes, with three equally filled at the beginning.
volume increases.
N! N!
p 1 = ------------------------------ ; p 2 = -------------------------
3 4
[ ( N ⁄ 3 )! ] 0! [ ( N ⁄ 4 )! ]
A similar application of Stirling’s approximation gives,

3
 [ ( N ⁄ 3 )! ] 0!11   
ΔS = k ln  ------------------------- ⋅ -------------------------------------  = – k  N ln  ---- – N – N ln  ---- + N  = nR ln  ---
N! N N 4
4 N!  4  3  3
 [ ( N ⁄ 4 )! ]   
We may generalize the result by noting the pattern with this result and the previous result,
V
( ΔS ) T = R ln ----- (ig) 4.6
i
V
where the subscript T indicates that this equation holds at constant T. For an isothermal ideal gas, ! Formulas for
we also may express this in terms of pressure by substituting V = RT/P in Eqn. 4.6 isothermal entropy
changes of an ideal
gas.
P
( ΔS ) T = – R ln ----- (ig) 4.7
i
P
Therefore, the entropy decreases when the pressure increases isothermally. Likewise, the
entropy decreases when the volume decreases isothermally. These concepts are extremely impor-
tant in developing an understanding of entropy, but by themselves, are not directly helpful in the
initial objective of this chapter—that of determining inefficiencies and maximum work. The fol-
lowing example provides an introduction to how these conceptual points relate to our practical
objectives.
Example 4.1 Entropy change and “lost work” in a gas expansion
An isothermal ideal gas expansion produces maximum work if carried out reversibly and less
work if friction or other losses are present. One way of generating “other losses” is if the force of
the gas on the piston is not balanced with the opposing force during the expansion, as shown in
part (b) below. Consider a piston/cylinder containing one mole of nitrogen at 5 bars and 300 K is
expanded isothermally to 1 bar.
(a) Suppose that the expansion is reversible. How much work could be obtained and how much
heat is transferred? What is the entropy change of the gas?
(b) Suppose the isothermal expansion is carried out irreversibly by removing a piston stop and
expanding against the atmosphere at 1 bar. Suppose that heat transfer is provided to permit this to
occur isothermally. How much work is done by the gas and how much heat is transferred? What
is the entropy change of the gas? How much work is lost compared to a reversible isothermal pro-
cess and what percent of the reversible work is obtained (the efficiency)?
Solution:
Basis: 1 mole, closed unsteady-state system.
(a) The energy balance for the piston/cylinder is ΔU = Q + W EC = 0 because the gas is iso-
thermal and ideal. dWEC = −PdV = −(nRT/V)dV; WEC = −nRTln(V2/V1) = −nRTln(P1/P2) =
−(1)8.314(300)ln(5) = −4014J. By the energy balance Q = 4014J .
The entropy change is by Eqn. 4.7, ΔS = –nRln(P2/P1) = –(1)8.314ln(1/5) = 13.38 J/K.
Example 4.1 Entropy change and “lost work” in a gas expansion

(Continued)
(b) The energy balance does not depend on whether the work is reversible and is the same.
Taking the atmosphere as the system, the work is WEC,atm = –Patm(V2,atm–V1,atm) =
–WEC = –Patm(V1–V2) = Patm(nRT/P2–nRT/P1) = nRT(Patm/P2–Patm/P1) =>
WEC = nRT(Patm/P1–Patm/P2) = (1)8.314(300)(1/5–1) = –1995J, Q = 1995J .
The entropy change depends on only the state change and this is the same as (a), 13.38 J/K.
The amount of lost work is Wlost = 4014 – 1995 = 2019J, the percent of reversible work
obtained (efficiency) is 1995/4014 · 100% = 49.7%.
An important point is suggested by Example 4.1, even though the example is limited to ideal gas
constraints. We saw that the isothermal entropy change for the gas was the same for the reversible
and irreversible changes because the gas state change was the same. Though Eqn. 4.7 is limited to
ideal gases, the relation between entropy changes and state changes is generalizable as we prove
later. We will show later that case (b) always generates more entropy.
Entropy of Mixing for Ideal Gases

Mixing is another important process to which we may apply the statistics that we have developed.
Suppose that one mole of pure oxygen vapor and three moles of pure nitrogen vapor at the same
temperature and pressure are brought into intimate contact and held in this fashion until the nitro-
gen and oxygen have completely mixed. The resultant vapor is a uniform, random mixture of nitro-
gen and oxygen molecules. Let us determine the entropy change associated with this mixing
process, assuming ideal-gas behavior.
Since the T i and Pi of both ideal gases are the same, V iN2 = 3ViO2 and Vitot = 4ViO2. Ideal gas
molecules are point masses, so the presence of O2 in the N2 does not affect anything as long as the
pressure is constant. The main effect is that the O2 now has a larger volume to access and so does
N2. The component contributions of entropy change versus volume change can be simply added.
Entropy change for O2:
ΔS = n O2 R ln ( 4 ) = n tot R [ – x O2 ln ( 0.25 ) ] = n tot R [ – x O2 ln ( x O2 ) ]
Entropy change for N2:
ΔS = n N2 R ln  --- = n tot R [ – x N2 ln ( 0.75 ) ] = n tot R [ – x N2 ln ( x N2 ) ]

4
 3
Entropy change for total fluid:
ΔS = – n tot R [ x O2 ln ( x O2 ) + x N2 ln ( x N2 ) ] = – 4R ( – 0.562 ) = 18.7 J/K
! Ideal entropy
of mixing.
ΔS mix
is = – R
 xi ln xi In general, ideal mixing. 4.8
i
This is an important result as it gives the entropy change of mixing for non-interacting parti-
cles. Remarkably, it is also a reasonable approximation for ideal solutions where energy and
total volume do not change on mixing. This equation provides the underpinning for much of the
discussion of mixtures and phase equilibrium in Unit III.
The entropy of a mixed ideal gas or an ideal solution, here both denoted with a superscript “is:”
S
is
=  ni Si + ΔSmix =  ni Si – R  ni ln xi or S
is
=  xi Si – R  xi ln xi 4.9
i i i i i
Note that these equations apply to ideal gases if we substitute y for x. In this section we have
shown that a system of ideal gas molecules at equilibrium is most likely to be found in the most
randomized (distributed) configuration because this is the macrostate with the largest fraction of
microstates. In other words, the entropy of a state is maximized at equilibrium for a system of fixed
U, V, and N.
But how can temperature be related to disorder? We consider this issue in the next subsection.
Entropy and Temperature Change: Thermal Entropy

One key to understanding the connection between thermal entropy and disorder is the appreciation
that energy is quantized. Thus, there are discrete energy levels in which particles may be arranged.
These energy levels are analogous to the boxes in the spatial distribution problem. The effect of
increasing the temperature is to increase the energy of the molecules and make higher energy levels
accessible.
To see how this affects the entropy, consider a system of three molecules and three energy lev-
els εo, ε1 = 2εo, ε3 = 3εo. Suppose we are at a low temperature and the total energy is U = 3εo. The
only way this can be achieved is by putting all three particles in the lowest energy level. The other
energy levels are not accessible, and S = So. Now consider raising the temperature to give the sys-
tem U = 4εo. One macrostate is possible (one molecule in ε1 and two in εo), but there are now three
microstates, ΔS = kln(3). Can you show when U = 6εo that the macrostate with one particle in each
level results in ΔS = kln(6)? Real systems are much larger and the molecules are more complex, but
the same qualitative behavior is exhibited: increasing T increases the accessible energy levels
which increases the microstates, increasing entropy.
We can advance our understanding of thermal effects on entropy by contemplating the Einstein Albert Einstein
solid.11 Albert Einstein’s (1907) proposal was that a solid could be treated as a large number of (1879 – 1955) was a
German-born
identical vibrating monatomic sites, modeling the potential energies as springs that follow Hooke’s physicist. He
law. The quantum mechanical analog to the energy balance is known as Shrödinger’s equation, contributed to an
which relates the momentum (kinetic energy) and potential energy. An exact solution is possible understanding of
quantum behavior
only for equally spaced energy levels, known as quantum levels. The equally spaced quantized and the general
states for each oscillator are separated by hf where h is Planck’s constant and f is the frequency of theory of relativity.
the oscillator. Thus, the system is described as a system of harmonic oscillators. Assuming that He was awarded
the 1921 Nobel
each oscillator and each dimension (x,y,z) is independent, we can develop an expression for the Prize in physics.
internal energy and the heat capacity.
The Einstein solid model was one of the earliest and most convincing demonstrations of the
limitations of classical mechanics. It serves today as a simple illustration of the manner in which
quantum mechanics and statistical mechanics lead to consistent and experimentally verifiable
descriptions of thermodynamic properties. The assumptions of the Einstein solid model are as fol-
lows:
11. Moore, Schroeder, 1997. Am. J. Phys. 65:26–36.

• The total energy in a solid is the sum of M harmonic oscillator energies where M/3 is the
number of atoms because the atoms oscillate independently in three dimensions. Since
the energy of each oscillator is quantized, we can say that the total internal energy is
U = qMεq + Mεq/2 for M/3 atoms 4.10

where εq is the (constant) energy step for each quantum level, and qM gives the total
quantum multiplier for all oscillator quantum energies added. The term Mεq/2 represents
the ground state energy that oscillators have in the lowest energy level. It is often conve-
nient to relate the energy to the average quantum multiplier,
<qM> = qM/M = U/Mεq – 1/2 4.11

• Each oscillator in each dimension is independent, so we can allocate integer multiples of
εq to any oscillator as long as the total sum of multipliers is qM. Each independent speci-
fication represents a microstate. For M = 3 oscillators, (3,1,1) specifies three units of
energy in the first oscillator and one unit in each of the other two for a total of qM = 5,
U = 5εq + 3εq/2.
• Raising the magnitude of qM (by adding heat to raise T) makes more microstates accessi-
ble, increasing the entropy.
For qM=3 units of energy distributed in an Einstein solid with M=4 oscillators, below is the
detailed listing of the possible distributions of the energy, a total of 20 different distributions for
three units of energy among four oscillators (a “multiplicity” of 20).
State 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Osc1 3 0 0 0 2 2 2 1 1 1 0 0 0 0 0 0 0 1 1 1
Osc2 0 3 0 0 1 0 0 2 0 0 2 2 1 1 0 0 1 0 1 1
Osc3 0 0 3 0 0 1 0 0 2 0 1 0 2 0 2 1 1 1 0 1
Osc4 0 0 0 3 0 0 1 0 0 2 0 1 0 2 1 2 1 1 1 0
If we are trying to develop a description of a real solid with Avogadro's number of oscillators,
enumeration is clearly impractical. Fortunately, mathematical expressions for the multiplicity make
the task manageable. Callen12 gives the general formula for the number of microstates as pi =
(qMi+Mi–1)!/[qMi!(Mi–1)!]. There is a clever way to understand this formula. Instead of distributing
qMi quanta among M oscillator “boxes,” consider that there are Mi – 1 “partitions” between oscilla-
tor “boxes.” In the table above, there are four oscillators, but there are three row boundaries. Con-
sider that the quanta can be redistributed by all the permutations of the particles and boundaries
(qMi+Mi–1)!. However, the permutations overcount in that the qMi are indistinguishable, so we
divide by qMi!, and that the (Mi–1) boundaries are indistinguishable, so we divide by (Mi–1)!. To
apply the formula for qM=2, M=2:
Instance Osc1 Osc2
1 2 0
2 0 2
3 1 1
pi = (2+2–1)!/[2!(1!)] = 3!/2! = 3. Check.
12. Callen, H.B. 1985. Thermodynamics and an Introduction to Thermostatistics, 2ed, Indianapolis IN: Wiley, p.333.
For the case with qM = 3 and M = 4, pi = (3+4–1)!/[3!(3!)] = 20, as enumerated above.
Example 4.2 Stirling’s approximation in the Einstein solid

(a) Show that Callen’s formula is consistent with enumeration for:
(1) qM = 3, M = 3; (2) qM = 4, M = 3
(b) Use the general formula to develop an expression for S = S(qM,M) when M > 100. Express
the answer in terms of the average quantum multiplier, <qM>.
(c) Plot S/Mk versus <qM>. What does this indicate about entropy changes when heat is added?
Solution:
(a) (1): (3,0,0),(0,3,0),(0,0,3),(2,1,0),(2,0,1),(1,2,0),(1,0,2),(0,2,1),(0,1,2),(1,1,1) = 10. Check.
(2): (4,0,0), (0,4,0), (0,0,4), (3,1,0), (3,0,1), (1,3,0), (1,0,3), (0,3,1), (0,1,3), (2,1,1),
(1,2,1), (1,1,2), (2,0,2), (2,2,0), (0,2,2) = 15. Check.
(b) Si = k ln(pi) = k { ln[(qMi+Mi–1)!] – ln[qMi!(Mi–1)!] }. Applying Stirling’s approximation,
S/k = [(qM+M–1)ln(qM+M–1)–(qM+M–1)] – qMlnqM + qM – (M–1)ln(M–1) + M–1 =

S/Mk = (qM/M)ln[(qM+M–1)/qM] + [(M–1)/M]ln[(qM+M–1)/(M–1)]
S/Mk = <qM>ln(1+1/<qM>) + ln(<qM>+1)
(c) Fig. 4.2 shows that S increases with <qM> = qM/M (=U/Mεq – ½). When T increases, U will
increase, meaning that <qM> and S increase. It would be nice to relate the change in entropy
quantitatively to the change in temperature, but a complete analysis of the entire temperature
range requires advanced derivative manipulations that distracts from the main concepts at this
stage. We return to this problem in Chapter 6.
You should notice that we represented the interactions of the monatomic sites as if they were
connected by Hooke’s law springs in the solid phase. They are not rigorously connected this way,
but the simple model approximates the behavior of two interacting molecules in a potential energy
8
7
6
5
S/Mk
4
3
2
1
0
-4 -2 0 2 4
log10<qM>
Figure 4.2 Entropy of the Einstein solid with increasing energy and T as explained in Example 4.2.
well. If the spring analogy were exact, the potential energy well would be a parabola (thus a har-
monic oscillator). Look back at the Lennard-Jones potential in Chapter 1 and you can see that the
shape is a good approximation if the atoms do not vibrate too far from the minimum in the well.
The Einstein model gives qualitatively the right behavior, but the Debye model that followed in
1912 is more accurate because it represents collective waves moving through the solid. We omit
discussion of the Debye model because our objectives are met with the Einstein model.13 We
briefly extend the concept of the Einstein model in Chapter 6 where we develop more powerful
methods for manipulation of derivatives.
In the present day, the subtle relations between entropy and molecular distributions are com-
plex but approachable. Imagine how difficult gaining this understanding must have been for Boltz-
mann in 1880, before the advent of quantum mechanics. Many scientists at the time refused even to
accept the existence of molecules. Trying to explain to people the nature and significance of his dis-
coveries must have been extremely frustrating. What we know for sure is that Boltzmann drowned
himself in 1903. Try not to take your frustrations with entropy quite so seriously.
Test Yourself
1. Does molar entropy increase, decrease, or stay about the same for an ideal gas if: (a) volume
increases isothermally?; (b) pressure increases isothermally?; (c) temperature increases iso-
barically?; (d) the gas at the vapor pressure condenses?; (e) two pure gas species are mixed?
2. Does molar entropy increase, decrease, or stay about the same for a liquid if: (a) tempera-
ture increases isobarically?; (b) pressure increases isothermally?; (c) the liquid evaporates
at the vapor pressure?; (d) two pure liquid species are mixed?
4.3 THE MACROSCOPIC VIEW OF ENTROPY

In the introduction to this chapter, we alluded to the relation between entropy and maximum pro-
cess efficiency. We have shown that entropy changes with volume (pressure) and temperature. How
can we use entropy to help us determine maximum work output or minimum work input? The
answer is best summarized by a series of statements. These statements refer to the entropy of the
universe. This does not mean that we imagine measuring entropy all over the universe. It simply
means that entropy may decrease in one part of a system but then it must increase at least as much
in another part of a system. In assessing the reversibility of the overall system, we must sum all
changes for each process in the overall system and its surroundings. This is the relevant part of the
universe for our purposes.
Molar or specific entropy is a state property which will assist us in the following ways.
1. Irreversible processes will result in an increase in entropy of the universe. (Irreversible pro-
cesses will result in entropy generation.) Irreversible processes result in loss of capability
for performing work.
2. Reversible processes result in no increase in entropy of the universe. (Reversible processes
result in zero entropy generation. This principle will be useful for calculation of maximum
work output or minimum work input for a process.)
3. Proposed processes which would result in a decrease of entropy of the universe are impos-
sible. (Impossible processes result in negative entropy generation.)
13. The Debye model is described by McQuarrie, D.A. 1976. Statistical Mechanics. Harper and Row.
Section 4.3 The Macroscopic View of Entropy 143
These three principles are summarized in the second law of thermodynamics: Reversible processes
! The entropy
and/or optimum work interactions occur without entropy generation, and irreversible processes balance is the
result in entropy generation. The microscopic descriptions in the previous section teach us very second law
effectively about the relation between entropy and disorder, but it is not fair to say that any increase of thermo-
dynamics.
in volume results in a loss of potentially useful work when the entropy of the system increases.
(Note that it is the entropy change of the universe that determines irreversibility, not the entropy
change of the system.) After all, the only way of obtaining any expansion/contraction work is by a
change in volume. To understand the relation between lost work and volume change, we must
appreciate the meaning of reversibility, and what types of phenomena are associated with entropy
generation. We will explore these concepts in the next sections.
Entropy Definition (Macroscopic)

Let us define the differential change in entropy of a closed simple system by the following equation:
dQ rev
dS ≡ -------------- 4.12
T sys
For a change in states, both sides of Eqn. 4.12 may be integrated,
state 2
dQ rev
ΔS =  --------------
T sys
4.13
state 1
where the following occurs:
1. The entropy change on the left-hand side of Eqn. 4.13 is dependent only on states 1 and 2
and not dependent on reversibility. However, to calculate the entropy change via the inte-
gral, the integral may be evaluated along any convenient reversible pathway between the
actual states.
2. Tsys is the temperature of the system boundary where heat is transferred. Only if the system
boundary temperature is constant along the pathway may this term be taken out of the inte-
gral sign.
A change in entropy is completely characterized for a pure single-phase fluid by any other two
state variables. It may be surprising that the integral is independent of the path since Q is a path- ! Entropy is a
dependent property. The key is to understand that the right-hand side integral is independent of the state property. For a
pure single-phase
path, as long as the path is reversible. Thus, a process between two states does not need to be fluid, specific en-
reversible to permit calculation of the entropy change, since we can evaluate it along any reversible tropy is character-
path of choice. If the actual path is reversible, then the actual heat transfer and pathway may be ized by two state
variables (e.g., T
used. If the process is irreversible, then any reversible path may be constructed for the calculation. and P ).
Look back at Example 4.1 and note that the entropy change for the isothermal process was cal-
culated by the microscopic formula. However, look at the process again from the perspective of
Eqn. 4.13 and subsequent statement 2. Because the process was isothermal, the entropy change can
be calculated ΔS = Q rev ⁄ T sys ; try it! Note that the irreversible process in that example exhibits
the same entropy change, calculated by the reversible pathway.
Now, look back at the integral of Eqn. 4.13 and consider an adiabatic, reversible process; the
process will be isentropic (constant entropy, ΔS = 0). Let us consider how the entropy can be used
as a state property to identify the final state along a reversible adiabatic process. Further, the prop-
erty does not depend on the limitations of the ideal gas law. The ideal gas law was convenient to
introduce the property. Consider the adiabatic reversible expansion of steam, a non-ideal gas. We
can read S values from the steam tables.
Example 4.3 Adiabatic, reversible expansion of steam

Steam is held at 450°C and 4.5 MPa in a piston/cylinder. The piston is adiabatically and revers-
ibly expanded to 2.0 MPa. What is the final temperature? How much reversible work can be
done?
Solution: The T, P are known in the initial state, and the value of S can be found in the steam
tables. Steam is not an ideal gas, but by Eqn. 4.12, the process is isentropic because it is revers-
ible and adiabatic. From the steam tables, the entropy at the initial state is 6.877 kJ/kgK. At 2
MPa, this entropy will be found between 300°C and 350°C. Interpolating,
6.877 – 6.7684
T = 300 + --------------------------------------- ( 350 – 300 ) = 300 + 0.572 ( 350 – 300 ) = 329°C
6.9583 – 6.7684
The P and Sf = Si are known in the final state and these two state properties can be used to find
all the other final state properties. The work is determined by the energy balance:
ΔU = Q + W EC . The initial value of U is 3005.8 kJ/kg. For the final state, interpolating U by
using Sf at Pf, U = 2773.2 + 0.572 ( 2860.5 – 2773.2 ) = 2823.1 kJ/kg , so
W EC = ( 2823.1 – 3005.8 ) = – 182.7 kJ/kg
Let us revisit the Carnot cycle of Section 3.1 in light of this new state property, entropy. The
Carnot cycle was developed with an ideal gas, but it is possible to prove that the cycle depends only
on the combination of two isothermal steps and two adiabatic steps, not the ideal gas as the working
fluid.14 Because the process is cyclic, the final state and initial state are identical, so the overall
entropy changes of the four steps must sum to zero, ΔS = 0. Because the reversible, adiabatic steps
are isentropic, ΔS = 0, the entropy change for the two isothermal steps must sum to zero. As we dis-
cussed above, for an isothermal step Eqn. 4.13 becomes ΔS = Qrev/T. Therefore, an analysis of the
Carnot cycle from the viewpoint of entropy is
QC
 ΔS = 0 = Q H Q C –TC
- + -------  -------- = ---------
------- - Carnot cycle 4.14
 TH TC  QH TH
This can be inserted into the formula for Carnot efficiency, Eqn. 3.6. Note that this relation is not
constrained to an ideal gas! In fact, there are only three constraints for this balance: The process is
cyclic; all heat is absorbed at TH; all heat is rejected at TC. Example 4.4 shows how the Carnot
cycle can be performed with steam including phase transformations.
14. Uffink, J. 2003. “Irreversibility and the Second Law of Thermodynamics,” Chapter 7, in Entropy, Greven, A., Keller, G.,
Warnecke, G. eds., Princeton, NJ: Princeton University Press.
Example 4.4 A Carnot cycle based on steam

Fig. 4.3 shows the path of a Carnot cycle operating on steam in a continuous cycle that parallel
the two isothermal steps and two adiabatic steps of Section 3.1. First, saturated liquid at 5 MPa
is boiled isothermally to saturated vapor in step (a→b). In step (b→c), steam is adiabatically and
reversibly expanded from saturated vapor at 5 MPa to 1 MPa. In (c→d), heat is isothermally
removed and the volume drops during condensation. Finally, in step (d→a), the steam is adiabat-
ically and reversibly compressed to 5 MPa and saturated liquid. (Hint: Challenge yourself to
solve the cycle without looking at the solution.).
(a) Compute W(a→b) and QH.

(b) Compute W(b→c).
(c) Compute W(d→a). (The last step in the cycle).
(d) Compute W(c→d) and QC. (The third step in the cycle).
(e) For the cycle, compute the thermal efficiency by ηθ = –Wnet/QH and compare to Carnot’s effi-
ciency, ηθ = (TH − TL)/TH.
T c.p.
a b
Liquid
d c Vapor
Two-phase Region
S
Figure 4.3 A T-S diagram illustrating a Carnot cycle based on steam.
Solution: The entropy change is zero for the expansion and compression steps because these
steps are adiabatic and reversible, as indicated by the vertical line segments in Fig. 4.3.
(a) E-balance: fixed P,T vaporization, QH = ΔU – WEC = (ΔU + PΔV) = ΔHvap = 1639.57 J/kg;
WEC(a→b) = PΔV = 5(0.0394 – 0.001286)*1000 = 191.1 J/kg.
(b) E-balance: isentropic, WEC(b→c) = ΔU; Ub = U(sat. vap., 5MPa) = 2596.98 kJ/kg;
S-balance: ΔS = 0; Sc = Sb = 5.9737 kJ/kg-K= qc(6.5850) + (1 − qc)2.1381; qc = 0.8625;
Uc = 0.8625(2582.75) + (1 – 0.8625)761.39 = 2332.31 kJ/kg;
WEC(b→c) = 2332.31 − 2596.98 = –264.67 kJ/kg.
(c) This is the last step. E-balance: isentropic. WEC(d→a) = ΔU; Ua = U(sat. liq., 5MPa) =
1148.21 kJ/kg; the quality at state d is not known, but we can use the entropy at state a to find it.
S-balance: ΔS = 0; Sd = Sa = 2.9210 kJ/kg-K= qd(6.5850) + (1 − qd)2.1381; qd = 0.1761;
Ud = 0.1761(2582.75) + (1 – 0.1761)761.39 = 1082.13 kJ/kg;
WEC(d→a) = 1082.13 − 1148.21 = –66.08 kJ/kg.
Example 4.4 A Carnot cycle based on steam (Continued)

(d) This is the third step using the quality for d calculated in part (c). This is a fixed T,P conden-
sation. E-balance: QC = ΔU – WEC = (ΔU+PΔV) = ΔH; Hd = 762.52 + 0.1761(2014.59) =
1117.29 kJ/kg; Hc= 762.52 + 0.8625(2014.59) = 2500.10 kJ/kg; QC = Hd − Hc = –1382.21 kJ/kg
WEC = PΔV ; Vc = 0.001127(1 – 0.8625) + 0.8625(0.1944) = 0.1678 m3/kg = 167.8 cm3/g
Vd = 0.001127(1 – 0.1761)+0.1761(0.1944) = 0.0352 m3/kg = 35.2 cm3/g
W(c→d) = 1.0(35.2 – 167.8) = –132.6 MPa-cm3/g = –132.6 kJ/kg
(e) ηθ = –Wnet/QH; Wnet = (264.67–66.08+191.1–132.6) = 257.1 kJ/kg;

ηθ = 257.1/1639.57 = 0.157; ηθ (Carnot) = (263.94–179.88)/(263.94+273.15) = 0.157.
The actual cycle matches the Carnot formula. Note that the cyclic nature of this process means
that we could have computed more quickly by
Wnet = –(QC + QH) = 1382.21 – 1639.57 = 257.4 kJ/kg.
The macroscopic view of entropy can be bewildering when first studied because students strive
to understand the physical connection. The microscopic view of entropy is helpful for some stu-
dents but a significant disconnect often persists. In either case, if you review the definitions at the
beginning of the chapter, both are mathematical, not physical. In Chapter 2 we discussed that Q was
a path-dependent property, but now we are demonstrating that dividing the quantity by T and inte-
grating along a path results in a quantity that is independent of the path!15 Some students find it
helpful to accept this as a mathematical relationship with the name of “entropy.” In fact, develop-
ment of the macroscopic definition of entropy was not obvious to the scientists who eventually
proved it to be a state property. The scientific literature at the time of Carnot can be confusing to
read because the realization of the state nature of the integral was not obvious, but was developed
by a significant amount of diligence and insight by the scientists of the day.
Note that entropy does not depend directly on the work done on a system. Therefore, it may be
used to decouple heat and work in the energy balance for reversible processes. Also for reversible
! Entropy can processes, entropy provides a second property that may be used to determine unknowns in a pro-
be used to decouple cess as we have seen in the previous two examples. In fact, the power of this property is that it can
heat and work.
be used to evaluate reversibility of processes, and such understanding is critical as we search sus-
tainable energy management practices, such as CO2 sequestration. Let us investigate some conve-
nient pathways for the evaluation of entropy changes before we develop examples that utilize the
pathways.
Calculation of Entropy Changes in Closed Systems

As with enthalpy and internal energy, tables and charts are useful sources for entropy information
for common fluids. Note the tabulation of S in the tables of Appendix E. These tables and charts are
calculated using the definition of entropy and procedures for non-ideal fluids that we will discuss in
upcoming chapters.
For manual calculations of entropy, we develop some simple procedures here, and more rigor-
ous procedures in Chapter 8. Since the integral of Eqn. 4.13 must be evaluated along a reversible
path, let us consider some easy choices for paths. For a closed reversible system without shaft work,
the energy balance in Eqn. 2.16 becomes,
15. Note, however, that Q is constrained to be reversible in the macroscopic definition, so it is not entirely arbitrary.
2
v g
d U + -------- + ----- z = dQ rev + dW S + dW EC 4.15
2g c g c
Inserting Eqn. 2.3,
[ dU + PdV ] = dQ rev 4.16
We now consider how this equation may be substituted in the integral of Eqn. 4.13 for calculating
entropy changes in several situations.
Constant Pressure (Isobaric) Pathway

Many process calculations involve state changes at constant pressure. Recognizing H = U + PV,
dH = dU + PdV + VdP. In the case at hand, dP happens to be zero; therefore, Eqn. 4.16 becomes
dH = dQrev 4.17
Since dH = CPdT at constant pressure, along a constant-pressure pathway, substituting for

dQrev in Eqn. 4.13, the entropy change is
CP
( dS ) P = ------- ( dT ) P 4.18
T
T2
CP
ΔS =
 ------- dT
T 4.19 ! Constant
pressure.
T1
Constant Volume Pathway

For a constant volume pathway, Eqn. 4.16 becomes
dU = dQ rev 4.20
Since dU = CV dT along a constant volume pathway, substituting for dQrev in Eqn. 4.13, the entropy
change is
T2
CV
ΔS =
 ------- dT
T 4.21 ! Constant
volume.
T1
Constant Temperature (Isothermal) Pathway

The behavior of entropy at constant temperature is more difficult to generalize in the absence of
charts and tables because dQrev depends on the state of aggregation. For the ideal gas, dU = 0 =
dQ − PdV, dQ = RTdV/V, and plugging into Eqn. 4.13,
V2 P2
or ΔS = – R ln -----
ig
! Isothermal. ΔS ig = R ln ------ - (ig) 4.22
V1 P1
For a liquid or solid, the effect of isothermal pressure of volume change is small as a first approxima-
tion; the precise relations for detailed calculations will be developed in Chapters 6–8. Looking at the
steam tables at constant temperature, entropy is very weakly dependent on pressure for liquid
water. This result may be generalized to other liquids below Tr = 0.75 and also to solids. For con-
densed phases, to a first approximation, entropy can be assumed to be independent of pressure (or
volume) at fixed temperature.
Adiabatic Pathway
A process that is adiabatic and reversible will result in an isentropic path. By Eqn. 4.13,
state 2 dQ rev
! Adiabatic and
reversible.
ΔS =
state 1
-------------- = 0 for reversible process only.
T sys 4.23
Note that a path that is adiabatic, but not reversible, will not be isentropic. This is because a revers-
ible adiabatic process starting at the same state 1 will not follow the same path, so it will not end at
state 2, and reversible heat transfer will be necessary to reach state 2.
Phase Transitions
In the absence of property charts or tables, entropy changes due to phase transitions can be easily
calculated. Since equilibrium phase transitions for pure substances occur at constant temperature
and pressure, for vaporization
dQ rev vap
 
vap 1 Q
ΔS = -------------- = --------- dQ rev = ------------
T sat sat
T T
where T sat is the equilibrium saturation temperature. Likewise for a solid-liquid transition,
fus
fus Q
ΔS = ----------
Tm
where Tm is the equilibrium melting temperature. Since either transition occurs at constant pressure
if along a reversible pathway, we may include Eqn. 4.17, giving
vap fus
= Δ = Δ
vap H fus H -
! Phase transi- ΔS --------------- and ΔS ------------- 4.24
sat Tm
tions. T
Now let us examine a process from Chapter 2 that was reversible, and study the entropy change.
We will show that the result is the same via two different paths, confirming that entropy is a state
function.
Example 4.5 Ideal gas entropy changes in an adiabatic, reversible

expansion
In Example 2.11 on page 75, we derived the temperature change for a closed-system adiabatic
expansion of an ideal gas. How does the entropy change along this pathway, and what does this
example show about changes in entropy with respect to temperature?
Solution: Reexamine the equation ( C V ⁄ T )dT = – ( R ⁄ V )dV , which may also be written
( C V ⁄ R )d ln T = – d ln V . We can sketch this path as shown by the diagonal line in Fig. 4.4.
Since our path is adiabatic (dQ = 0) and reversible, and our definition of entropy is
dS = ( dQ rev ) ⁄ T , we expect that this implies that the path is also isentropic (a constant-
entropy path). Since entropy is a state property, we can verify this by calculating entropy along
the other pathway of the figure consisting of a constant temperature (step A) and a constant vol-
ume (step B)
For the reversible isothermal step we have
dU = dQrev − PdV = 0 or dQrev = PdV (ig)
Step A
lnT Adiabatic, Step B

Reversible
Path
lnV
Figure 4.4 Equivalence of an adiabatic and an
alternate path on a T-V diagram.
Thus,
dQ rev
- = PdV
( dS ) T = ------------- ----------- (ig)
T T
Substituting the ideal gas law,
RTdV dV
( dS ig ) T = -------------- = R ------- (ig) 4.25
VT V
Example 4.5 Ideal gas entropy changes in an adiabatic, reversible

expansion (Continued)
For the constant volume step, we have
dU = dQrev or CVdT = dQrev

Thus,
dQ rev dT
( dS ) V = -------------
- = C V ------ 4.26
T T
We could replace a differential step along the adiabat (adiabatic pathway) with the equivalent
! The entropy differential steps along the alternate pathways; therefore, we can see that the change in entropy
change along the is zero,
adiabatic, revers-
ible path is the
same as along (step ig CV R
A + step B) illustrat- dS adiabat = ( dS ) V + ( dS ig ) T = ------- dT + --- dV = 0 (ig) 4.27
T V
ing that S is a state
property.
which was shown by the energy balance in Eqn. 2.62, and we verify that the overall expansion is
isentropic. Trials with additional pathways would show that ΔS is the same.
The method of subdividing state changes into individual temperature and volume changes can
be generalized to any process, not just the adiabatic process of the previous example, giving
ig CV R
dS = ------- dT + --- dV (ig) 4.28
T V
We may integrate steps A and B independently. We also could use temperature and pressure steps to
calculate entropy changes, resulting in an alternate formula:
ig T- + R ln ----
V- ig T- – R ln ----
P-
! Formulas for ΔS = C V ln ---- or ΔS = C P ln ---- (*ig) 4.29
i i i i
an ideal gas. T V T P
As an exercise, you may wish to choose two states and find the change in S along two different
pathways: first with a step in T and then in P, and then by inverting the steps. The heat and work
will be different along the two paths, but the change in entropy will be the same.
Looking back at Eqn. 4.26, we realize that it does not depend on the ideal gas assumption, and
it is a general result,
∂S 
 ----- C
! - = ------V-
Temperature  ∂T V T 4.30
derivatives of en-
tropy are related to
CP and CV . which provides a relationship between CV and entropy. Similarly, looking back at Eqn. 4.18,
∂S-
 ----- C
= ------P-
 ∂T P T 4.31
Eqns. 4.30 and 4.31 are particularly easy to apply for ideal gases. In fact, the most common method
for evaluating entropy changes with temperature applies Eqn. 4.31 in this way, as shown below.
Example 4.6 Ideal gas entropy change: Integrating CPig(T)

Propane gas undergoes a change of state from an initial condition of 5 bar and 105°C to 25 bar
and 190°C. Compute the change in entropy using the ideal gas law.
Solution: Because P and T are specified in each state, the ideal gas change is calculated most eas-
ily by combining an isobaric temperature step, Eqns. 4.19, and an isothermal pressure change,
Eqn. 4.22. The heat capacity constants are obtained from Appendix E.
T 2 C ig ig
P 2 T2 CP T2
( A + BT + CT + DT )
2 3
  
P
S2ig − S1ig = -------
- dT – R ln ------ ; -------
- dT = --------------------------------------------------------- dT
T1 T P1 T T
1 T1 T
T2 P
S2ig − S1ig = A ln  ----- + B ( T 2 – T 1 ) + ---- ( T 2 – T 1 ) + ---- ( T 2 – T 1 ) – R ln -----2-
C 2 2 D 3 3
 T 1 2 3 P 1
–4
463.15 – 1.586 ×10
= −4.224 ln ---------------- + 0.3063(463.15 − 378.15) + ------------------------------- (463.152
378.15 2
–8
3.215 ×10 25
−378.152) + ---------------------------- (463.153 − 378.153) − 8.314ln ------ = 6.613 J/mol-K
3 5
Entropy Generation
At the beginning of Section 4.3 on page 142, statement number one declares that irreversible pro-
cesses generate entropy. Now that some methods for calculating entropy have been presented, this
principle can be explored.
Example 4.7 Entropy generation and “lost work”

In Example 4.1 consider the surroundings at 300 K: (a) Consider the entropy change in the sur-
roundings and the universe for parts 4.1(a) and 4.1(b) and comment on the connection between
entropy generation and lost work; (b) How would entropy generation be affected if the surround-
ings are at 310 K?
Example 4.7 Entropy generation and “lost work” (Continued)

Solution:
(a) For 4.1(a) the entropy change of the surroundings is

dQ Q
 ----------- = --------- = –--------------
4014
ΔS surr = - = – 13.38J/K . This is equal and opposite to the entropy
T surr 300 300
change of the piston/cylinder, so the overall entropy change is ΔS universe = 0 .
For part 4.1(b), the entropy change of the universe is
ΔS surr = Q ⁄ 300 = – 1995 ⁄ 300 = – 6.65J/K . The total entropy change is
ΔS universe = 13.38 – 6.65 = 6.73J/K > 0 , thus entropy is generated when work is lost.
(b) If the temperature of the surroundings is raised to 310K, then for the reversible piston cylin-
der expansion for 4.1(a), ΔS surr = – 4014 ⁄ 310 = – 12.948J/K , and
ΔS universe = 13.38 – 12.95 = 0.43J/K > 0 . This process now will have some ‘lost work’ due
to the temperature difference at the boundary even though the piston/cylinder and work was fric-
tionless without other losses. We will reexamine heat transfer in a gradient in a later example.
For case 4.1(b), the entropy generation is still greater, indicating more lost work,
ΔS surr = – 1995 ⁄ 310 = – 6.43J/K , ΔS universe = 13.38 – 6.43 = 6.95J/K > 0 .
! This is an irre- Note: When the entropy change for the universe is positive the process is irre-
versible process be- versible. Because entropy is a state property, the integrals that we calculate may
cause entropy is
generated. be along any reversible pathway, and the time dependence along that pathway is
unimportant.
We discussed in Chapter 2 that friction and velocity gradients result in irreversibilities and thus
entropy generation occurs. Entropy generation can also occur during heat transfer, so let us con-
sider that possibility.
Example 4.8 Entropy generation in a temperature gradient

A 500 mL glass of chilled water at 283 K is removed from a refrigerator. It slowly equilibrates to
room temperature at 298 K. The process occurs at 1 bar. Calculate the entropy change of the
water, ΔSwater, the entropy change of the surroundings, ΔSsurr, and the entropy change of the uni-
verse, ΔSuniv. Neglect the heat capacity of the container. For liquid water CP = 4.184 J/g-K.
Solution:
Water: The system is closed at constant pressure with T i = 283 K and T f = 298 K. We choose
any reversible pathway along which to evaluate Eqn. 4.13, a convenient path being constant-
pressure heating. Thus,
dQ rev = dH = mC P dT
Section 4.4 The Entropy Balance 153
Example 4.8 Entropy generation in a temperature gradient (Continued)

Substituting this into our definition for a change in entropy, and assuming a T-independent CP,
f
T
mC P dT  T f
------------------ = mC P ln  ---- = 500 ( 4.184 ) ln  --------- = 108.0 ----

298 J
ΔS water = (*)
T sys T  i  283  K
i
T
Surroundings: The surroundings also undergo a constant pressure process as a closed system;
however, the heat transfer from the glass causes no change in temperature—the surroundings act
as a reservoir and the temperature is 298 K throughout the process. The heat transfer of the sur-
roundings is the negative of the heat transfer of the water, so we have
f f
T T
dQ rev dQ rev, water – m C P ΔT water
 
J
- = –
31380J- = – 105.3 ---
ΔS surr = -------------- = – --------------------------
- = -------------------------------- -------------------- - (*)
T surr T surr T surr 298K K
i i
T T
Note that the temperature of the surroundings was constant, which simplified the integration.
Universe: For the universe we sum the entropy changes of the two subsystems that we have
defined. Summing the entropy change for the water and the surroundings we have
J
ΔS univ = 2.7 ----
K
Entropy has been generated. The process is irreversible.
4.4 THE ENTROPY BALANCE

In Chapter 2 we used the energy balance to track energy changes of the system by the three types of
interactions with the surroundings—flow, heat, and work. This method was extremely helpful
because we could use the balance as a checklist to account for all interactions. Therefore, we present
a general entropy balance in the same manner. To solve a process problem we can use an analogous
balance approach of starting with an equation including all the possible contributions that might
occur and eliminating the balance terms that do not apply for the situation under consideration.
Entropy change within a system boundary will be given by the difference between entropy
which is transported in and out, plus entropy changes due to the heat flow across the boundaries,
and in addition, since entropy may be generated by an irreversible process, an additional term for
entropy generation is added. A general entropy balance is
·
  
dS in in out out Q ·
------ = S m· – S m· + ---------- + S gen 4.32 ! General en-
dt T sys tropy balance.
inlets outlets surfaces
Like the energy balance, the quantity to the left of the equals sign represents the entropy change of
the system. The term representing heat transfer should be applied at each location where heat is
transferred and the Tsys for each term is the system temperature at each boundary where the heat
transfer occurs. The heat transfer represented in the general entropy balance is the heat transfer
which occurs in the actual process. We may simplify the balance for steady-state or closed systems:
·
in out Q ·
! ·
0 = m ( S – S ) + ---- + S gen 4.33
Open, steady-
state entropy
T
balance.
dQ
! Closed system dS = ------- + dS gen 4.34
entropy balance.
T
The heat flow term(s) are always written in the balance with a “plus” from the perspective of the
system for which the balance is written.
Caution: The entropy balance provides us with an additional equation which may
be used in solving thermodynamic problems; however, in irreversible processes,
the entropy generation term usually cannot be calculated from first principles.
Thus, it is an unknown in Eqns. 4.32–4.34. The balance equation is not useful for
·
calculating any other unknowns when S gen is unknown. In Example 4.8 the prob-
lem would have been difficult if we applied the entropy balance to the water or the
·
surroundings independently, because we did not know how to calculate S gen for
each subsystem. However, we could calculate ΔS for each subsystem along
reversible pathways. Summing the entropy changes for the subsystems of the
universe, we obtain the entropy change of the universe. Consider the right-hand
side of the entropy balance when written for the universe in this example. There
is no mass flow in and out of the universe—it all occurs between the subsystems
of the universe. In addition, heat flow also occurs between subsystems of the uni-
verse, and the first three terms on the right-hand side of the entropy balance are
zero. Therefore, the entropy change of the universe is equal to the entropy gener-
ated in the universe.
Caution: The criterion for the feasibility of a process is that the entropy genera-
tion term must be greater than or equal to zero. The feasibility may not be deter-
mined unequivocally by ΔS for the system unless the system is the universe.
Note: As we work examples for irreversible processes, note that we do not apply the entropy bal-
ance to find entropy changes. We always calculate entropy changes by alternative reversible
pathways that reach the same states, then we apply the entropy balance to find how much
entropy was generated.
Alternatively, for reversible processes, we do apply the entropy balance because we set the
entropy generation term to zero.
Let us now apply the entropy balance—first to another heat conduction problem. In Example 4.8
we studied an unsteady-state system. Now let us consider steady-state heat transfer to show which
entropy balance terms are important in this application. In this example, we show that such heat
conduction results in entropy generation because entropy generation occurs where the temperature
gradient exists.
Example 4.9 Entropy balances for steady-state composite systems
Imagine heat transfer occurring between two reservoirs.
(a) A steady-state temperature profile for such a system is illustrated in Fig. (a) below. (Note that
the process is an unsteady state with respect to the reservoirs, but the focus of the analysis here is
on the wall.) The entire temperature gradient occurs within the wall. In this ideal case, there is no
temperature gradient within either reservoir (therefore, the reservoirs are not a source of entropy
generation). Note that the wall is at steady state. Derive the relevant energy and entropy balances,
carefully analyzing three subsystems: the hot reservoir, the cold reservoir, and the wall. Note
that a superficial view of the reservoirs and wall is shown in Fig. (b).
(b) Suppose the wall was replaced by a reversible Carnot engine across the same reservoirs, as
illustrated in Fig. (c). Combine the energy and entropy balances to obtain the thermal efficiency.
Hot Reservoir Hot Reservoir
Temperature Profile TH TH
Wall
TC = 300 K QH QH
TH = 500 K
dQH
Hot WS
Reservoir dQC Wall
Cold
Reservoir
QC QC
0 b
x Cold Reservoir Cold Reservoir
TC TC
(a) (b) (c)
Note: Keeping track of signs and variables can be confusing when the uni-
verse is divided into multiple subsystems. Heat flow on the hot side of the wall
will be negative for the hot reservoir, but positive for the wall. Since the focus
of the problem is on the wall or the engine, we will write all symbols from the
perspective of the wall or engine and relate to the reservoirs using negative
signs and subscripts.
Solution:
(a) Since the wall is at steady state, the energy balance for the wall shows that the heat flows in
and out are equal and opposite:
0 =  Q· = Q· H + Q· C  Q· H = – Q· C 4.35
boundaries

(Continued)
The entropy balance in each reservoir simplifies:
·
dS H or C Q ·
 S
in in out out
-------------------- = S m· – ·
m + ---------- + S gen
dt T sys
in out
The entropy generation term drops out because there is no temperature gradient in the reservoirs.
Taking the hot reservoir as the subsystem and noting that we have defined QH and QC to be
based on the wall, we write:
· · · · ·
dS H Q – Q H,wall dS C Q – Q C,wall Q H,wall
---------- = ------- = --------------------- ; --------- = ------ = -------------------- = ----------------- 4.36
dt TH TH dt TC TC TC
where the heat fluxes are equated by the energy balance.
Now consider the entropy balance for the wall subsystem. Entropy is a state property, and since
no state properties throughout the wall are changing with time, entropy of the wall is constant,
and the left-hand side of the entropy balance is equal to zero. Note that the entropy generation
term is kept because we know there is a temperature gradient:
· ·
dS wall QH QC ·
-------------- = 0 = -------- + ------- + S gen, W
dt TH TC
Noting the relation between the heat flows in Eqn. 4.35, we may then write for the wall:
· ·
S gen,wall = Q H  -----
1-
1- – ------ 4.37
T T 
C H
Then the wall with the temperature gradient is a source of entropy generation. Summarizing,
· ·
dS univ dS H dS wall dS C – Q H,wall – Q C,wall
--------------- = ---------- + -------------- + --------- = --------------------- + -------------------- = S· gen,wall 4.38
dt dt dt dt TH TC
! Entropy is gen- Hence we see that the wall is the source of entropy generation of the universe, which is positive.
erated by a temper- Notice that inclusion of the wall is important in accounting for the entropy generation by the
ature gradient.
entropy balance equations.
(b) The overall energy balance relative for the engine is:
–W ·  Q· C

· · · · ·
0 = Q + W = Q H + Q C + W S  η θ = ----------
S
=  1 + -------
- 4.39
Q· H  Q· H
boundaries

(Continued)
The engine operates a steady-state cycle, dS engine ⁄ dt = 0 (it is internally reversible):
· · · ·

Q · QH QC QC –TC
 S
in in out out
0 = S m· – m· + ---- + S gen = -------- + -------  -------
· - = ---------
- 4.40
T TH TC QH TH
in out boundaries
As before, η θ = – W · ⁄ Q· = ( 1 – T ⁄ T ) and we have derived it using the entropy balance.

S H C H
Note that the heat flows are no longer equal and are such that the entropy changes of the reser-
voirs sum to zero.
We have concluded that heat transfer in a gradient results in entropy production. How can we
transfer heat reversibly? If the size of the gradient is decreased, the right-hand side of Eqn. 4.37
decreases in magnitude; coincidentally, heat conduction slows, through the following relation:16
dT
Q· = Ak ------ where A = cross-sectional area
dx
A smaller temperature gradient decreases the rate of production of entropy, but from a practical
standpoint, it requires a longer time to transfer a fixed amount of heat. If we wish to transfer heat
reversibly from two reservoirs at finitely different temperatures, we must use a heat engine, as
described in part (b). In addition to transferring the heat reversibly, use of a heat engine generates
work.
Summary: This example has shown that boundaries (walls) between systems can ! Entropy may be
generate entropy. In this example, entropy was not generated in either reservoir generated at system
because no temperature profile existed. The entropy generation occurred within boundaries.
the wall.
Note that we could have written the engine work of part (b) as follows:
T C
W S, net = Q H  1 – ------
- = T C ⋅ Q H  ------ – ------
1-
1 4.41
 T  T T 
H C H
Compare this to Eqn. 4.37, the result of the steady-state entropy generation. If we run the heat
transfer process without obtaining work, then the universe loses a quantity of work equal to the fol-
lowing:
·
W ·
lost = T C S gen 4.42
Note that TC , the colder temperature of our engine, is important in relating the entropy generation
to the lost work. TC can be called the temperature at which the work is lost. Lost work is explored
more completely in Section 4.12. Also note that we have chosen to operate the heat engine at tem-
peratures which match the reservoir temperatures. This is arbitrary, but is required to obtain the
maximum amount of work. The heat engine may be reversible without this constraint, but the entire
process will not be reversible. These details are clarified in the next section.
16. This relation is known as Fourier’s law and is studied in heat-transfer courses.
An entirely analogous analysis of heat transfer would apply if we ran the heat engine in
reverse, as a heat pump. Only the signs would change on the direction the heat and work were flow-
ing relative to the heat pump. Therefore, the use of entropy permits us to reiterate the Carnot formu-
las in the context of all fluids, not just ideal gases.
· ·
– W S, net  Q C  T C
! η θ = ------------------
· - =  1 + -------
· - =  1 – ------
- , Carnot heat engine 4.43
Carnot thermal
efficiency. QH  Q H T H
·
QC T H  –1 TC
! COP ≡ · - =  ------
--------------- -–1 = -------------------
T  T , Carnot refrigerator 4.44
H – TC
Carnot coeffi-
cient of perfor- W S, net C
mance.
4.5 INTERNAL REVERSIBILITY

A process may be irreversible due to interactions at the boundaries (such as discussed in Example 4.9
on page 155) even when each system in the process is reversible. Such a process is called inter-
nally reversible. Such a system has no entropy generation inside the system boundaries. We have
derived equations for Carnot engines and heat pumps, assuming that the devices operate between
temperatures that match the reservoir temperatures. While such restrictions are not necessary for
internal reversibility, we show here that the work is maximized in a Carnot engine at these condi-
tions and minimized in a Carnot heat pump. Note that in development of the Carnot devices, the
only temperatures of concern are the operating temperatures at the hot and cold portions of the
cycle. In the following illustrations, the internally reversible engine or pump operates between TH
and TC, and the reservoir temperatures are T2 and T1.
Heat Engine
A schematic for a Carnot engine is shown in Fig 4.5(a). Heat is being transferred from the reservoir
at T2 to the reservoir at T1, and work is being obtained as a result. In order for heat transfer to occur
! The operating between the reservoirs and the heat engine in the desired direction, we must satisfy
temperatures of a T 2 ≥ T H > T C ≥ T 1 , and since the thermal efficiency is given by Eqn. 3.6, for maximum efficiency
reversible heat en- (maximum work), TC should be as low as possible and TH as high as possible, i.e., set TH = T2, TC =
gine or heat pump
are not necessarily T1.
equal to the sur-
rounding’s tempera-
tures; however, the
optimum work inter-
actions occur if they T2 T2
match the surround-
ing’s temperature
because matching TH TH
the temperatures WS,net WS,net
eliminates the finite
temperature-driving TC TC
force that gener-
ates entropy.
T1 T1
(a) Heat engine (b) Heat pump
Figure 4.5 Schematic of a heat engine (a) and heat pump (b). The temperatures of the reservoirs are not
required to match the reversible engine temperatures, but work is optimized if they do, as discussed
in the text.
Section 4.6 Entropy Balances for Process Equipment 159
Heat Pump
A schematic for a Carnot heat pump is shown in Fig. 4.5(b). Heat is being transferred from a reser-
voir at T1 to the reservoir at T2, and work is being supplied to achieve the transfer. In order for heat
transfer to occur between the reservoirs and the heat engine in the desired direction, we must satisfy
T 2 ≤ T H > T C ≤ T 1 . Since the COP is given by Eqn. 4.44, for maximum COP (minimum work), TC
should be as high as possible and TH as low as possible, i.e., set TC = T1, TH = T2. Therefore, opti-
mum work interactions occur when the Carnot device operating temperatures match the surround-
ing temperatures. We use this feature in future calculations without special notice.
4.6 ENTROPY BALANCES FOR PROCESS EQUIPMENT

Before analysis involving multiple process units, it is helpful to consider the entropy balance for
common steady-state process equipment. Familiarity with these common units will facilitate rapid
analysis of situations with multiple units, because understanding these balances is a key step for the
calculation of reversible heat and work interactions.
Simple Closed Systems

Changes in entropy affect all kinds of systems. We have previously worked with piston/cylinders
and even a glass of water. You should be ready to adapt the entropy balance in creative ways to
everyday occurrences as well as sophisticated equipment.
Example 4.10 Entropy generation by quenching

A carbon-steel engine casting [CP = 0.5 kJ/kg°C] weighing 100 kg and having a temperature of
700 K is heat-treated to control hardness by quenching in 300 kg of oil [CP = 2.5 kJ/kg°C] initially
at 298 K. If there are no heat losses from the system, what is the change in entropy of: (a) the
casting; (b) the oil; (c) both considered together; and (d) is this process reversible?
Solution: Unlike the previous examples, there are no reservoirs, and the casting and oil will
both change temperature. The final temperature of the oil and the steel casting is found by an
energy balance. Let T f be the final temperature in Κ.
Energy balance: The total change in energy of the oil and steel is zero.
Heat lost by casting:
Q = mCpΔT = 100 (0.5) (700 − T f )
Heat gained by oil:
Q = mCpΔT = 300 (2.5) (T f − 298)  balancing the heat flow, T f = 323.1 K
Entropy balance: The entropy change of the universe will be the sum of the entropy changes of
the oil and casting. We will not use the entropy balance directly except to note that ΔSuniv = Sgen.
We can calculate the change of entropy of the casting and oil by any reversible pathway which
begins and ends at the same states. Consider an isobaric path:
dQ CP T2
Using the macroscopic definition  ΔS =
 ------T- = m  ------T- dT = mCP ln  -----
T 1
 (*)
Example 4.10 Entropy generation by quenching (Continued)

(a) Change in entropy of the casting:
ΔS = 100 (0.5) ln[323.1/700] = −38.7 kJ/K (*)

(b) Change in entropy of the oil (the oil bath is of finite size and will change temperature as heat
is transferred to it):
ΔS = 300 (2.5) ln[323.1/298] = 60.65 kJ/K (*)

(c) Total entropy change: Sgen = Δ Suniv = 60.65 − 38.7 = 21.9 kJ/K
! Compare with (d) Sgen > 0; therefore irreversible; compare the principles with Example 4.8 on page 152 to note
Example 4.8 on the similarities. The difference is that both subsystems changed temperature.
page 152.
Heat Exchangers
The entropy balance for a standard two-stream heat exchanger is given by Eqn. 4.45. Since the unit
is at steady state, the left-hand side is zero. Applying the entropy balance around the entire heat
exchanger, there is no heat transfer across the system boundaries (in the absence of heat loss), so
the heat-transfer term is eliminated. Since heat exchangers operate by conducting heat across tub-
ing walls with finite temperature driving forces, we would expect the devices to be irreversible.
Indeed, if the inlet and outlet states are known, the flow terms may be evaluated, thus permitting
calculation of entropy generation.
·
Q ·
 S
dS in in out out
------ = S m· – ·
m + ---------- + S gen 4.45
dt T sys
in out
We also may perform “paper” design of ideal heat transfer devices that operate reversibly. If
we set the entropy generation term equal to zero, we find that the inlet and outlet states are con-
strained. Since there are multiple streams, the temperature changes of the streams are coupled to
satisfy the entropy balance. In order to construct such a reversible heat transfer device, the unit
would need to be impracticably large to only have small temperature gradients.
Example 4.11 Entropy in a heat exchanger

A heat exchanger for cooling a hot hydrocarbon liquid uses 10 kg/min of cooling H2O which
enters the exchanger at 25°C. Five kg/min of hot oil enters at 300°C and leaves at 150°C and has
an average specific heat of 2.51 kJ/kg-K.
(a)Demonstrate that the process is irreversible as it operates now.
(b)Assuming no heat losses from the unit, calculate the maximum work which could be obtained
if we replaced the heat exchanger with a Carnot device which eliminates the water stream and
transfers heat to the surroundings at 25°C
Example 4.11 Entropy in a heat exchanger (Continued)
Oil 300°C Oil 150°C
Water, Twout (°C) Water 25°C
Solution:
(a) System is heat exchanger (open system in steady-state flow)

Energy balance:
ΔH oil m· oil + ΔH water m· water = 0
10(4.184)(Twout – 25) + 5(2.51)(150 – 300) = 0; Twout = 70°C

Entropy balance:
ΔS oil m· oil + ΔS water m· water = S· gen
dSi = dQ/T = CP dT/T  ΔSi = CPi ln (Ti out/Tiin) (*)
ΔSoil = CP ln (Tout/T in) = (2.51)ln(423.15/573.15) = −0.7616 kJ/kgK (*)
ΔSwater = CP ln (T out/T in) = (4.184) ln(343.15/298.15) = 0.5881 kJ/kgK (*)
S· gen = ΔS oil m· oil + ΔS water m· water = 5 ( – 0.7616 ) + 10 ( 0.5881 ) = 2.073 kJ/K-min
The process is irreversible because entropy is generated.
(b)The modified process is represented by the “device” shown below. Note that we avoid calling
the device a “heat exchanger” to avoid confusion with the conventional heat exchanger. To sim-
plify analysis, the overall system boundary is used.
Oil 300°C Oil 150°C
·
QH
·
Carnot W S, net
Engine
·
QC
Overall System Boundary
25°C
Example 4.11 Entropy in a heat exchanger (Continued)

in out · ·
By an energy balance around the overall system, 0 = n· ( H – H ) + Q C + W S .
We can only solve for the enthalpy term,
in out in out
m· ( H – H ) = m· C P ( T – T ) = 5 ( 2.51 ) ( 300 – 150 ) = 1882.5 kJ/min
Since heat and work are both unknown, we need another equation. Consider the entropy bal-
ance, which, since it is a reversible process, S· gen = 0 , gives
·
· in out QC ·
0 = m ( S – S ) + ------- , Q C = 298.15· (−0.7616)·5 = −1135 kJ/min
T
Now inserting these results into the overall energy balance gives the work,
· net = –1883. + 1135. = –748 kJ/min

W S
Throttle Valves
Steady-state throttle valves are typically assumed to be adiabatic, but a finite pressure drop with
·
zero recovery of work or kinetic energy indicates that S gen > 0 . Throttles are isenthalpic, and for
ig i in
an ideal gas, they are thus isothermal, ΔS = C P ln ( T ⁄ T ) – R ln ( P out ⁄ P ) . For a real fluid,
temperature changes can be significant. The entropy increase is large for gases, and small, but non-
zero for liquids. It is important to recall that liquid streams near saturation may flash as they pass
through throttle valves, which also produces large entropy changes and significant cooling of the
process fluid even when the process is isenthalpic. Throttles involving flash are common in the liq-
uefaction and refrigeration processes discussed in the next chapter. Throttles are always irrevers-
ible.
Nozzles
Steady-state nozzles can be designed to operate nearly reversibly; therefore, we may assume
·
S gen = 0 , and Eqn. 4.47 applies. Under these conditions, thrust is maximized as enthalpy is con-
verted into kinetic energy. The distinction between a nozzle and a throttle is based on the reversibil-
ity of the expansion. Recall from Chapter 2 that a nozzle is specially designed with a special taper to
avoid turbulence and irreversibilities. Naturally, any real nozzle will approximate a reversible one
and a poorly designed nozzle may operate more like a throttle. Proper design of nozzles is a matter
of fluid mechanics. We can illustrate the basic thermodynamic concepts of a properly designed noz-
zle with an example.
Example 4.12 Isentropic expansion in a nozzle

Steam at 1000°C and 1.1 bars passes through a horizontal adiabatic converging nozzle, dropping
to 1 bar. Estimate the temperature, velocity, and kinetic energy of the steam at the outlet assuming
the nozzle is reversible and the steam can be modeled with the ideal gas law under the conditions.
Consider the initial velocity to be negligible. The highest exit velocity possible in a converging
nozzle is the speed of sound. Use the NIST web sitea as a resource for the speed of sound in steam
at the exit conditions.
Example 4.12 Isentropic expansion in a nozzle (Continued)

Solution:
Energy balance: ΔH = −mΔv2/2 Entropy balance (reversible): ΔS = 0.
For an isentropic reversible expansion the temperature will drop. We will approximate the heat
capacity with an average value. Let us initially use a CP for 1273 K. Estimating the heat capacity
from Appendix E at 1273 K, the polynomial gives CP = 44.37 J/mol, R/CP ~ 8.314/44.37 =
0.1874. The following relation satisfies the entropy balance for an adiabatic, reversible, ideal gas
(Eqn. 4.29):
T P R ⁄ CP
 -----2 =  -----2- = ( 1.1 )
– 0.1874
= 0.9823 Τ2 = 1273(0.9823) = 1250.5 Κ (*)
 T 1  P 1
The temperature change is small, so the constant heat capacity assumption is fine. The enthalpy
change is −ΔH = −CPΔT = 44.6(1273 – 1250.5)(J/mol) = 1004 J/mol.
Assuming that the inlet velocity is low, v1 ~ 0 and converting the enthalpy change to the change
in velocity gives v2 = –2ΔH/m = 2·1004J/mol(mol/18.01g)(1000g/kg)(1kg-m2/s2)/J =
111,500 m2/s2, or v = 334 m/s. According to the NIST web site at 1250K and 0.1MPa, the speed
of sound is 843 m/s. The design is reasonable.
a. Lemmon, E.W., McLinden, M.O., Friend, D.G. “Thermophysical Properties of Fluid Systems.” in NIST
Chemistry WebBook, NIST Standard Reference Database Number 69, P.J. Linstrom, W.G. Mallard (eds.)
National Institute of Standards and Technology, Gaithersburg, MD. http://webbook.nist.gov, (retrieved
November 12, 2011).
Adiabatic Turbine, Compressor, and Pump

The entropy balance for a steady-state adiabatic device is:
·
Q ·
 S
dS in in out out
------ = S m· – ·
m + ---------- + S gen 4.46
dt T sys
in out
·
The left-hand side drops out because the system is at steady state. If the device is reversible, S gen
17 · in · out
is zero. Further, these devices typically have a single inlet or outlet, and m = m , thus,
Sout’ = Sin 4.47 ! Adiabatic

reversible turbine,
Therefore, if we know the inlet state, we can find S in. The outlet pressure is generally given, so compressor, and
pump.
for a pure fluid, the reversible outlet state is completely specified by the two state variables S out’
and P out. We then use thermodynamic relations to find the other thermodynamic variables at this
state, and use the energy balance at this state to find Wrev. Turbines, compressors, and pumps are
very common equipment in chemical processes. Guidelines exist for estimating the degree of irre-
versibility in each piece of equipment based on experience. These guidelines take the form of an
estimated efficiency. For example, a large expensive turbine might be 85% efficient, but a small
cheap one might be 65% efficient. To apply these guidelines, we must formally define efficiency,
17. In multistage units, the stages may be considered individually.

then familiarize ourselves with variations on how to characterize the capacity and operating condi-
tions of these operations.
4.7 TURBINE, COMPRESSOR, AND PUMP EFFICIENCY

Our analysis of the Carnot devices supports statement 2 at the beginning of Section 4.3. We have
seen that work is maximized/minimized when the entropy generation is zero. Analysis of other pro-
cesses would verify this useful conclusion. Work is lost by processes which generate entropy. If a
device is not internally reversible, work will be lost within the device. Also, even if the device is
internally reversible, work may be lost by irreversible interactions with the surroundings. There-
fore, in setting up and solving problems to find maximum/minimum work, the objectives must be
clear as to whether the system is internally reversible or whether the entire process is reversible.
When we apply the entropy balance to a reversible process, the term representing entropy genera-
tion is zero.
In Chapter 2, both velocity gradients and friction were discussed as phenomena that lead to
irreversibilities. Indeed, entropy is generated by both of these phenomena as well as by heat con-
duction along temperature gradients discussed in this chapter. Considering factors which affect
reversibility (generation of entropy), you may have challenged yourself to consider a practical way
to transfer heat with only infinitesimal temperature differences, or move fluid with only infinitesi-
mal velocity gradients. You are probably convinced that such a process would not be practical.
Indeed, the rate at which heat is transferred increases as the temperature driving forces increase,
and we need finite temperature differences to transfer heat practically. Likewise, a pump will have
large velocity gradients. Although we can measure changes in other properties by which we can
calculate entropy changes arising from irreversibilities, an a priori prediction of lost work (Wlost) or
entropy generated (Sgen) is extremely difficult and generally impractical. Direct evaluation of lost
work in process equipment, such as turbines and compressors, is far beyond routine calculation and
determined by empirical experience. It may seem that all of the effort to characterize reversible pro-
cesses will be difficult to relate to real processes.
However, we can use practical experience to relate real processes to the idealized reversible
processes. Therefore, in analyzing or designing processes involving operations of this nature, it is
often necessary to approximate the real situation with a reversible one in which (Wlost) = 0 (no
entropy generation). Past experience with many devices, such as compressors and turbines, often
permits the engineer to relate performance under hypothetical reversible conditions to actual opera-
tion under real conditions. The relation is usually expressed by means of an efficiency factor.
Equipment manufacturers typically provide performance curves as a function of process condi-
tions. For introductory purposes, in this text we use a fixed factor. For devices such as pumps and
compressors which utilize work from the surroundings, efficiency is defined as
W'
! Primes are pump or compressor efficiency = η C = ------ × 100% 4.48
W
used to denote re-
versible processes.
where the ' denotes the reversible work. This notation will be used throughout the text when irre-
versible and reversible calculations are performed in the same problem. For turbines and other
expansion devices that supply work to the surroundings, the definition is inverted to give
Section 4.8 Visualizing Energy and Entropy Changes 165
W
turbine or expander efficiency = η E = ------ × 100% 4.49
W'
For adiabatic pumps, compressors, turbines, or expanders, the work terms may be calculated
from the reversible and irreversible enthalpy changes by application of the energy balance.
Note: The strategy is to first calculate the work involved in a reversible process, then apply an
efficiency which is empirically derived from previous experience with similar equipment. The
outlet pressure of an irreversible adiabatic turbine or pump is always at the same pressure as a
reversible device, but the enthalpy is always higher for the same inlet state. This means that if
the outlet of the reversible adiabatic device is a single phase, the outlet of the irreversible adia-
batic device will be at a higher temperature. If the outlet of the reversible adiabatic device is a
two-phase mixture, the quality for the irreversible adiabatic device will be higher or the outlet
could potentially be a single phase.
4.8 VISUALIZING ENERGY AND ENTROPY CHANGES

Turbines, compressors, and pumps occur so frequently that we need convenient tools to aid in pro-
cess calculations. Visualization of the state change is possible by plotting entropy on charts. This ! Visualizing state
technique also permits the charts to be used directly in the process calculations. One common rep- changes on charts
resentation is the T-S chart shown in Fig. 4.6. The phase envelope appears as a fairly symmetrical will be helpful when
using tables or com-
hump. A reversible turbine, compressor, or pump creates state changes along a vertical line on puters for physical
these coordinates. Lines of constant enthalpy and pressure are also shown on these diagrams, as properties.
sketched in the figure. Volumes are also usually plotted, but they lie so close to the pressure lines
that they are not illustrated in the figure here to ensure clarity.
P-H diagrams shown in Fig. 4.7 are also useful; they are used frequently for refrigeration pro- ! A 3D diagram
cesses. The phase envelope tends to lean to the right because the enthalpies of vapor and liquid are for steam is avail-
both increasing along the saturation curve until the critical point is approached, where the vapor- able in PHT.m. The
diagram can be
phase enthalpy decreases due to significant non-idealities. Lines of constant entropy on these plots rotated.
are slightly diagonal with a positive slope as shown in Fig. 4.7(a). For some hydrocarbons and
const. H
const. P
T Crit.Pt.
Liquid
Vapor
Two-Phase Region
S
Figure 4.6 Illustration of a T-S diagram showing lines of constant pressure and enthalpy.
Crit.Pt.
P Liquid
Vapor
Two-Phase
Region
H
(a)
Crit.Pt.
P Liquid
Vapor
Two-Phase
Region
H
(b)
const. S
Figure 4.7 Illustration of a P-H diagram showing (a) lines of constant entropy for a
species where the saturation curve leans less than isentropes (e.g.,
water) and (b) illustration of a P-H diagram showing lines of constant
entropy for a species where the saturation curve leans more than isentropes
(e.g., hexane).
halogenated compounds, the phase envelope can lean more sharply than the isentropic lines as
shown in Fig. 4.7(b). A reversible compressor will operate along a line of constant entropy.
Another convenient representation of entropy is the H-S diagram (Mollier diagram). In this
diagram, lines of constant pressure are diagonal, and isotherms have a downward curvature as in
Fig. 4.8. The saturation curve is quite skewed.
4.9 TURBINE CALCULATIONS

! The outlet For a reversible adiabatic turbine, the entropy balance in Section 4.6 shows that the outlet entropy
entropy of an irre-
versible adiabatic
must equal the inlet entropy. For an irreversible turbine, the outlet entropy must be greater than the
turbine will be inlet entropy. We may now visualize the state change on the diagrams sketched in Section 4.8. For
greater than the out- example, on a T-S diagram, the performance of a turbine can be visualized as shown in Fig. 4.9.
let entropy of a re-
versible adiabatic
Note that the isobars are important in sketching the behavior because the outlet pressure must be
turbine with the the same for the reversible and irreversible turbines, but the outlet enthalpies (not shown) and
same outlet entropies must be different.
pressure.
Section 4.9 Turbine Calculations 167
const. P
const. T
H CritPt.
Vapor
Liquid
Two-Phase
Region
S
Figure 4.8 Illustration of an H-S (Mollier) diagram showing lines of
constant pressure and temperature.
const. P
rev. actual
T Crit.Pt.
Liquid
Vapor
Two-Phase Region
S
Figure 4.9 Illustration of a reversible and actual
(irreversible) turbine on a T-S diagram.
Steam Quality Calculations

A common problem encountered when adiabatically reducing the pressure of real fluids like steam,
methane, or refrigerants is the formation of a vapor-liquid mixture. Since the thermodynamic prop-
erties change dramatically depending on the mass fraction that is vapor (the quality), it is important
to know how to calculate that fraction. The calculation procedure may differ from the case shown
in Fig. 4.9 where the outlets for the reversible and irreversible cases are both one phase. Since the
reversible adiabatic turbine is isentropic, the line representing the reversible process must be verti-
cal. As shown in Fig. 4.10, if the upstream entropy is less than the saturated vapor entropy at the
outlet pressure, the reversible outlet ends up inside the liquid-vapor region, to the left of the satu-
rated vapor curve. In this case, we must perform a quality calculation to determine the vapor frac-
tion. Since the actual turbine must have an outlet state of higher entropy, due to entropy generation,
the outlet state can lie inside the phase envelope, on the saturation curve, or outside the phase enve-
lope, depending on the proximity of the reversible outlet state to the saturation curve and also ! The actual out-
depending on the turbine efficiency. A frequent question is, “How do I know when I need a quality let state might be
calculation?” The calculation is required if the inlet entropy is less than the saturation entropy at the in the one-phase
region when the re-
outlet pressure as illustrated in the figure. A quality calculation may also be required for the actual versible outlet state
state, if the actual enthalpy turns out to be less than the saturation enthalpy at the outlet pressure. is in the two-phase
region.
Supercritical P out
T actual
rev.
Liquid Vapor
Liquid + Vapor
Tie Line
S
Figure 4.10 Illustration of need for quality
calculation on turbine outlet where
the actual outlet is saturated steam.
The best way to master turbine calculations is to practice; the examples in this section are
designed to facilitate your effort. Example 4.13 explores the inference of outlet conditions and
proper application of turbine efficiency. Example 4.14 illustrates calculation of turbine efficiency.
Example 4.15 illustrates the determination of inlet conditions to match a desired outlet. The combi-
nations of inlet and outlet specifications are too many to enumerate. Therefore, you need to practice
inferring the necessary procedure for any given situation. Challenge yourself to repeat the examples
without looking at the steps. Several practice problems are also given at the end of the chapter, with
detailed solutions available at the textbook web site. As you practice, pay attention to the results
and look for generalities that broaden your comprehension.
Determining Turbine Outlet Conditions

Let us work a series of examples illustrating the various situations that may arise in calculation of
turbine outlets. Usually, the design of a turbine involves a given inlet state and outlet pressure. That
outlet pressure may be specified explicitly, or it may be implicit in a statement giving the outlet
temperature and the quality; it may be inferred then that the outlet pressure is the saturation pres-
sure at the given temperature. An important skill is to quickly determine whether the reversible tur-
bine follows Fig. 4.9 or whether it follows Fig. 4.10. Subsequently, for the cases that follow Fig.
4.10, the outlet state may lie inside or outside the phase envelope. The determination depends on
the efficiency and the inlet entropy, with the following cases:
(i) Reversible outlet one phase, actual outlet one phase;
(ii) Reversible outlet two phase, actual outlet one phase;
(iii) Reversible outlet two phase, actual outlet two phase.
This example, though long, comprehensively covers the solution methods to determine turbine
outlets for single-stage turbines from a known inlet state and specified pressure drop.
Example 4.13 Various cases of turbine outlet conditions

An adiabatic turbine inlet (state 1) is 500°C and 1.4 MPa. For each of the following outlet condi-
tions (state 2), determine the specified quantities.
(a) P2 = 0.6 MPa, ηE = 0.85. Find WS, H2, S2, and T2.
(b) P2 = 0.03 MPa, ηE = 0.85. Find WS, H2, S2, and T2.
(c) P2 = 0.01 MPa, ηE = 0.9. Find WS, H2, S2, and T2.
Example 4.13 Various cases of turbine outlet conditions (Continued)

Note that using a common inlet state for each of the cases will permit us to skip the steps to
determine the inlet state as we work the different alternatives.
Solution: First, the inlet properties are determined: H1 = 3474.8 kJ/kg, S1 = 7.6047 kJ/kg-K. The
reversible calculation is performed for each outlet condition, recognizing that a reversible tur-
bine is isentropic.
(a) S2' = S1 = 7.6047 kJ/kg-K. Comparing with SsatV= 6.7593 kJ/kg-K at P2 = 0.6 MPa, S2' >
SsatV, so the reversible outlet state is superheated and any irreversibility must lead to
greater entropy and greater superheat (case (i)). This is the case of Fig. 4.9. Interpolating:
T (°C) H (kJ/kg) S (kJ/kg-K)
350 3166.1 7.5481
7.6047
400 3270.8 7.7097
7.6047 – 7.5481
H 2 ′ = 3166.1 + --------------------------------------- ( 3270.8 – 3166.1 ) = 3202.8 kJ/kg
7.7097 – 7.5481
By similar interpolation, T2' = 367.5°C.
ΔH' = WS’ = 3202.8 − 3474.8 = −272.0 kJ/kg

Applying ηE calculation, ΔH = WS = ηE ΔH' = 0.85(−272) = −231.2 kJ/kg,
H2 = H1 + ΔH = 3474.8 − 231.2 = 3243.6 kJ/kg

Preparing for interpolation:
350 3166.1 7.5481
3243.6
400 3270.8 7.7097
3243.6 – 3166.1
S 2 = 7.5481 + --------------------------------------- ( 7.7097 – 7.5481 ) = 7.6677 kJ/kg-K
3270.8 – 3166.1
By similar interpolation, T2 = 387.0°C. We see that irreversibility has warmed the outlet, but not
“heated” it, because it was adiabatic. With a one-phase outlet, T2 > T2' if ηE < 1.
(b) The pressure is lower than part (a), and the saturated vapor S will be larger, and near
the saturation boundary.
Recall that S2' = S1 = 7.6047 kJ/kg-K. Comparing with SsatV= 7.7675 kJ/kg-K at P2 = 0.03 MPa,
S2' < SsatV, so the reversible outlet state is two-phase. This is the case of Fig. 4.10 and we need to
proceed further to determine if the actual state is inside or outside the phase envelope. Interpo-
lating using the saturation entropy values along with the S2' at T2' = 69.1°C,
S – S satL 7.6047 – 0.9441

q' = --------------------- = --------------------------------------- = 0.976
ΔS vap 6.8234
Using Eqn. 1.27:


H 2 ′ = 289.27 + 0.976 ( 2335.28 ) = 2568.5 kJ/kg
ΔH' = WS’ = 2568.5 − 3474.8 = − 906.3 kJ/kg

Applying ηE calculation, ΔH = WS = ηE ΔH' = 0.85(−906.3) = −770.35 kJ/kg,
H2 = H1 + ΔH = 3474.8 − 770.35 = 2704.4 kJ/kg

Comparing H2 with H = 2624.55 kJ/kg at P2 = 0.03 MPa, H2 > HsatV, so the outlet state is
satV
superheated (outside the phase envelope). This is an instance of case (ii).

To conclude the calculations, a double interpolation is required. Performing the first interpola-
tion between 0.01 and 0.05 MPa will bracket the outlet state. (Note: 0.03 MPa is halfway
between 0.01 and 0.05 MPa, so tabulated values are obtained by averaging rather than by a
slower interpolation.)
100 (2687.5 + 2682.4)/2 = 2684.95 (8.4489 + 7.6953)/2 = 8.0721
2704.4
150 (2783.0 + 2780.2)/2 = 2781.6 (8.6892 + 7.9413)/2 = 8.3153
Interpolating:
2704.4 – 2684.95
S 2 = 8.0721 + ------------------------------------------ ( 8.3153 – 8.0721 ) = 8.121 kJ/kg-K
2781.6 – 2684.95
Similarly, by interpolation, T2 = 110.1°C.
Note: The reversible state is two-phase, and the actual outlet is one-phase for part (b). Also,
S2 > S2' = S1 and H2 > H2' which are always true for irreversible turbines. T2 > T2', which is a
general result for one-phase output.
(c) Very low-outlet pressures shifts the saturation value of S to even higher values, making
it more likely that the outlet will be two phase, case (iii).
S2' = S1 = 7.6047 kJ/kg-K. Comparing with SsatV= 8.1488 kJ/kg-K at P2 = 0.01 MPa,
S2' < SsatV, so the reversible outlet state is two-phase. This is the case of Fig. 4.10 and we need to
proceed further to determine if the actual state is inside or outside the phase envelope. Interpo-
lating at P = 0.01 MPa (T2' = 45.81°C),
7.6047 – 0.6492
q' = --------------------------------------- = 0.9274
7.4996
Using Eqn. 1.27,
H 2 ′ = 191.81 + 0.9274 ( 2392.05 ) = 2410.2 kJ/kg
ΔH' = WS' = 2410.3 − 3474.8 = − 1064.6 kJ/kg

Applying ηE calculation, ΔH = WS = ηE ΔH' = 0.90(−1064.6) = −958.1 kJ/kg,
H2 = H1 + ΔH = 3474.8 − 958.1 = 2516.7 kJ/kg.

Comparing H2 with HsatV= 2583.86 kJ/kg at P2 = 0.01 MPa, H2 < HsatV, so the actual outlet
state is two-phase as well as the reversible outlet (case (iii)). For the actual outlet, H2 gives:

2516.7 – 191.81
q = --------------------------------------- = 0.972
2392.05
Using Eqn. 1.27,
S 2 = 0.6492 + 0.972 ( 7.4996 ) = 7.9388 kJ/kg
The actual outlet is wet steam at T2 = 45.81°C. The reversible outlet and the actual outlet are
both wet steam for part (c). Also, S2 > S2' = S1 and H2 > H2' which are always true for irrevers-
ible turbines. For case (c), T2 = T2', however q2 > q2', a general result for a two-phase outlet.
This example has exhaustively covered the possibilities that may occur when performing tur-
bine analysis given a specified pressure drop and known inlet condition. The actual outlet enthalpy
and entropy are always greater than the reversible values. The actual outlet T will be the same as
the reversible T if both states are wet steam. Note that many variations could generate calculations
that appear to be different from these cases, but are actually similar. For example, the quality could
be specified at the outlet instead of the efficiency. Similarly, the steam outlet H or S, etc. could be
specified rather than the quality. For any problem, the details of the interpolation may differ for a
given application depending on the region of the steam tables. Nevertheless, the overall procedures
of using entropy to identify the reversible state and then correcting for the actual state are always
the same. The following example illustrates a typical turbine calculation that might be used to char-
acterize the efficiency of a working turbine.
Example 4.14 Turbine efficiency calculation

An adiabatic turbine inlet is at 500°C and 1.4 MPa. Its outlet is at 0.01MPa and q = 99%.
(a) Compute the work of the turbine.

(b) Compute the work of a reversible turbine.
(c) Compute the efficiency of the turbine and the entropy generation of the actual turbine.
Solution: The energy balance is ΔH = WS.
(a) The inlet is the same as Example 4.13: H1 = 3474.8; S1 = 7.6047. At the outlet,
H 2 = 191.81 + 0.99 ( 2392.05 ) = 2559.9 kJ/kg
ΔH = WS = 2559.9 − 3474.8 = −914.9 kJ/kg

(b) Entropy balance: ΔS' = 0 => S2' = S1 = 7.6047 kJ/kg-K.
It is slightly ambiguous whether we should match the outlet pressure or the specification of
quality. By convention, it is assumed that pressure is the desired criterion (or temperature in a
similar situation) because this pertains to the physical constraints of the design. This means that
the reversible work is the same as Example 4.13(c) and WS' = –1064.6 kJ/kg.
(c) The turbine efficiency is defined by ηE = WS/WS' = 914.9/1064.6 = 85.9%.

The entropy generation is given by Sgen = S2 – S2'.
Example 4.14 Turbine efficiency calculation (Continued)

S 2 = 0.6492 + 0.99 ( 7.4996 ) = 8.0738 kJ/kg-K
Referring to the entropy balance, S2' = S1 = 7.3046 so Sgen = 8.0738 – 7.6047 = 0.4691 J/g-K.
Another type of calculation involves determining a turbine inlet that will result in a certain out-
let. The procedure is to use the outlet state to estimate the inlet entropy as a crude guess, and then
use trial and error inlet conditions until the desired outlet state is matched.
Example 4.15 Turbine inlet calculation given efficiency and outlet

An adiabatic turbine outlet (state 2) is 99% quality steam at 0.01 MPa, ηE = 85%. The inlet pres-
sure has been specified as 0.6 MPa. An absolute pressure of 0.6 MPa is conventionally defined
as low pressure steam and is often applied in chemical processing. Find WS, H1, S1, and T1.
Solution: “Coincidentally,” the outlet properties were determined in Example 4.14:

H2 = 2559.9; S2 = 8.0738. Referring to the superheated steam tables at 0.6 MPa, we seek an
entropy value that is less than 8.0738 kJ/kg-K because ηE < 100% means entropy is generated.
This occurs around 500°C. Trying 500°C, gives H1 = 3483.4 kJ/kg and S1 = 8.0041 kJ/kg-K.
Then WS = –923.5 kJ/kg; q' = (8.0041 − 0.6492)/7.4996 = 0.9807;
So H1' = 191.8 + 0.9807(2392)=2537.6 kJ/kg; WS' = 2537.6 − 3483.4 = –945.8 kJ/kg;
Wlost = 945.8 – 923.5 = 22.3 kJ/kg; ηE = –923.5/(–923.5 – 22.3) = 97.7%.
Further trials generate the values tabulated below. The last temperature is estimated by interpo-
lation. (Hint: It would be great practice for you to compute these and check your answers.).
T H1 S1 WS Wlost ηE
450 3376.5 7.8611 –816.6 67.9 92.3%
400 3270.8 7.7097 –710.9 116.2 86.0%
350 3166.1 7.5481 –606.2 167.8 78.3%
393.8 3257.7 7.6895 –697.8 122.6 85.0%
Multistage Turbines
Commonly, turbines are staged for several reasons that we explore in Chapter 5. Generally, some
steam is drawn off at intermediate pressures for other uses. The important point that needs to be
stressed now is that the convention used for characterizing efficiency is important. Consider the
three-stage turbine shown in Fig. 4.11 and the schematic that represents the overall reversible path
and the actual path. The isobars on the H-S diagram for water curve slightly upward, and are spaced
slightly closer together at the bottom of the diagram than at the top. The overall efficiency is given
overall H4 – H1
by η E - , and the efficiency of an individual stage is given by
= ------------------------
ΔH' overall
H –H
η E, i = ------------------------
i+1
-i . If we consider the reversible work as ΔH'overall, that quantity must be smaller
ΔH' i
Section 4.10 Pumps and Compressors 173
actual path
1 2 3 4 overall 1
I II III reversible
ΔH'I
path
2
ΔH'overall ΔH'II
3
H CrPt. 4 ΔH'III
(a) Explicit representation of stages
1 4 Vapor
Two-Phase
Liquid Region
2 3 S
(b) Stages sharing a common housing, equivalent to (a) (c)
Figure 4.11 Illustration that overall efficiency of an adiabatic turbine will be higher than the
efficiency of the individual stages.
than
 ΔH'i . In fact, because the isobar spacing is increasing to the right of the diagram, the
stages
vertical drop between any isobars on the line marked as the overall reversible path must be smaller
than the vertical drop between the same two isobars starting along the actual path (except for the
very first turbine). Therefore, the efficiency calculated for the overall system must be higher than ! Overall turbine
the efficiency for the individual stages. This comparison does not imply that staging turbines alters efficiency will be
their performance. The difference in efficiencies is due to differences in what is considered to be greater than stage
efficiencies for the
the basis for the reversible calculation. The cautionary note to retain from this discussion is that the same total work out-
distinction between overall or individual efficiencies is important when communicating the perfor- put.
mance of a staged turbine system.
4.10 PUMPS AND COMPRESSORS

An irreversible, adiabatic pump or compressor generates entropy. If these devices are reversible,
they are isentropic. Examples of both are shown in Fig. 4.12. The calculations are generally
straightforward. Consider the case where the inlet state and the outlet pressure is known. First, the
reversible outlet state is determined based on the isentropic condition, and the enthalpy at the
reversible state is known. The most common estimate for compressors is described in Example
2.12 on page 76. Even though it is intended for ideal gases, it is convenient for many applications
and often provides a reasonable first approximation. The most common estimate for pumps is
described in Eqn. 2.32 on page 55. These both pertain to reversible processes. The efficiency can
then be used to determine the actual outlet enthalpy and work, using Eqn. 4.46.
Example 4.16 Isothermal reversible compression of steam

In Example 2.12 on page 76, we mentioned that computing the work for isothermal compression
of steam was different from computing the work for an ideal gas. Now that you know about the
entropy balance, use it to compute the work of continuously, isothermally, and reversibly com-
pressing steam from 5 bars and 224°C to 25 bars. Compare to the result of the ideal gas formula.
Example 4.16 Isothermal reversible compression of steam (Continued)

Solution: Energy balance: ΔH = Q + W. Entropy balance: ΔS = Q/T. Note that ΔS ≠ 0, even
though this is a reversible process. Sgen = 0, but the process is not adiabatic. From the steam
tables, we note that 224°C and 25 bars is practically equal to the saturated vapor. For the vapor
at 224°C and 25 bars, interpolation gives H = 2910.5, S = 7.1709. Noting Q = TΔS,
Q = (224 + 273.15)(6.2558 – 7.1709) = –454.94; W = (2801.9 – 2910.5) + 454.94 = 346.3 J/g.
By the ideal gas formula, W = 8.314(4.04)(224 + 273.15)ln(5)/18 = 1493.1 J/g.
The work is less for the real vapor because of the intermolecular attractions. The difference was
particularly large in this case because the final pressure was fairly high (> 10 bars).
Compressor
Pump
rev. rev. Compressor
P actual
T
Pump rev. actual actual
rev. actual
S H
Figure 4.12 Illustrations of pathways for reversible and irreversible pumps and compressors. The P-H
diagram is for a system like Fig. 4.7(a).
Multistage Compression
During adiabatic compression of vapors, the temperature rises. This can cause equipment problems
if the temperature rise or pressure ratio (P out/Pin) is too large. To address this problem, interstage
cooling is used to lower the gas temperature between compression stages. Such operations are com-
mon when high pressures need to be reached. A schematic of a compressor with interstage cooling
is shown in Fig. 4.13. The total work for multistage compression is generally given by summing the
work of each stage using Eqn. 2.69 on page 77. However, the ideal gas law becomes less reliable as
the stagewise inlet pressure increases. If the inlet pressure is above 10 bars and the reduced temper-
ature is less than 1.5, nonideality effects should be evaluated. Methods to evaluate gas non-ideali-
ties and to calculate entropy for all manner of non-ideal gases are discussed in Unit II. For common
refrigerants, it is convenient to apply charts that are functionally equivalent to the steam tables. The
charts are difficult to read and precision is relatively low compared to using the steam tables.
Example 4.17 illustrates the procedure using the refrigerant R134a.
Example 4.17 Compression of R134a using P-H chart

A compressor operates on R134a. The inlet to the compressor is saturated vapor at –20°C. The
outlet of the compressor is at 7.7 bar and ηC = 0.8. Find the reversible and required work (kJ/kg)
and the outlet temperature of the compressor.
Section 4.11 Strategies for Applying the Entropy Balance 175
P T
H S
Figure 4.13 Illustration of a multistage compression and the corresponding P-H diagram. On the P-H
diagram, the compressors appear as the curves of increasing pressure and the heat exchangers
are the horizontal lines at constant pressure.
Example 4.17 Compression of R134a using P-H chart (Continued)

Solution: An inset of the P-H diagram from Appendix E is shown below. The axis labels and
superheated temperature labels have been translated on the inset diagram.
.
H (kJ/kg)
2’
2
P (bar)
The inlet state is located at the intersection of the –20°C isotherm and the saturated vapor line.
The enthalpy is found by following the vertical lines to the axis and H = 386.5 kJ/kg. (Note: This
accurate value was found from the accompanying saturation table, but the schematic value is
consistent, though less accurate.) The reversible outlet state is found by following an isentropic
state up to 7.7 bars. One set of the diagonal lines are isentropes, and we visually interpolate to
keep the same relative position between the isentropes at 7.7 bar at the state labeled 2'. By fol-
lowing the vertical lines to the axis, H2' = 424 kJ/kg. The reversible work is WS' = 424 – 386.5 =
37.5 kJ/kg. The actual work is WS = WS' / 0.8 = 47 kJ/kg. The actual outlet state is shifted to the
right at 7.7 bar at an enthalpy value of H2 = 386.5 + 47 = 433.5 kJ/kg. The reversible outlet is
just near 38°C. The actual outlet is near 48°C.
4.11 STRATEGIES FOR APPLYING THE ENTROPY

BALANCE
! New key words
When solving thermodynamic problems, usually the best approach is to begin by applying the have been defined
mass and energy balances. The entropy balance provides another balance, but it is not always nec- that specify con-
essary for every problem. In this chapter, we have introduced some new terms which can specify straints.
additional constraints when used in the problem statement, e.g., “isentropic,” “reversible,” “inter-
nally reversible,” “irreversible,” “thermal efficiency,” and “turbine/expander or compressor/pump
efficiency.”
The entropy balance is useful to calculate maximum work available from a process or to eval-
uate reversibility. The entropy balance should be introduced with care because it is often redundant
with the energy balance when simplified with information from step 5 from the strategies of Sec-
! In some cases, tion 2.13. (For example, the entropy balance applied to Example 2.11 on page 75 results in the same
T and P are known, simplified equation as the energy balance.) In general, if the pressures and temperatures of the pro-
so S can be deter- cess are already known, the entropies at each point, and the entropy changes, can be determined
mined without the
entropy balance in a without direct use of the entropy balance. However, if either the pressure or the temperature is
pure system. unknown for a process, the entropy balance may be the key to the solution.
Before beginning more examples, it is also helpful to keep in mind those processes which gener-
ate entropy. This is important because, in the event that such processes arise, the entropy-generation
term cannot be set to zero unless we modify the process to eliminate the source of the generation.
Entropy is generated by the following processes.
1. Heat conduction along a temperature gradient.

2. Diffusion along a concentration gradient.
3. Mixing of substances of different composition.
4. Adiabatic mixing at constant system volume of identical substances initially at different
molar entropies due to (T, P) differences.
5. Velocity gradients within equipment. This is accounted for in pipe flow by the friction fac-
tor developed in textbooks on fluid flow.
6. Friction.
7. Electrical resistance.
8. Chemical reactions proceeding at measurable rates.
In an open system, irreversibilities are always introduced when streams of different temperatures
are mixed at constant pressure (item 4 above) because we could have obtained work by operating a
! Problem state- heat engine between the two streams to make them isothermal before mixing. If the streams are isother-
ments will rarely mal, but of different composition, mixing will still generate entropy (e.g., see Eqn. 4.8 on page 138), and
explicitly point out we have not yet devised a general method to obtain work from motion on this molecular scale.
entropy generation,
so you will need to
look for causes.
As chemical engineers, it is important to recognize that all chemical reactions proceeding at a
finite rate generate entropy. The fundamental proof of this is provided in Section 17.16 and requires
discussion of the chemical potential discussed much later in the text. Like the other processes listed
here, reactions proceed spontaneously toward an equilibrium state due to finite driving forces. It is
possible to calculate the rate of entropy generation if the chemical potentials are known at the reac-
tion conditions. However, do not be deceived into thinking that a realistic reaction is thermodynam-
ically reversible. Reaction engineering literature refers to reactions as reversible if the equilibrium
constant (to be discussed later) is near 1 because the reaction can go “in either direction” (forward/
backward) depending on the driving forces. This type of reversibility is not the same as thermody-
namic reversibility. The reaction proceeding in either direction at measurable rates will generate
entropy and be thermodynamically irreversible.
Section 4.12 Optimum Work and Heat Transfer 177
When a situation requires the minimum work input, or the maximum work output, the system
is designed to minimize entropy generation, or make it zero if possible considering the limitations
discussed here. As we work examples, recall the comments from Section 3.4 which we repeat here:
Note: For irreversible processes, note that we do not apply the entropy balance to find
entropy changes. We always calculate the entropy change by an alternate reversible pathway
that reaches the final state, then we apply the entropy balance to find how much entropy was
generated, or we find the reversible work, apply an efficiency factor, and identify the final
state via the energy balance.
Alternately, for reversible processes, we do apply the entropy balance because we set the
entropy generation term to zero.
4.12 OPTIMUM WORK AND HEAT TRANSFER

Let us consider how to calculate the optimum work interactions for a general system. For an open
system where kinetic energy and potential energy changes are negligible,
dU =  Hin dn in –  H out dnout + dQ – PdV + dWS 4.50

inlets outlets
 Sin dn in –  Sout dnout + ---------

dQ
dS = - + dS gen 4.51
T sys
inlets outlets
where dSgen = 0 for an internally reversible process. If all the heat is transferred at a single temper-
ature Tsys, elimination of dQ in the first balance provides
dU =  ( Hin – Tsys Sin )dn in –  ( Hout – Tsys Sout )dn out 4.52
inlets outlets
+ T sys dS – PdV + dW S – T sys dS gen
If we wish to apply this balance to a process that is conceptually reversible, we must use care
to avoid any processes that are inherently irreversible (throttle valves, composition mixing pro-
cesses, mixing of streams with identical composition but different temperatures, standard heat
exchangers, chemical reactions at finite rates). Thus, if we consider a process that involves mixing
compositions or reactions, we must include realistic estimates of these terms before determining the
optimum work interaction. Once we recognize these limitations, we are ready to consider the gen-
eral problem of finding optimum work interactions.
Availability (Exergy)
Section 4.5 considered optimum work interactions between a closed system and reservoir and
found that optimum work interactions occur when the system temperature where heat transfer
occurs is equal to the reservoir temperature. Therefore, for optimum work interactions with the sur-
roundings, Tsys in Eqn. 4.52 should be replaced with the surrounding’s temperature To. Though it
leads to optimum work, it is an idealized condition because the rate of heat transfer is proportional
to the temperature difference (as studied in heat transfer courses), and the heat transfer with infini-
tesimal temperature differences will be infinitesimally slow. The surrounding’s temperature and
pressure (To and Po) are often considered the dead state, because when the system reaches this T
and P, energy input of some type is necessary to obtain expansion/contraction work, shaft work, or
heat transfer; without energy input the process is dead. However, departures from this dead state do
provide opportunities for work and heat interactions. Further, it is desirable to give a name to the
combination of variables that results. For the combination of variables in the summations of Eqn.
4.52 modified with To, we will use the term availability, or exergy, B,
B = H – To S availability or exergy 4.53
where H and S are state properties of the system at T and P, but To is the temperature of the dead
state. The terms “availability” and “exergy” are both used in literature for this property. At a given
T and P, the availability changes with To, so B is somewhat different from other state properties
used to this point. Inserting the availability into Eqn. 4.52, and collecting the state changes of the
system on the left-hand side, results in a general balance (ignoring kinetic and potential energy like
before),
dU + PdV – T o dS =  ( Bin )dn in –  ( Bout )dn out + dWS – To dSgen 4.54

inlets outlets
Steady-State Flow
For a system at steady-state flow, all terms on the left-hand side drop out, resulting in
 ( Bout )dn out –  ( Bin )dn in = dWS – To dSgen steady-state open system 4.55
outlets inlets
and we conclude that the difference in availability from the inlets to outlets is related to the opti-
mum shaft work. Note that TodSgen ≥ 0 and always subtracts from work input when dWS ≥ 0 which
means work input for an irreversible process is always greater than a reversible process for a given
state change. Similarly, for a given state change producing work, an irreversible process will
Josiah Willard always produce less work compared to a reversible process. The quantity ToSgen is called the lost
Gibbs (1839–1903)
was an American
work and the reason for the term should now be obvious. To is ambiguous when no heat is trans-
chemist, mathemati- ferred to the surroundings and drops out for an adiabatic process such as an adiabatic turbine with-
cian, and physicist. out any loss in applicability of the equation,
Yale University
awarded Gibbs the
first American Ph.D. ( ΔH – T o ΔS )dn out = dW S – T o dS gen but ΔH = W S and –T o ΔS = –T o S gen 4.56
in Engineering in
1863 and Gibbs
spent his career Closed System
there. Gibbs is rec-
ognized for apply- For a closed system, Eqn. 4.54 becomes
ing calculus to
thermodynamics
and combining the
dU + PdV – T o dS = dW S – T o dS gen closed system 4.57
first and second
laws. Gibbs studied For a constant-pressure closed system, VdP can be added to the left side (because it is zero in mag-
the concept of
chemical potential,
nitude), which then results in dU + PdV + VdP = dU + d(PV) = dH. Thus, the left-hand side can be
the Gibbs phase replaced with dB, though it is usually easier to calculate dH and TodS independently. We can define
rule, and many the Gibbs energy G ≡ H – TS. Then dG = dU + PdV + VdP – TdS – SdT. Thus, if the pressure is
other relations.
constant and the temperature is constant at To, then the change in Gibbs energy is related to the non-
Section 4.12 Optimum Work and Heat Transfer 179
expansion/contraction work. Another interesting analysis can be done if both work terms are on the
right-hand side of the equation: Hermann Ludwig
Ferdinand von
dU – T o dS = dW S – PdV – T o dS gen closed system Helmholtz (1821–
4.58
1894) was a Ger-
man physician and
We can define the Helmholtz energy A ≡ U – TS. Then dA = dU – TdS – SdT. When the system is physicist.
Besides studying
isothermal at To, then the change in Helmholtz energy is related to the sum of all forms of work.
optics of the eye, he
studied the concept
Availability Analysis of conservation of
energy.
As the world population grows and energy use increases, energy conservation will become increas-
ingly important. Not only is the energy balance important, but so is the wise use of existing
resources. Availability analysis can be used to determine how much entropy is generated by a pro-
cess. Availability analysis is sometimes used in process design analysis,18 and may be used more
widely in the future as we consider wise stewardship of energy resources.
Minimum Work for Separation

A key challenge in the development of a fermentation process is the titer, or yield from the fermen-
tation. Fermentation is used in the pharmaceutical industry to develop natural molecules. For exam-
ple, bacterial production of insulin is a feasible technology. Much of the cost of production depends
on the dilution level. We can estimate the minimum energy cost for concentrating a product by
combining the energy and entropy balances. Suppose that for a feed F we wish to obtain a pure
product P and by-product water, B, in an isothermal process. For continuous separation of a mixed
stream, the steady-state energy balance for a reversible separation is
0 = H F n· F – H B n· B – H P n· P + Q· rev + W
·
s 4.59
Assuming an ideal solution, we can recognize that because the heat of mixing is zero the energy
balance becomes
H F n· F – H B n· B – H P n· P = 
  xi Hi n· f – HB n· B – HP n· P = 0 4.60
The energy balance thus simplifies to
Q· rev = – W
·
s 4.61
The steady-state entropy balance for reversible separation exchanging heat at T is:
0 = T ( S F n· F – S B n· B – S P n· P ) + Q· rev 4.62
The strategy will be to determine the heat transfer from the entropy balance and then use it in the
energy balance to find the work.
The entropy of the feed stream will be (using Eqn. 4.9)
18. Bejan, A. 2006. Advanced Engineering Thermodynamics, 3ed, New York: John Wiley & Sons.
n· F S F = n· F  xi Si – n· F R  xi ln xi 4.63
i i
Inserting,
 
 
0 = T  n· F x i S i – n· F R x i ln x i – S B n· B – S P n· P + Q· rev = – n· F RT x i ln x i + Q· rev
 
 4.64
i i i
which becomes
·
RTn· F ( x 1 ln x 1 + x 2 ln x 2 ) F = Q rev 4.65
Let us suppose that component 2 is the desired species. On the basis of heat transfer per mole of
component 2,
RTn· F ( x 1 ln x 1 + x 2 ln x 2 ) F RT ( x 1 ln x 1 + x 2 ln x 2 ) F Q· rev
------------------------------------------------------------
- = ------------------------------------------------------
- = ----------
- 4.66
n· 2 x2 n· 2
Combining with the energy balance, the minimum work per mole of desired species is
– R T ( x 1 ln x 1 + x 2 ln x 2 ) F W ·
-s
---------------------------------------------------------- = ------ 4.67
x2 n· 2
Example 4.18 Minimum heat and work of purificationa

Products produced by biological systems can range over mole fractions from 10–1 to 10–9.
(a) Estimate the minimum reversible heat and work requirement to purify one mole of product at
298.15 K over this range.
(b) To understand the concentrations in dilute mixtures, calculate the mole fraction of insulin in
0.1wt% aqueous solution.
Solution: The work is from Eqn. 4.67, and the heat will have the opposite sign.
– R T ( x 1 ln x 1 + x 2 ln x 2 ) F W ·
-s
---------------------------------------------------------- = ------
x2 n· 2
For x2 = 0.10, x1 = 0.9. At 298.15K,

W· ⁄ n· = –8.314(298.15)(0.1ln(0.1) + 0.9ln(0.9)) / 0.1 = 8.1kJ
s 2
Repeating the calculation for other values of x2:.
x2 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9

· ⁄ n· (kJ/mol)
W 8.1 13.9 19.6 25.3 31.0 36.7 42.4 48.1 53.8
s 2
Section 4.13 The Irreversibility of Biological Life 181
Example 4.18 Minimum heat and work of purificationa (Continued)

Note that heat must be rejected. If a process is envisioned that requires heat, then the rejected
heat must be increased by an equal amount. For example, if a solution of concentration x2 = 0.10
is purified by adding 1 kJ of heat, then 9.1 kJ must be rejected.
(b) Searching for the molecular weight of insulin reveals a value of 5808 g/mol. Therefore,
x1 = 0.001/5808 = 1.72(10-7). The point is that biomolecules are often large, and therefore their
concentrations can be quite small on a mole fraction basis.
a. This problem was suggested by O’Connell, J.P. et al. July 2010. NSF BioEMB Workshop, San Jose, CA
4.13 THE IRREVERSIBILITY OF BIOLOGICAL LIFE

A fascinating feature of living systems is that they organize small molecules into large structures.
Towering pines grow with energy from the sun, CO2, water, and minerals extracted from the
ground. Mammals grow into sophisticated thinking creatures by consuming small bits of food, con-
suming water, and breathing air. Small mindless flagella are known to swim “up” a concentration
gradient toward a food source in a process known as chemotaxis. All of biological life builds mole-
cules that are chiral rather than racemic. Don’t these processes violate the principles developed thus
far in this chapter where we indicated the tendency of a system to move toward randomness? A
careful analysis shows that the answer is no.
The key is that the feasibility of a process is determined by the entropy change of the universe,
not the system itself. If organisms build molecules with lower entropy than the reactants, then the
surroundings must increase in entropy by a larger amount. These changes can occur by control of
the flux of molecules in/out of the system or by heat transfer. Mammals in particular are warm-
blooded, and are virtually isothermal. The body temperature of a healthy human being is univer-
sally 37°C (310 K). Rearrangement of the entropy balance for a human provides
( d ( nS ) ) ⁄ ( dt ) – TS· gen = TS n· in – TS n· out + Q·

in out
4.68
Technically, if we assume T = 310K, we also should recognize that entropy is generated at the
boundary between the human and the surroundings (at a lower temperature) and this is not
included.
Every biochemical reaction in the body continuously generates entropy. If the organism is fully
grown, we can approximate an adult as a steady-state process, so the first term on the left is nearly
zero. The second term on the left contributes a negative value because entropy is generated con-
stantly by the biochemical reactions. Ignoring transport terms initially, we can see that the heat
transfer is expected to be negative. The magnitude depends on the entropy flows entering and leav-
ing the system. Considering the other limiting possibility of negligible heat transfer, the entropy
flow “in” must be less than the entropy flow “out.” In practice, these fluxes are not sufficient to sus-
tain life. For humans, we know that our bodies reject heat at a rate of about 100 J/s. Thus, in addi-
tion to changing the entropy of our food to waste products, our existence depends on the ability to
reject heat to the surroundings and thus contribute to increase the entropy of the surroundings via
heat transfer. In the event that the surrounding temperature rises, humans experience heat stroke
because the biological processes stop working when the heat transfer is not possible.
Trees and plants use photosynthesis to convert light energy (photons), to run the reaction
nCO2 + nH2O + light → (CH2O)n + nO2 4.69
We have not explicitly included photons in our energy balance thus far, but it is a form of radiation
similar to heat. A key point is that this reaction is not spontaneous as written. We discuss the driv-
ing forces for chemical reactions towards the end of the text, but a superficial discussion is relevant
here. This reaction is an oversimplification of the actual process. In fact, more than 100 steps are
needed for photosynthetic construction of glucose,19 but these steps drive the overall reaction
above. To create a forward reaction, biological systems have developed a complex series of steps,
each spontaneous and coupled such that carbohydrate production is possible. Plants are able to
maintain this reaction by increasing the entropy of the surroundings to a greater extent than this
reaction decreases the entropy when turning small molecules into carbohydrates.
Energy usage is inherently less efficient as we move up the food chain. When a herbivore or
omnivore eats plant material, the stomach and intestinal enzymes break down the carbohydrates to
simple sugars in catabolic reactions (a step that increases entropy). These sugars are then “burned”
to produce CO2 (increasing entropy) as we showed in the previous chapter and the energy is used to
maintain the life cycle and continuously produce new cells (anabolic reactions, decreasing
entropy20) to replace dying cells and maintain tissue. Also, ingested proteins are broken into amino
acids (increasing entropy) and then reassembled into new proteins (decreasing entropy2). As dis-
cussed above, only a portion of the energy provided by glucose can be utilized for biological main-
tenance; some must be rejected as heat. Each creature in the food chain repeats this “loss” of energy
as heat is rejected. As engineers grapple with the challenge to use energy efficiently, it is helpful to
keep in perspective that despite the complexity of living entities, the fundamentals of life are gov-
erned by the same principles as those developed in this chapter. Furthermore, life is made possible
in humans by rejecting heat to the surroundings to drive the biological machinery. Despite their
complexity, humans are not able to use all the energy generated by burning sugars.
4.14 UNSTEADY-STATE OPEN SYSTEMS

We end the chapter by providing examples of unsteady-state open systems. The first example shows
that analysis of such systems can produce results quite consistent with expansion in a piston/cylin-
der.
Example 4.19 Entropy change in a leaky tank

Consider air (an ideal gas) leaking from a tank. How does the entropy of the gas in the tank
change? Use this perspective to develop a relation between T f and P f and compare it to the
expression we obtained previously by the energy balance.
Pi, Ti Pf, Tf Pout, Tout
19. Kondepudi, D. 2008. Introduction to Modern Thermodynamics. New York: Wiley, p. 386.
20. Though the structure building decreases entropy, the reactions are proceeding at a finite rate which generates entropy.
Section 4.14 Unsteady-State Open Systems 183
Example 4.19 Entropy change in a leaky tank (Continued)

Solution:
m-Balance: dn = − dnout
out
d ( nS ) = – out dn out out
S-Balance: -------------
- S -------------  ndS + Sdn = – S dn
dt dt
But physically, we know that the leaking fluid is at the same state as the fluid in the tank; there-
out out
fore, the S-balance becomes ndS + Sdn = – S dn , or ΔS = 0 .
For an ideal gas with a constant heat capacity:
ΔS = C V ln ( T 2 ⁄ T 1 ) + R ln ( V 2 ⁄ V 1 ) = 0 (*ig)
ΔS = C V ln ( T 2 ⁄ T 1 ) + R ln ( ( T 2 P 1 ) ⁄ ( P 2 T 1 ) ) = ( C V + R ) ln ( T 2 ⁄ T 1 ) – R ln ( P 2 ⁄ P 1 ) (*ig)
( R ⁄ CP )
( T2 ⁄ T1 ) = ( P2 ⁄ P1 ) (*ig)
Compare with Example 2.15 on page 81. The entropy balance and energy balance in this case ! Illustration that
are not independent. Either can be used to derive the same result. This also shows that our anal- the energy and en-
tropy balances may
ysis in Example 2.15 was assumed to be reversible. not be independent.
The next example builds on the first by adding a turbine to the tank. Note the method by which the
system is subdivided to solve the problem.
Example 4.20 An ideal gas leaking through a turbine (unsteady state)

A portable power supply consists of a 28-liter bottle of compressed helium, charged to 13.8 MPa
at 300 K, connected to a small turbine. During operation, the helium drives the turbine continu-
ously until the pressure in the bottle drops to 0.69 MPa. The turbine exhausts at 0.1 MPa.
Neglecting heat transfer, calculate the maximum possible work from the turbine. Assume helium
to be an ideal gas with CP = 20.9 J/mol-K.
WS
Pi, Ti Pf, Tf Pout, Tout
28 L
Consider a balance on the tank only. The result of the balance will match the result of Example
4.19.
Writing an entropy balance for a reversible adiabatic turbine only,
(Sout − Sin) n· = 0 ΔS = 0

Example 4.20 An ideal gas leaking through a turbine (unsteady state)

which shows that the turbine also does not change the molar entropy. Thus, the molar entropy of
the exiting fluid is the same as the entropy in the tank, which is identical to the molar entropy at
the start of the process. Therefore, the molar entropy and the pressure of the exiting gas are
fixed. Since only two intensive properties fix all other intensive properties for a pure fluid, the
exiting temperature is also fixed. The relation for an ideal gas along a reversible adiabat gives:
T out = T i (P out / P i) R/CP = 42.3 K (*ig)
Likewise: T f = T i (P f / P i) R/CP = 91.1 K (*ig)
Solution by overall energy balance:

d(nU) = H out dn + dWS and H out is fixed since T out, P out are fixed; therefore, we may apply hint
4(a) from Section 2.14.
Integrating this expression:
n fU f − niU i = H out(n f − ni) + WS

Rearranging:
f f out i i out
WS = n ( U – H ) – n (U – H ) 4.70
Determining variables in the equation:
n f = P f V/RT f; n f = 25.5gmol; ni = 154.9 gmol (ig)

Choose reference temperature, TR ≡ 300 K,  setting UR = 0, then since HR = UR + (PV)R, and
since the fluid is an ideal gas, CV = CP − R = 20.9 − 8.314 = 12.586 J/mol-K:
HR = (PV)R = RTR = R(300) (ig) 4.71
! Illustration Note:  H(T) = CP(T – TR) + HR = CP(T – 300) + R(300) (*ig)

using a reference
state.
H out = –2892 J/mol (*ig)
f
U = C V ( T – T R ) + U R = – 2629 J/mol ; U i = 0 (*ig)
Now, plugging into Eqn. 4.70:
WS = 25.5(−2629 + 2892) − 154.9(0 + 2892)
 WS = −441,200 J
Section 4.16 Summary 185
4.15 THE ENTROPY BALANCE IN BRIEF

In this section, we refer to a division of the universe into the same three subsystems described in
Section 2.14 on page 74.
·
Q ·
  
dS in in out out
------ = S m· – S m· + ---- + S gen
dt T
inlets outlets surfaces
1. T is the system temperature at the location where Q is transferred.

2. Sin, Sout are state variables, and any pathway may be used to calculate the change from
inlet to outlet. The pathway for calculation does not need to be the pathway for the actual
process.
3. S· gen represents entropy generation due to irreversibilities within the system, e.g., inter-
nal heat transfer or conduction, viscous dissipation or mixing of streams of differing
composition, or degradation of mechanical energy to thermal energy. Entropy generation
at system boundaries is not included in the balance.
4. Entropy generation may occur at container walls. The entropy generation of the universe must
be calculated by summing S· gen for all three subsystems, not just system 1 and system 3.
Test Yourself
1. What are the constraints on the sign of S· gen ?
2. Consider two isothermal processes both rejecting heat at the same temperature. One pro-
cess is reversible and the other is irreversible. Which has a larger absolute value of heat
transfer?
4.16 SUMMARY
We began the chapter introducing microscopic methods to calculate entropy. We demonstrated that
entropy increases when volume (for a gas) or temperature increases. Thermal energy is really a
means of representing the randomness due to accessible microstates, such that the concept is best
understood in terms of the microscopic definition of entropy. We showed that the macroscopic def-
inition was consistent with the microscopic definition. We showed that entropy is essential for anal-
ysis of reversibility for processes, because irreversible processes generate entropy. We
demonstrated that reversible Carnot cycle thermal efficiency was easily evaluated using entropy.
The primary impact for pure-fluid applications is that compressors and turbines can be analyzed
using empirical efficiencies relative to reversible devices. On a broader scale, however, you should
appreciate the limitations of the conversion of heat into work.
This chapter is relatively long because mastering computations involving entropy can be chal-
lenging. Students may be familiar with energy balances and heats of reaction from previous
courses, but entropy may seem new and abstract. Therefore, many examples have been provided.
Students are encouraged to review these and the practice problems at the end of the chapter. The
best way to develop a comfort level with entropy is to practice and learn by doing.
Important Equations
Entropy is a state change, and for an ideal gas,
ig T V ig T P
ΔS = C V ln ----- + R ln ----- or ΔS = C P ln ----- – R ln ----- (*ig) 4.29
i i i i
T V T P
For a condensed phase, the first term of the second equation should be used for a first approxi-
mation using the heat capacity for the appropriate phase.
Of course, the most important equation of this chapter is the complete entropy balance, but it
may be convenient to remember some of its most common simplifications.
ΔS = 0 for a fluid in an adiabatic reversible process, like across a steady-state adiabatic

reversible compressor or turbine or within an unsteady-state adiabatic reversible piston/cylinder.
ΔS = Qrev/T for a fluid in any process, like an isothermal reversible compressor. For an irre-
versible process, we design a reversible pathway to the actual final state.
ΔS = 0 for a the entropy in a reversible adiabatic leaking tank.
Pay careful attention to the subtle distinctions between these equations. A common mistake is
to write ΔS = 0 whenever you see the word “reversible.” Remember that reversibility is coupled to
entropy generation, not directly to S or ΔS. For entropy changes of a fluid, a smart approach is to
write ΔS = Qrev/T always and then scratch a line through Qrev after you deliberately determine that
the process is adiabatic and reversible. A fluid in an irreversible adiabatic process will have an
entropy change (and Qrev) even though the actual heat transfer is zero. Note that the entropy bal-
ance uses the actual heat transfer, Q, not Qrev. Only for a reversible process are they identical.
The distinction between ΔS = 0 and ΔS = 0 is perhaps subtler. By writing ΔS = 0, we emphasize

that only the specific entropy of the fluid remains constant. When ΔS = 0 for an open system, the
quantity ΔS = nfSf – niSi = SΔn will be non-zero whenever S is not at the reference state.
Disorder must increase if two different gases are mixed slowly and adiabatically, but it is diffi-
cult to see how to compute the entropy change from the macroscopic definition of dS. For ideal
solutions, the relation developed from the microscopic approach is:
ΔS mix
is = – R
 xi ln xi 4.8
i
This equation is useful for estimating the effects of mixing in many situations, even beyond the
assumption of ideal gases from which it derives. Eqn. 4.8 also conveys how disorder and mixing
are not strictly related to heating, as one might infer from the macroscopic definition of entropy.
The entropy of mixing will be of major importance in Unit III in the discussion of mixtures.
Section 4.17 Practice Problems 187
4.17 PRACTICE PROBLEMS

P4.1 Call placement of a particle in box A, “heads” and placement in box B, “tails.” Given one
particle, there are two ways of arranging it, H or T. For two particles, there are four ways of
arranging them, {HH,HT,TH,TT}.We can treat the microstates by considering each particle
in order. For example, {H T H H} means the first particle is in box A, the second in box B,
the third in box A, and the fourth in box A.
(a) List and count the ways of arranging three particles. Now consider four particles. What
is the general formula for the number of arrangements versus the number of particles?
(ANS. 2N)
(b) How many arrangements correspond to having two particles in box A and one in box
B? What is the probability of {2H,1T}? (ANS. 3/8)
(c) How many arrangements correspond to {2H,2T}. {3H,2T}. {4H,2T}. {3H,3T}? (ANS.
N!/[(N − m)!m!])
(d) List the macrostates and corresponding number of microstates for an eight-particle,
two-box system. What portion of all microstates are parts of either 5:3, 4:4, or 3:5
macrostates? (ANS. 71%)
(e) What is the change of entropy in going from a 5:3 macrostate to a 4:4 macrostate?
(ANS. 3.08E-24 J/K)
(f) Use Stirling’s approximation to estimate the change of entropy in going from a distri-
bution of 50.1% of 6.022E23 in box A to a distribution of 50.001%, and from 50.001%
to 50.000%. (ANS. 1.2E18 J/K)
P4.2 Twenty molecules are contained in a piston + cylinder at low pressure. The piston moves
such that the volume is expanded by a factor of 4 with no work produced of any kind.
Compute ΔS/k. (ANS. 23.19)
P4.3 Fifteen molecules are distributed as 9:4:2 between equal-sized boxes A:B:C, respectively.
The partitions between the boxes are removed, and the molecules distribute themselves
evenly between the boxes. Compute ΔS /k. (ANS. 11.23)
P4.4 Rolling two die (six-sided cubes with numbers between 1 and 6 on each side) is like putting
two particles in six boxes. Compute ΔS/k for going from double sixes to a four and three.
(ANS. 0.693)
P4.5 Estimate the change in entropy when one mole of nitrogen is compressed by a piston in a
cylinder from 300 K and 23 liters/mol to 400 K and 460 liters/mol. (CP = 7/2R)
(ANS. 1.07 kJ/kgK)
P4.6 Steam at 400°C and 10 bar is left in an insulated 10 m3 cylinder. The cylinder has a small leak,
however. Compute the conditions of the steam after the pressure has dropped to 1 bar. What is
the change in the specific entropy of the steam in the cylinder? Is this a reversible process? The
mass of the cylinder is 600 kg, and its heat capacity is 0.1 cal/g-K. Solve the problem with and
without considering the heat capacity of the cylinder. (ANS. (a)~120°C; (b) 360°C)
P4.7 A mixture of 1CO:2H2 is adiabatically and continuously compressed from 5 atm and 100°F
to 100 atm and 1100°F. Hint: For this mixture, CP = x1CP1 + x2CP2.
(a) Estimate the work of compressing 1 ton/h of the gas. (CP = 7/2R) (ANS. 1.3E6 BTU/h)
(b) Determine the efficiency of the compressor. (ANS. 76%)
P4.8 An adiabatic compressor is used to continuously compress nitrogen (CP /R = 7/2) from 2 bar
and 300 K to 15 bar. The compressed nitrogen is found to have an outlet temperature of 625 K.
How much work is required (kJ/kg)? What is the efficiency of the compressor? (ANS. 9.46
kJ/mol, 72%)
P4.9 An adiabatic compressor is used to continuously compress low-pressure steam from 0.8
MPa and 200°C to 4.0 MPa and 500°C in a steady-state process. What is the work required
per kg of steam through this compressor? Compute the efficiency of the compressor. (ANS.
606 J/g, 67%)
P4.10 An adiabatic turbine is supplied with steam at 2.0 MPa and 600°C and the steam exhausts
at 98% quality and 24°C. Compute the work output per kg of steam. Compute the effi-
ciency of the turbine. (ANS. 1.2E3 kJ, 85%)
P4.11 An adiabatic compressor has been designed to continuously compress 1 kg/s of saturated
vapor steam from 1 bar to 100 bar and 1100°C. Estimate the power requirement of this com-
pressor in horsepower. Determine the efficiency of the compressor. (ANS. 3000 hp, 60%)
P4.12 Ethylene gas is to be continuously compressed from an initial state of 1 bar and 20°C to a
final pressure of 18 bar in an adiabatic compressor. If compression is 70% efficient com-
pared with an isentropic process, what will be the work requirement and what will be the
final temperature of the ethylene? Assume the ethylene behaves as an ideal gas with CP =
44 J/mol-K. (ANS. 13.4 kJ/mol, 596 K)
P4.13 Operating a wind tunnel for aircraft experiments begins with adiabatically and reversibly
compressing atmospheric air (300 K) into long cylinders comprising a total volume of 20
m3 at 200 bars. The cylinders are initially at 1 bar. Estimate the minimal amount of work
required (MJ) to perform the compression step. (ANS. online.)
(a) Write the most appropriate energy balance(s) for this process. Clearly identify the sys-
tem(s) pertaining to your energy balance(s). Explain your reasoning briefly.
(b) Write the most appropriate entropy balance(s) for this process. Clearly identify the sys-
tem(s) pertaining to your entropy balance(s). Explain your reasoning briefly.
(c) Solve for the minimal amount of work required (MJ) to perform the compression step.
P4.14 As part of a refrigeration cycle, Freon 134a is adiabatically compressed from the saturated
vapor at –60°C (note the negative sign on temperature) to 1017 kPa and 100°C.
(a) How much work is required in kJ/kg?
(b) Estimate the efficiency of the compressor.
(ANS. 121, 75%)
P4.15 Steam is produced at 30 bar and some unknown temperature. A small amount of steam is
bled off and goes through an adiabatic throttling valve to 1 bar. The temperature of the
steam exiting the throttling valve is 110°C. What is the value of the specific entropy of the
steam before entering the throttle? (ANS. 5.9736 J/g-K)
P4.16 Suppose the expansion in problem P2.19 was completely adiabatic instead of isothermal
and CP = 7 cal/(mol-K). How would the height of the piston be affected? Must we generate
heat or consume heat to maintain isothermal operation? (ANS. decrease, generate)
P4.17 It is desired to determine the volume of an initially evacuated tank by filling it from an 80
liter cylinder of air at 300 bar and 300 K. The final pressure of both tanks is 5 bars. Esti-
mate the volume in liters. (ANS. 4720 L)
P4.18 An insulated cylinder is fitted with a freely floating piston, and contains 0.5 kg of steam at
9 bar and 90% quality. The space above the piston, initially 0.05m3, contains air at 300 K to
maintain the pressure on the steam. Additional air is forced into the upper chamber, forcing
the piston down and increasing the steam pressure until the steam has 100% quality. The
final steam pressure is 30 bars, and the work done on the steam is 360 kJ, but the air above
Section 4.18 Homework Problems 189
the steam has not had time to exchange heat with the piston, cylinder, or surroundings. The
air supply line is at 50 bar and 300 K. What is the final temperature of the air in the upper
chamber? (ANS. online)
P4.19 A well-insulated cylinder, fitted with a frictionless piston, initially contained 9 kg of liquid
water and 0.4 kg of water vapor at a pressure of 1.4 MPa. 2 kg of steam at 1.6 MPa was
admitted to the cylinder while the pressure was held constant by allowing the piston to
expand. (ANS. online)
(a) Write the energy balance for this process.
(b) If the final volume of the contents of the cylinder was six times the initial volume,
determine the temperature of the superheated steam that was admitted to the cylinder.
P4.20 Many action movies show gas cylinders that have their caps knocked off. The tanks go fly-
ing around wreaking havoc (only on the bad guys, of course). How much velocity could a
tank like that really generate? For an upper bound, consider a tank traveling horizontally on
a frictionless surface with an isentropic nozzle taking the place of the cap that has been
knocked off. Suppose the cylinder weighs 70 kg and holds 50 L of He at 100bar, 300 K.
(a) Write the most appropriate energy balance(s) for this process. Clearly identify the sys-
tem(s) pertaining to your energy balance(s). Explain your reasoning briefly.
(b) Write the most appropriate entropy balance(s) for this process. Clearly identify the sys-
tem(s) pertaining to your entropy balance(s). Explain your reasoning briefly.
(c) Solve for the total kinetic energy (MJ) developed by the tank and its velocity.
4.18 HOMEWORK PROBLEMS

4.1 Extending Example 4.2 on page 141 from solids to gases is straightforward if you recall the
development of Eqn. 1.13 on page 19. Consider N2 for example. Being diatomic, we
should expect that Uig = 2(3NAkT/2) = 6RT/2 in the limit of classical vibrations. Vibrational
energy means that heat can be absorbed in the vibration of a bond. Since N2 has only one
bond, it can only absorb energy in one way, removing one degree of freedom. We show in
Eqn. 6.49 on page 240 that ΔUvib/RT = βε/[exp(–βε) – 1] is the change in energy due to
vibration. For now, without concern for the proof, assume ΔUvib as given. Adapting Exam-
ple 4.2 for N2 then gives: Uig/RT = 2.5 + βε/[exp(–βε) – 1].
a. Use the NIST WebBook to plot data for CV of N2 at 0.1 MPa and T = [150, 2000 K].
b. Derive an expression for CV based on above dissussion. Evaluate your expression at
1000K assuming ε/k = 1000K.
c. Regress an optimal value for ε/k of N2 and plot a comparison of the calculated results to
experimental data. Show the calculated results as a curve with no points.
4.2 An ideal gas, with temperature-independent CP = (7/2)R, at 15°C and having an initial vol-
ume of 60 m3, is heated at constant pressure (P = 0.1013 MPa) to 30°C by transfer of heat
from a reservoir at 50°C. Calculate ΔSgas, ΔSheat reservoir, ΔS universe. What is the irreversible
feature of this process?
4.3 Steam undergoes a state change from 450°C and 3.5 MPa to 150°C and 0.3 MPa. Deter-
mine ΔH and ΔS using the following:
(a) Steam table data

(b) Ideal gas assumptions (be sure to use the ideal gas heat capacity for water)
4.4 The following problems involve one mole of an ideal monatomic gas, C P = 5R/2 , in a
variable volume piston/cylinder with a stirring paddle, an electric heater, and a cooling coil
through which refrigerant can flow (see figure). The piston is perfectly insulated. The piston
contains 1 gmole of gas. Unless specified, the initial conditions are: T i = 25°C, P i = 5 bar.
Heater Coil
Cooling Coil
(a) Status: Heater on; cooler off; paddle off; piston fixed. Five kJ are added by the heater.
Find ΔU, ΔS, ΔP, and ΔT.
(b) Status: Heater off; cooler off; paddle off; piston moveable. What reversible volume
change will give the same temperature rise as in part (a)? Also find ΔU, ΔS, and ΔP.
(c) Status: Heater off; cooler off; paddle on; piston fixed. What shaft work will give the
same ΔU, ΔS as part (a)?
(d) Status: Heater off; cooler off; paddle on; piston fixed. The stirring motor is consuming
55 watts and is 70% efficient. What rate is the temperature changing? At what initial
rates are U and S changing?
(e) Status: Heater unknown; cooler unknown; paddle off; piston free. We wish to perform a
reversible isothermal compression until the volume is half of the initial volume. If the
volume is decreasing at 2.0 cm3/s, at what rate should we heat or cool? Express your
answer in terms of the instantaneous volume. What is the total heat transfer necessary?
4.5 When a compressed gas storage tank fails, the resultant explosion occurs so rapidly that the
gas cloud can be considered adiabatic and assumed to not mix appreciably with the sur-
rounding atmosphere. Consider the failure of a 2.5-m3 air storage tank initially at 15 bar.
Atmospheric pressure is 1 bar, CP = 7R/2. Provide an estimate by assuming reversibility.
(a) Calculate the work done on the atmosphere. Does the reversibility approximation over-
estimate or under-estimate the actual work?
(b) A detonation of 1 kg of TNT releases about 4.5 MJ of work. Calculate the equivalent
mass of TNT that performs the same work as in part (a).
4.6 Work problem 4.5 but consider a steam boiler that fails. The boiler is 250 L in size, operat-
ing at 4 MPa, and half full of liquid.
4.7 An isolated chamber with rigid walls is divided into two equal compartments, one contain-
ing gas at 600 K and 1 MPa and the other evacuated. The partition between the two com-
partments ruptures. Compute the final T, P, and ΔS for the following:
(a) An ideal gas with CP /R = 7/ 2

(b) Steam.
4.8 An isolated chamber is divided into two equal compartments, one containing gas and the
other evacuated. The partition between the two compartments ruptures. At the end of the
process, the temperature and pressure are uniform throughout the chamber.
(a) If the filled compartment initially contains an ideal gas at 25 MPa and 650 K, what is
the final temperature and pressure in the chamber? What is ΔS for the process? Assume
a constant heat capacity of CP/R = 4.041.
(b) If the filled chamber initially contains steam at 25 MPa and 650 K, what is the final
temperature and pressure in the chamber? What is ΔS for the process? (Use the steam
tables.)
4.9 Airplanes are launched from aircraft carriers by means of a steam catapult. The catapult is
a well-insulated cylinder that contains steam, and is fitted with a frictionless piston. The
piston is connected to the airplane by a cable. As the steam expands, the movement of the
piston causes movement of the plane. A catapult design calls for 270 kg of steam at 15 MPa
and 450°C to be expanded to 0.4 MPa. How much work can this catapult generate during a
single stroke? Compare this to the energy required to accelerate a 30,000 kg aircraft from
rest to 350 km per hour.
4.10 We have considered heat and work to be path-dependent. However, if all heat transfer with
surroundings is performed using a reversible heat transfer device (some type of reversible
Carnot-type device), work can be performed by the heat transfer device during heat trans-
fer to the surroundings. The net heat transferred to the surroundings and the net work done
will be independent of the path. Demonstrate this by calculating the work and heat interac-
tions for the system, the heat transfer device, and the sum for each of the following paths
where the surroundings are at Tsurr = 273 K. The state change is from state 1, P1 = 0.1 MPa,
T1 = 298 K and state 2, P2 = 0.5 MPa and T2 which will be found in part (a). CP = 7R/2.
(a) Consider a state change for an ideal gas in a piston/cylinder. Find T2 by an adiabatic
reversible path. Find the heat and work such that no entropy is generated in the uni-
verse. This is path a. Sketch path a qualitatively on a P-T diagram.
(b) Now consider a path consisting of step b, an isothermal step at T1, and step c, an iso-
baric step at P2. Sketch and label the step on the same P-T diagram created in (a). To
avoid generation of entropy in the universe, use heat engines/pumps to transfer heat
during the steps. Calculate the WEC and WS as well as the heat transfer with the sur-
roundings for each of the steps and overall. Compare to part (a) the total heat and work
interactions with the surroundings.
(c) Now consider a path consisting of step d, an isobaric step at P1, and step e, an isother-
mal step at T2. Calculate the WEC and WS as well as the heat transfer with the surround-
ings for each of the steps and overall. Compare to part (a) using this pathway and
provide the same documentation as in (b).
4.11 Consider the wintertime heating of a house with a furnace compared to addition of Carnot
heat engines/pumps. To compensate for heat losses to the surroundings, the· house is main-
tained at a constant temperature Thouse by a constant rate of heat transfer, Q house . The fur-
nace operates at a constant
· temperature
· TF, and with direct heat transfer, the heat required
from the furnace, Q F is equal to Q house .
(a) Instead of direct heat transfer, if we utilize the surroundings, at TS , as an additional heat
·
source and include heat pump technology, Q F may be reduced by generating work
from a heat engine operating between TF and TS, then applying that work energy to a
heat pump operating between TS and Thouse. Given that TF = 800 K, T = 293 K, TS = 265
· ·
K, and Q house = 40 kJ/h, determine Q F utilizing heat pump technology. No other
sources of energy may be used.
(b) Another option is to run a heat engine between TF and Thouse and the heat pump
between TS and Thouse. Compare this method with part (a).
4.12 An ideal gas enters a valve at 500 K and 3 MPa at a steady-state rate of 3 mol/min. It is
throttled to 0.5 MPa. What is the rate of entropy generation? Is the process irreversible?
4.13 SO2 vapor enters a heat exchanger at 100°C and at a flowrate of 45 mole/h. If heat is trans-
ferred to the SO2 at a rate of 1,300 kJ/h, what is the rate of entropy transport in the gas at
out in
the outlet relative to the inlet in kJ/K/h given by ( S – S )n· ?
4.14 An ideal gas stream (Stream A), CP = 5R /2, 50 mole/h, is heated by a steady-state heat
exchanger from 20°C to 100°C by another stream (Stream B) of another ideal gas, CP = 7R/ 2,
45 mole/h, which enters at 180°C. Heat losses from the exchanger are negligible.
(a) For concurrent flow in the heat· exchanger, calculate the molar entropy changes
(Sout − Sin) for each stream, and S gen for the heat exchanger.
(b) For countercurrent flow in the ·heat exchanger, calculate the molar entropy changes
(Sout − Sin) for each stream, and S gen for the heat exchanger. Comment on the compari-
son of results from parts (a) and (b).
4.15 An inventor has applied for a patent on a device that is claimed to utilize 1 mole/min of air
(assumed to be an ideal gas) with temperature independent CP = (7/2)R which enters at 500 K
and 2 bar, and leaves at 350 K and 1 bar. The process is claimed to produce 2000 J/min of
work and to require an undisclosed amount of heat transfer with a heat reservoir at 300 K.
Should the inventor be issued a patent on this device?
4.16 Two streams of air are mixed in a steady-state process shown below. Assume air is an ideal
gas with a constant heat capacity CP = 7R/ 2.
(a) What is the temperature of the stream leaving the tank if the process is adiabatic?
(b) What is the rate of entropy generation within the tank if the process is adiabatic?
(c) If we duplicated the stream conditions (temperatures, pressures, and flowrates) with an
internally reversible process, what is the maximum rate at which work could be
obtained? If desirable, you are permitted to transfer heat to the surroundings at the sur-
roundings’ temperature of 295 K.
Stream A
0.167 mol/s
250 K
1 bar Stream C
1 bar
Stream B
0.833 mol/s
310 K
1 bar
4.17 Air is flowing at steady state through a 5 cm diameter pipe at a flow rate of 0.35 mole/min
at P = 5 bar and T = 500 K. It flows through a throttle valve and exits at 1 bar. Assume air
is an ideal gas with CP = 29.1 J/mol-K. If the throttle valve was replaced by a reversible
steady-state flow device to permit exactly the same state change for the air in this steady-
state process, at what rate could work could be obtained? Heat transfer, if desired, can
occur with the surroundings at 298 K, which may be considered a reservoir.
4.18 A common problem in the design of chemical processes is the steady-state compression of
gases from a low pressure P1 to a much higher pressure P2. We can gain some insight about
optimal design of this process by considering adiabatic reversible compression of ideal
gases with stage-wise intercooling. If the compression is to be done in two stages, first
compressing the gas from P1 to P*, then cooling the gas at constant pressure down to the
compressor inlet temperature T1, and then compressing the gas to P2, what should the value
of the intermediate pressure be to accomplish the compression with minimum work?
4.19 Steam flowing at steady state enters a turbine at 400°C and 7 MPa. The exit is at 0.275 MPa.
The turbine is 85% efficient. What is the quality of the exiting stream? How much work is
generated per kg of steam?
4.20 An adiabatic steam turbine inlet is to be 4 MPa. The outlet of the turbine is to operate at
0.01 MPa, and provide saturated steam. The turbine has an efficiency of 85%. Determine
the superheat which is required on the turbine inlet, and the work produced by the turbine.
4.21 Steam is fed to an adiabatic turbine at 4 MPa and 500°C. It exits at 0.1 MPa.
(a) If the turbine is reversible, how much work is produced per kg of steam?
(b) If the turbine is 80% efficient, how much work is produced per kg of steam?
4.22 Methane is compressed in a steady-state adiabatic compressor (87% efficient) to 0.4 MPa.
What is the required work per mole of methane in kJ? If the flow is to be 17.5 kmol/h, how
much work must be furnished by the compressor (in kW)? What is the rate of entropy gen-
eration (in kJ/K/h)? (a) the inlet is at 0.1013 MPa and −240°F; (b) the inlet is 0.1013 MPa
and 200 K.
4.23 Methane is to be compressed from 0.05 MPa and −120°F to 5 MPa in a two-stage compres-
sor. In between adiabatic, reversible stages, a heat exchanger returns the temperature to −
120°F. The intermediate pressure is 1.5 MPa.
(a) What is the work required (kJ/kg) in the first compressor of methane?
(b) What is the temperature at the exit of the first compressor (°C)?
(c) What is the cooling requirement (kJ/kg) in the interstage cooler?
4.24 A steady stream (1000 kg/hr) of air flows through a compressor, entering at (300 K, 0.1 MPa)
and leaving at (425 K, 1 MPa). The compressor has a cooling jacket where water flows at
1500 kg/hr and undergoes a 20 K temperature rise. Assuming air is an ideal gas, calculate
the work furnished by the compressor, and also determine the minimum work required for
the same state change of air.
4.25 Propane is to be compressed from 0.4 MPa and 360 K to 4 MPa using a two-stage com-
pressor. An interstage cooler returns the temperature of the propane to 360 K before it
enters the second compressor. The intermediate pressure is 1.2 MPa. Both adiabatic com-
pressors have a compressor efficiency of 80%.
(a) What is the work required in the first compressor per kg of propane?
(b) What is the temperature at the exit of the first compressor?
(c) What is the cooling requirement in the interstage cooler per kg of propane?
4.26 (a) A steam turbine in a small electric power plant is designed to accept 5000 kg/h of steam
at 60 bar and 500°C and exhaust the steam at 1 bar. Assuming that the turbine is adia-
batic and reversible, compute the exit temperature of the steam and the power gener-
ated by the turbine.
(b) If the turbine in part (a) is adiabatic but only 80% efficient, what would be the exit tem-
perature of the steam? At what rate would entropy be generated within the turbine?
(c) One simple way to reduce the power output of the turbine in part (a) (100% efficient) is
by adjusting a throttling valve that reduces the turbine inlet steam pressure to 30 bar.
Compute the steam temperature to the turbine, the rate of entropy generation, and the
power output of the turbine for this case. Is this a thermodynamically efficient way of
reducing the power output? Can you think of a better way?
4.27 Steam is used in the following adiabatic turbine system to generate electricity; 15% of the
mass flow from the first turbine is diverted for other use.
P = 8 MPa
T = 550°C P = 5 MPa
300 kg/hr P = 0.8 MPa

15% withdrawn
for other use
(a) How much work (in kJ/h) is generated by the first turbine which is 80% efficient?
(b) How much work (in kJ/h) is generated by the second turbine which is 80% efficient?
(c) Steam for the turbines is generated by a boiler. How much heat must be supplied to
the boiler (not shown) which has 300 kg/h of flow? The stream entering the boiler is
T = 170°C, P = 8 MPa. The stream exiting the boiler matches the inlet to the first turbine.
4.28 Liquid nitrogen is useful for medical purposes and for research laboratories. Determine the
minimum shaft work needed to liquefy nitrogen initially at 298 K and 0.1013 MPa and
ending with saturated liquid at the normal boiling point, 77.4 K and 0.1013 MPa. The heat
of vaporization at the normal boiling point is 5.577 kJ/mol, and the surroundings are at 298 K.
The constant pressure heat capacity of gaseous nitrogen can be assumed to be independent
of temperature at 7/2R for the purpose of this calculation.
(a) Consider nitrogen entering a flow device at 1 mol/min. Give shaft work in kW.
(b) Consider nitrogen in a piston/cylinder device. Give the work in kJ per mole liquefied.
(c) Compare the minimum shaft work for the two processes. Is one of the processes more
advantageous than the other on a molar basis?
4.29 Propane flows into a steady-state process at 0.2 MPa and 280 K. The final product is to be
saturated liquid propane at 300 K. Liquid propane is to be produced at 1000 kg/h. The sur-
roundings are at 295 K. Using a propane property chart, determine the rate of heat transfer
and minimum work requirement if the process is to operate reversibly.
4.30 Propane (1000 kg/hr) is to be liquefied following a two-stage compression. The inlet gas is
to be at 300 K and 0.1 MPa. The outlet of the adiabatic compressor I is 0.65 MPa, and the
propane enters the interstage cooler where it exits at 320 K, then adiabatic compressor II
raises the propane pressure to 4.5 MPa. The final cooler lowers the temperature to 320 K
before it is throttled adiabatically to 0.1 MPa. The adiabatic compressors have an effi-
ciency of 80%.
(a) Determine the work required by each compressor.

(b) If the drive motors and linkages are 80% efficient (taken together), what size motors
(hp) are required?
(c) What cooling is required in the interstage cooler and the final cooler?
(d) What percentage of propane is liquefied, and what is the final temperature of the pro-
pane liquid?
4.31 A heat exchanger operates with the following streams: Water in at 20°C, 30 kg/hr; water
out at 70°C; Organic in at 100°C, 41.8 kg/hr; organic out at 40°C.
(a) What is the maximum work that could be obtained if the flow rates and temperatures of
the streams remain the same, but heat transfer is permitted with the surroundings at 298 K?
(CP water = 4.184 kJ/(kgK), CP organic = 2.5 kJ/(kgK).)
(b) What is the maximum work that could be obtained by replacing the heat exchanger
with a reversible heat transfer device, where the inlet flowrates and temperatures are to
remain the same, the organic outlet temperature remains the same, and no heat transfer
with the surroundings occurs?
4.32 Presently, benzene vapors are condensed in a heat exchanger using cooling water. The ben-
zene (100 kmol/h) enters at 0.1013 MPa and 120°C, and exits at 0.1013 MPa and 50°C.
Cooling water enters at 10°C and exits at 40°C.
(a) What is the current demand for water (kg/h)?

(b) To what flowrate could the water demand be lowered by introducing a reversible heat
transfer device that is adiabatic with the surroundings? The temperature rise of water is
to remain the same. What work could be obtained from the new heat transfer device?
4.33 A Hilsch vortex tube is an unusual device that takes an inlet gas stream and produces a hot
stream and a cold stream without moving parts. A high-pressure inlet stream (A) enters
towards one end of the tube. The cold gas exits at outlet B on the end of the tube near the
inlet where the port is centered in the end cap. The hot stream exits at outlet C on the other
end of the tube where the exit is a series of holes or openings around the outer edge of the
end cap.
The tube works in the following way. The inlet stream A enters tangent to the edge of the
tube, and swirls as it cools by expansion. Some of the cool fluid exits at port B. The
remainder of the fluid has high kinetic energy produced by the volume change during
expansion, and the swirling motion dissipates the kinetic energy back into internal energy,
so the temperature rises before the gas exits at port C.
C
B
Inlet A is at 5 bar and 310 K and 3.2 mol/min. Outlet B is at 1 bar and 260 K. Outlet C is at
1 bar and 315 K. The tube is insulated and the fluid is air with CP = 7R/ 2.
(a) Determine the

· flowrates of streams B and C.
(b) Determine S gen for the Hilsch tube.
(c) Suppose a reversible heat engine is connected between the outlet streams B and C
which is run to produce the maximum work possible. The proposed heat engine may
only exchange heat between the streams and not with the surroundings as shown. The
final temperature of streams B and C will be TB' as they exit the apparatus. What is TB'?
C
B
B' WS C'
·
(d) What work output is possible in W? What is S gen for the entire system including the
tube plus the heat engine?
(e) Suppose that instead of using the heat engine, streams B and C were mixed directly
with one another to form a single outlet stream. What would
· this temperature be,· and
how does it compare with TB' from part (c)? Calculate S gen and compare it with S gen
from part (c). What do you conclude from the comparison?
4.34 Methane gas is contained in a 0.65-m3 gas cylinder at 6.9 MPa and 300 K. The cylinder is
vented rapidly until the pressure falls to 0.5 MPa. The venting occurs rapidly enough that
heat transfer between the cylinder walls and the gas can be neglected, as well as between
the cylinder and the surroundings. What is the final temperature and the final number of
moles of gas in the tank immediately after depressurization? Assume the expansion within
the tank is reversible, and the following:
(a) Methane is considered to be an ideal gas with CP /R = 4.298

(b) Methane is considered to be a real gas with properties given by a property chart.
4.35 A thermodynamically interesting problem is to analyze the fundamentals behind the prod-
uct called “fix-a-flat.” In reality, this product is a 500 mL can that contains a volatile com-
pound under pressure, such that most of it is liquid. Nevertheless, we can make an initial
approximation of this process by treating the contents of the can as an ideal gas. If the ini-
tial temperature of both the compressed air and the air in the tire is 300 K, estimate the initial
pressure in the compressed air can necessary to reinflate one tire from 1 bar to 3 bar. Also,
estimate the final air temperature in the tire and in the can. For the purposes of this calcula-
tion you may assume: air is an ideal gas with CP /R = 7/2, the tire does not change its size or
shape during the inflation process, and the inner tube of the tire has a volume of 40,000 cm3. We
will reconsider this problem with liquid contents, after discussing phase equilibrium in a
pure fluid.
4.36 Wouldn’t it be great if a turbine could be put in place of the throttle in problem 4.35? Then
you could light a small bulb during the inflation to see what you were doing at night. How
much energy (J) could possibly be generated by such a turbine if the other conditions were
the same as in problem 4.35?
4.37 A 1 m3 tank is to be filled using N2 at 300 K and 20 MPa. Instead of throttling the N2 into
the tank, a reversible turbine is put in line to get some work out of the pressure drop. If the
pressure in the tank is initially zero, and the final pressure is 20 MPa, what will be the final
temperature in the tank? How much work will be accomplished over the course of the
entire process? (Hint: Consider the entropy balance carefully.)
4.38 Two well-insulated tanks are attached as shown in the figure below. The tank volumes are
given in the figure. There is a mass-flow controller between the two tanks. Initially, the
flow controller is closed. At t = 0, the mass flow controller is opened to a flow of 0.1 mol/
s. After a time of 500 seconds, what are the temperatures of the two tanks? Neglect the heat
capacity of the tanks and piping. No heat transfer occurs between the two tanks. (After 500
seconds, the pressure in the left tank is still higher than the pressure in the right tank.) The
working fluid is nitrogen and the ideal gas law may be assumed. The ideal gas heat capac-
ity CP = 7/2·R may be assumed to be independent of T.
FC
5 m3 7 m3
TAi = 500 K
TBi = 300 K
PAi = 0.5 MPa
PBi = 0.09 MPa
4.39 Two storage tanks (0.1 m3 each) contain air at 2 bar. They are connected across a small
reversible compressor. The tanks, connecting lines, and compressor are immersed in a con-
stant temperature bath at 280 K. The compressor will take suction from one tank, compress
the gas, and discharge it to the other tank. The gas is at 280 K at all times. Assume that air
is an ideal gas with CP = 29.3 J/mol-K.
(a) What is the minimum work interaction required to compress the gas in one tank to
3 bar?
(b) What is the heat interaction with the constant temperature bath?
4.40 A constant pressure air supply is connected to a small tank (A) as shown in the figure
below. With valves B and C, the tank can be pressurized or depressurized. The initial con-
ditions are T = 300 K, P = 1.013 bar, CP = 29.3 J/(mol-K). Consider the system adiabatic.
(a) The tank is pressurized with valve B open and valve C closed. What is the final temper-
ature of the tank? Neglect the heat capacity of the tank and valves.
(b) Taking the system as the tank plus the valves, what is the entropy change of the system
due to pressurization? What is the entropy change of the air supply reservoir? What is
the entropy change of the universe? Use a reference state of 300 K and 1.013 bar.
(c) During depressurization with valve B closed and valve C open, how does the molar
entropy entering valve C compare with the molar entropy leaving? What is the temper-
ature of the tank following depressurization?
Atmosphere
Air supply B A C 1.013 bar
9 bar V = 1m3 295 K
292 K
4.41 The pressurization of problem 4.40 is performed by replacing the inlet valve with a revers-
ible device that permits pressurization that is internally reversible. The system is to remain
adiabatic with respect to heat transfer of the surroundings.
(a) What is the final temperature of the tank?

(b) How much work could be obtained?
4.42 A 2m3 tank is at 292 K and 0.1 MPa and it is desired to pressurize the tank to 3 MPa. The
gas is available from an infinite supply at 350 K and 5 MPa connected to the tank via a
throttle valve. Assume that the gas follows the ideal gas law with a constant heat capacity
of CP = 29 J/(mol-K).
(a) Modeling the pressurization as adiabatic, what is the final temperature in the tank and
the final number of moles when the pressure equals 3 MPa?
(b) Identify factors included in the idealized calculation of part (a) that contribute to irre-
versibilities.
(c) Identify factors neglected in the analysis of part (a) that would contribute to irrevers-
ibilities in a real process.
(d) If the pressurization could be performed reversibly, the final temperature might be dif-
ferent from that found in part (a). Clearly outline a procedure to calculate the tempera-
ture indicating that enough equations are provided for all unknowns. Also clearly state
how you would use the equations. Additional equipment is permissible provided that
the process remains adiabatic with regard to heat transfer to the surroundings.
(e) In part (d), would work be added, removed, or not involved in making the process
reversible? Provide equations to calculate the work interaction.
4.43 Two gas storage tanks are interconnected through an isothermal expander. Tank 1 (V = 1
m3) is initially at 298 K and 30 bar. Tank 2 (V = 1 m3) is initially at 298 K and 1 bar.
Reversible heat transfer is provided between the tanks, the expander, and the surroundings
at 298 K. What is the maximum work that can be obtained from the expander when isother-
mal flow occurs from tank 1 to tank 2?

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CHAPTER

Chapter Objectives: You Should Be Able to...

4.1 THE CONCEPT OF ENTROPY

Entropy may be contemplated microscopically and macroscopically. The microscopic perspec-

Macroscopic definition—Intensive entropy is a state property of the system. For a differential

Microscopic definition—Entropy is a measure of the molecular disorder of the system. Its

2. A simple system is not acted on by external force fields or inertial forces.

4.2 THE MICROSCOPIC VIEW OF ENTROPY

Entropy and Spatial Distributions: Configurational Entropy

Box A Box B Box A Box B Box A Box B Box A Box B

Microstate α Microstate β Microstate γ Microstate δ

(a) One particle in Box A (b) Two particles in Box A

Generalized Microstate Formulas

The general formula for M boxes is:10

8. In statistics, this is called the number of permutations.

Entropy and Isothermal Volume/Pressure Change for

We can develop an answer by applying Eqn. 4.4, and noting that 0! = 1:

Stirling’s approximation may be used for ln(N!) when N > 100,

A similar application of Stirling’s approximation gives,

Example 4.1 Entropy change and “lost work” in a gas expansion

Example 4.1 Entropy change and “lost work” in a gas expansion

Entropy of Mixing for Ideal Gases

ΔS = n O2 R ln ( 4 ) = n tot R [ – x O2 ln ( 0.25 ) ] = n tot R [ – x O2 ln ( x O2 ) ]

Entropy change for N2:

ΔS = n N2 R ln  --- = n tot R [ – x N2 ln ( 0.75 ) ] = n tot R [ – x N2 ln ( x N2 ) ]

Entropy change for total fluid:

ΔS = – n tot R [ x O2 ln ( x O2 ) + x N2 ln ( x N2 ) ] = – 4R ( – 0.562 ) = 18.7 J/K

Entropy and Temperature Change: Thermal Entropy

11. Moore, Schroeder, 1997. Am. J. Phys. 65:26–36.

U = qMεq + Mεq/2 for M/3 atoms 4.10

<qM> = qM/M = U/Mεq – 1/2 4.11

pi = (2+2–1)!/[2!(1!)] = 3!/2! = 3. Check.

For the case with qM = 3 and M = 4, pi = (3+4–1)!/[3!(3!)] = 20, as enumerated above.

Example 4.2 Stirling’s approximation in the Einstein solid

(a) (1): (3,0,0),(0,3,0),(0,0,3),(2,1,0),(2,0,1),(1,2,0),(1,0,2),(0,2,1),(0,1,2),(1,1,1) = 10. Check.

(b) Si = k ln(pi) = k { ln[(qMi+Mi–1)!] – ln[qMi!(Mi–1)!] }. Applying Stirling’s approximation,

S/k = [(qM+M–1)ln(qM+M–1)–(qM+M–1)] – qMlnqM + qM – (M–1)ln(M–1) + M–1 =

S/Mk = <qM>ln(1+1/<qM>) + ln(<qM>+1)

4.3 THE MACROSCOPIC VIEW OF ENTROPY

Entropy Definition (Macroscopic)

For a change in states, both sides of Eqn. 4.12 may be integrated,

where the following occurs:

Example 4.3 Adiabatic, reversible expansion of steam

W EC = ( 2823.1 – 3005.8 ) = – 182.7 kJ/kg

Example 4.4 A Carnot cycle based on steam

(a) Compute W(a→b) and QH.

Example 4.4 A Carnot cycle based on steam (Continued)

(e) ηθ = –Wnet/QH; Wnet = (264.67–66.08+191.1–132.6) = 257.1 kJ/kg;

Calculation of Entropy Changes in Closed Systems

Inserting Eqn. 2.3,

[ dU + PdV ] = dQ rev 4.16

Constant Pressure (Isobaric) Pathway

Since dH = CPdT at constant pressure, along a constant-pressure pathway, substituting for

Constant Volume Pathway

Constant Temperature (Isothermal) Pathway

Example 4.5 Ideal gas entropy changes in an adiabatic, reversible

For the reversible isothermal step we have

dU = dQrev − PdV = 0 or dQrev = PdV (ig)