1779

Chapter 19
The Second Law of Thermodynamics

Conceptual Problems

1 • Modern automobile gasoline engines have efficiencies of about 25%.
About what percentage of the heat of combustion is not used for work but
released as heat? (a) 25%, (b) 50%, (c) 75%, (d) 100%, (e) You cannot tell from
the data given.

Determine the Concept The efficiency of a heat engine is the ratio of the work
done per cycle W to the heat absorbed from the high-temperature reservoir Q
h
.
The percentage of the heat of combustion (heat absorbed from the high-
temperature reservoir) is the ratio of Q
c
to Q
h
. We can use the relationship
between W, Q
h
, and Q
c
(
c h
Q Q W − = ) to find Q
c
/ Q
h
.

Use the definition of efficiency and
the relationship between W, Q
h
, and
Q
c
to obtain:

h
c
h
c h
h
1
Q
Q
Q
Q Q
Q
W
− =

= = ε
Solving for Q
c
/ Q
h
yields:
ε − =1
h
c
Q
Q


Substitute for ε to obtain:
75 . 0 25 . 0 1
h
c
= − =
Q
Q

and ( ) c is correct.

2 • If a heat engine does 100 kJ of work per cycle while releasing 400 kJ
of heat, what is its efficiency? (a) 20%, (b) 25%, (c) 80%, (d) 400%, (e) You
cannot tell from the data given.

Determine the Concept The efficiency of a heat engine is the ratio of the work
done per cycle W to the heat absorbed from the high-temperature reservoir Q
h
. We
can use the relationship between W, Q
h
, and Q
c
(
c h
Q Q W − = ) to express the
efficiency of the heat engine in terms of Q
c
and W.

Use the definition of efficiency and
the relationship between W, Q
h
, and
Q
c
to obtain:

W
Q
Q W
W
Q
W
c
c h
1
1
+
=
+
= = ε
Chapter 19


1780

Substitute for Q
c
and W to obtain:
2 . 0
kJ 100
kJ 400
1
1
=
+
= ε
and ( ) a is correct.

3 • If the heat absorbed by a heat engine is 600 kJ per cycle, and it
releases 480 kJ of heat each cycle, what is its efficiency? (a) 20%, (b) 80%,
(c) 100%, (d) You cannot tell from the data given.

Determine the Concept The efficiency of a heat engine is the ratio of the work
done per cycle W to the heat absorbed from the high-temperature reservoir Q
h
. We
can use the relationship between W, Q
h
, and Q
c
(
c h
Q Q W − = ) to express the
efficiency of the heat engine in terms of Q
c
and Q
h
.

Use the definition of efficiency and
the relationship between W, Q
h
, and
Q
c
to obtain:

h
c
h
c h
h
1
Q
Q
Q
Q Q
Q
W
− =

= = ε
Substitute for Q
c
and Q
h
to obtain:
2 . 0
kJ 600
kJ 480
1 = − = ε
and ( ) a is correct.

4 • Explain what distinguishes a refrigerator from a ″heat pump.″

Determine the Concept The job of a refrigerator is to move heat from its cold
interior to the warmer kitchen environment. This process moves heat in a
direction that is opposite its ″natural″ direction of flow, analogous to the use of a
water pump to pump water out of a boat. The term heat pumps is used to describe
devices, such as air conditioners, that are used to cool living and working spaces
in the summer and warm them in the winter.

5 • [SSM] An air conditioner’s COP is mathematically identical to that
of a refrigerator, that is,
c
AC ref
COP COP = =
Q
W
. However a heat pump’s COP is
defined differently, as
h
hp
COP =
Q
W
. Explain clearly why the two COPs are
defined differently. Hint: Think of the end use of the three different devices.




Determine the Concept The COP is defined so as to be a measure of the
The Second Law of Thermodynamics


1781
effectiveness of the device. For a refrigerator or air conditioner, the important
quantity is the heat drawn from the already colder interior, Q
c
. For a heat pump,
the ideas is to focus on the heat drawn into the warm interior of the house, Q
h
.

6 • Explain why you cannot cool your kitchen by leaving your refrigerator
door open on a hot day. (Why does turning on a room air conditioner cool down
the room, but opening a refrigerator door does not?)

Determine the Concept As described by the second law of thermodynamics,
more heat must be transmitted to the outside world than is removed by a
refrigerator or air conditioner. The heating coils on a refrigerator are inside the
room, so the refrigerator actually heats the room in which it is located. The
heating coils on an air conditioner are outside one’s living space, so the waste
heat is vented to the outside.

7 • Why do steam-power-plant designers try to increase the temperature
of the steam as much as possible?

Determine the Concept Increasing the temperature of the steam increases its
energy content. In addition, it increases the Carnot efficiency, and generally
increases the efficiency of any heat engine.

8 • To increase the efficiency of a Carnot engine, you should
(a) decrease the temperature of the hot reservoir, (b) increase the temperature of
the cold reservoir, (c) increase the temperature of the hot reservoir, (d) change the
ratio of maximum volume to minimum volume.

Determine the Concept Because the efficiency of a Carnot cycle engine is given
by
h
c
C
1
T
T
− = ε , you should increase the temperature of the hot reservoir. ( ) c is
correct.

9 •• [SSM] Explain why the following statement is true: To increase the
efficiency of a Carnot engine, you should make the difference between the two
operating temperatures as large as possible; but to increase the efficiency of a
Carnot cycle refrigerator, you should make the difference between the two
operating temperatures as small as possible.

Determine the Concept A Carnot-cycle refrigerator is more efficient when the
temperatures are close together because it requires less work to extract heat from
an already cold interior if the temperature of the exterior is close to the
temperature of the interior of the refrigerator. A Carnot-cycle heat engine is more
efficient when the temperature difference is large because then more work is done
by the engine for each unit of heat absorbed from the hot reservoir.
10 •• A Carnot engine operates between a cold temperature reservoir of
Chapter 19


1782
27°C and a high temperature reservoir of 127°C. Its efficiency is (a) 21%,
(b) 25%, (c) 75%, (d) 79%.

Determine the Concept The efficiency of a Carnot cycle engine is given by
h c C
1 T T − = ε where T
c
and T
h
(in kelvins) are the temperatures of the cold and hot
reservoirs, respectively.

Substituting numerical values for T
c

and T
h
yields:
25 . 0
K 400
K 300
1
C
= − = ε
( ) b is correct.

11 •• The Carnot engine in Problem 10 is run in reverse as a refrigerator. Its
COP is (a) 0.33, (b) 1.3, (c) 3.0 (d) 4.7.

Determine the Concept The coefficient of performance of a Carnot cycle engine
run in reverse as refrigerator is given by
W
Q
c
ref
COP = . We can use the relationship
between W, Q
c
, and Q
h
to eliminate W from this expression and then use the
relationship, applicable only to a device operating in a Carnot cycle,
h
c
h
c
T
T
Q
Q
= to
express the refrigerator’s COP in terms of T
c
and T
h
.

The coefficient of performance of a
refrigerator is given by:
W
Q
c
ref
COP =
or, because
c h
Q Q W − = ,
c h
c
ref
COP
Q Q
Q

=

Dividing the numerator and
denominator of this fraction by Q
c
yields:
1
1
COP
c
h
ref

=
Q
Q


For a device operating in a Carnot
cycle:

h
c
h
c
T
T
Q
Q
=

Substitute in the expression for
COP
ref
to obtain:
1
1
COP
c
h
C ref,

=
T
T


The Second Law of Thermodynamics


1783

Substitute numerical values and
evaluate COP
ref, C
:
0 . 3
1
K 300
K 400
1
COP
C ref,
=

=
( ) c is correct.

12 •• On a humid day, water vapor condenses on a cold surface. During
condensation, the entropy of the water (a) increases, (b) remains constant,
(c) decreases, (d) may decrease or remain unchanged. Explain your answer.

Determine the Concept When water vapor condenses, its entropy decreases (the
liquid state is a more ordered state than is the vapor state). ) (c is correct.

13 •• An ideal gas is taken reversibly from an initial state P
i
, V
i
, T
i
to the
final state P
f
, V
f
, T
f
. Two possible paths are (A) an isothermal expansion followed
by an adiabatic compression and (B) an adiabatic compression followed by an
isothermal expansion. For these two paths, (a) ΔE
int A
> ΔE
int B
, (b) ΔS
A
> ΔS
B
,
(c) ΔS
A
< ΔS
B
, (d) None of the above.

Determine the Concept The two paths
are shown on the PV diagram to the
right. We can use the concept of a state
function to choose from among the
alternatives given as possible answers
to the problem.

P
V

i
V
f
V

f
P

i
P
i
f
B
B
A
A

i
T

f
T


(a) Because E
int
is a state function and the initial and final states are the same for
the two paths,
B int, A int,
E E Δ = Δ .

(b) and (c) S, like E
int
, is a state function and its change when the system moves
from one state to another depends only on the system’s initial and final states. It
is not dependent on the process by which the change occurs. Thus
B A
S S Δ = Δ .

(d) ) (d is correct.

14 •• Figure 19-12 shows a thermodynamic cycle for an ideal gas on an ST
diagram. Identify this cycle and sketch it on a PV diagram.
Chapter 19


1784
Determine the Concept The processes
A→B and C→D are adiabatic and the
processes B→C and D→A are
isothermal. Therefore, the cycle is the
Carnot cycle shown in the adjacent PV
diagram.
P
V
A
B
C
D


15 •• Figure 19-13 shows a thermodynamic cycle for an ideal gas on an SV
diagram. Identify the type of engine represented by this diagram.

Determine the Concept Note that A→B is an adiabatic expansion, B→C is a
constant-volume process in which the entropy decreases, C→D is an adiabatic
compression and D→A is a constant-volume process that returns the gas to its
original state. The cycle is that of the Otto engine (see Figure 19-3). The points A,
B, C, and D in Figure 19-13 correspond to points c, d, a, and b, respectively, in
Figure 19-3.

16 •• Sketch an ST diagram of the Otto cycle. (The Otto cycle is discussed
in Section 19-1.)

Determine the Concept The Otto cycle consists of four quasi-static steps. Refer
to Figure 19-3. There a→b is an adiabatic compression, b→c is a constant volume
heating, c→d is an adiabatic expansion and d→a is a constant-volume cooling.
So, from a to b, S is constant and T increases, from b to c, heat is added to the
system and both S and T increase, from c→d S is constant while T decreases, and
from d to a both S and T decrease.

To determine how S depends on T
along b→c and d→a, consider the
entropy change of the gas from point
b to an arbitrary point on the path
b→c where the entropy and
temperature of the gas are S and T,
respectively:

T
Q
S = Δ
where, because heat is entering the
system, Q is positive.
Because W
on
= 0 for this constant-
volume process:

( )
b
T T C T C Q Q E − = Δ = = = Δ
V V in int

Substituting for Q yields:
( )






− =

= Δ
T
T
C
T
T T C
S
b b
1
V
V


The Second Law of Thermodynamics


1785
On path b→c the entropy is given by:







− + = Δ + =
T
T
C S S S S
b
b b
1
V


The first and second derivatives,
dT dS and
2 2
dT S d , give the slope
and concavity of the path. Calculate
these derivatives assuming C
V
is
constant. (For an ideal gas C
V
is a
positive constant.):

2
V
T
T
C
dT
dS
b
=
3
V
2
2
2
T
T
C
dT
S d
b
− =
These results tell us that, along path b→c, the slope of the path is positive and the
slope decreases as T increases. The concavity of the path is negative for all T.

Following the same procedure on
path d→a gives:







− + =
T
T
C S S
d
d
1
V

2
V
T
T
C
dT
dS
d
=
3
V
2
2
2
T
T
C
dT
S d
d
− =

These results tell us that, along path d→a, the slope of the path is positive and the
slope decreases as T increases. The concavity of the path is negative for all T.

An ST diagram for the Otto cycle is
shown to the right.
S
T
a
b
c
d


17 •• [SSM] Sketch an SV diagram of the Carnot cycle for an ideal gas.

Determine the Concept Referring to Figure 19-8, process 1→2 is an isothermal
expansion. In this process heat is added to the system and the entropy and volume
increase. Process 2→3 is adiabatic, so S is constant as V increases. Process 3→4
is an isothermal compression in which S decreases and V also decreases. Finally,
process 4→1 is adiabatic, that is, isentropic, and S is constant while V decreases.

Chapter 19


1786
During the isothermal expansion (from
point 1 to point 2) the work done by
the gas equals the heat added to the
gas. The change in entropy of the gas
from point 1 (where the temperature is
T
1
) to an arbitrary point on the curve is
given by:

1
T
Q
S = Δ

For an isothermal expansion, the
work done by the gas, and thus the
heat added to the gas, are given by:









= =
1
1
ln
V
V
nRT W Q
Substituting for Q yields:









= Δ
1
ln
V
V
nR S

Since S S S Δ + =
1
, we have:









+ =
1
1
ln
V
V
nR S S

The graph of S as a function of V for an
isothermal expansion shown to the right
was plotted using a spreadsheet
program. This graph establishes the
curvature of the 1→2 and 3→4 paths
for the SV graph.

V
S
An SV graph for the Carnot cycle
(see Figure 19-8) is shown to the
right.
V
S
1
2
3
4


18 •• Sketch an SV diagram of the Otto cycle. (The Otto cycle is discussed in
Section 19-1.)


The Second Law of Thermodynamics


1787
Determine the Concept The Otto cycle is shown in Figure 19-3. Process a→b
takes place adiabatically and so both Q = 0 and ΔS = 0 along this path. Process
b→c takes place at constant volume. Q
in
, however, is positive and so, while
ΔV = 0 along this path, Q > 0 and, therefore ΔS > 0. Process c→d also takes
place adiabatically and so, again, both Q = 0 and ΔS = 0 along this path. Finally,
process d→a is a constant-volume process, this time with heat leaving the
system and ΔS < 0. A sketch of the SV diagram for the Otto cycle follows:
a
b
c
d
S
V


19 •• Figure 19-14 shows a thermodynamic cycle for an ideal gas on an SP
diagram. Make a sketch of this cycle on a PV diagram.

Determine the Concept Process A→B
is at constant entropy; that is, it is an
adiabatic process in which the pressure
increases. Process B→C is one in
which P is constant and S decreases;
heat is exhausted from the system and
the volume decreases. Process C→D is
an adiabatic compression. Process
D→A returns the system to its original
state at constant pressure. The cycle is
shown in the adjacent PV diagram.

P
V
A
B
C
D


20 •• One afternoon, the mother of one of your friends walks into his room
and finds a mess. She asks your friend how the room came to be in such a state,
and your friend replies, ″Well, it is the natural destiny of any closed system to
degenerate toward greater and greater levels of entropy. That’s all, Mom.″ Her
reply is a sharp ″Nevertheless, you’d better clean your room!″ Your friend retorts,
″But that can’t happen. It would violate the second law of thermodynamics.″
Critique your friend’s response. Is his mother correct to ground him for not
cleaning his room, or is cleaning the room really impossible?

Determine the Concept The son is out of line, here, but besides that, he’s also
wrong. While it is true that systems tend to degenerate to greater levels of
disorder, it is not true that order cannot be brought forth from disorder. What is
Chapter 19


1788
required is an agent doing work – for example, your friend – on the system in
order to reduce the level of chaos and bring about order. His cleanup efforts will
be rewarded with an orderly system after a sufficient time for him to complete the
task. It is true that order will not come about from the disordered chaos of his
room – unless he applies some elbow grease.

Estimation and Approximation

21 • Estimate the change in COP of your electric food freezer when it is
removed from your kitchen to its new location in your basement, which is 8°C
cooler than your kitchen.

Picture the Problem We can use the definition of the coefficient of performance
to express the ratio of the coefficient of performance in your basement to the
coefficient of performance in the kitchen. If we further assume that the freezer
operates in a Carnot cycle, then we can use the proportion
c h c h
T T Q Q = to
express the ratio of the coefficients of performance in terms of the temperatures in
the kitchen, basement, and freezer.

The ratio of the coefficients of
performance in the basement and
kitchen is given by:
kit c,
kit c,
basement c,
basement c,
kit
basement
COP
COP
W
Q
W
Q
=

Because
c h
Q Q W − = for a heat
engine or refrigerator:
kit c, kit h,
kit c,
basement c, basement h,
basement c,
kit
basement
COP
COP
Q Q
Q
Q Q
Q


=

Divide the numerators and
denominators by Q
c,basement
and Q
c,kit

and simplify to obtain:
1
1
1
1
1
1
COP
COP
basement c,
basement h,
kit c,
kit h,
kit c,
kit h,
basement c,
basement h,
kit
basement


=


=
Q
Q
Q
Q
Q
Q
Q
Q

The Second Law of Thermodynamics


1789
If we assume that the freezer unit
operates in a Carnot cycle, then
c
h
c
h
T
T
Q
Q
= and our expression for the
ratio of the COPs becomes:

1
1
COP
COP
basement c,
basement h,
kit c,
kit h,
kit
basement


=
T
T
T
T

Assuming that the temperature in
your kitchen is 20°C and that the
temperature of the interior of your
freezer is −5°C, substitute numerical
values and evaluate the ratio of the
coefficients of performance:
47 . 1
1
K 268
K 285
1
K 268
K 93 2
COP
COP
kit
basement
=


=
or an increase of % 47 in the
performance of the freezer!


22 •• Estimate the probability that all the molecules in your bedroom are
located in the (open) closet which accounts for about 10% of the total volume of
the room.

Picture the Problem The probability that all the molecules in your bedroom are
located in the (open) closet is given by
N
V
V
p








=
1
2
where N is the number of air
molecules in your bedroom and V
1
and V
2
are the volumes of your bedroom and
closet, respectively. We can use the ideal-gas law to find the number of molecules
N. We’ll assume that the volume of your room is about 50 m
3
and that the
temperature of the air is 20°C.

If the original volume of the air in
your bedroom is V
1
, the probability
p of finding the N molecules,
normally in your bedroom, confined
to your closet whose volume is V
2
is
given by:

N
V
V
p








=
1
2

or, because
1 10
1
2
V V = ,
N
p






=
10
1
(1)

Use the ideal-gas law to express N:
kT
PV
N =

Substitute numerical values and
evaluate N:
( )( )
( )( )
molecules 10 252 . 1
K 293 J/K 10 381 . 1
m 50 kPa 325 . 101
27
23
3
× =
×
=

N


Chapter 19


1790
Substitute for N in equation (1) and
evaluate p:
27
27
27
27
10
10 252 . 1
10 252 . 1
10 252 . 1
10
10
10
1
10
1

× −
×
×

= =






= p

23 •• [SSM] Estimate the maximum efficiency of an automobile engine
that has a compression ratio of 8.0:1.0. Assume the engine operates according to
the Otto cycle and assume γ = 1.4. (The Otto cycle is discussed in Section 19-1. )

Picture the Problem The maximum efficiency of an automobile engine is given
by the efficiency of a Carnot engine operating between the same two
temperatures. We can use the expression for the Carnot efficiency and the
equation relating V and T for a quasi-static adiabatic expansion to express the
Carnot efficiency of the engine in terms of its compression ratio.

Express the Carnot efficiency of an
engine operating between the
temperatures T
c
and T
h
:

h
c
C
1
T
T
− = ε
Relate the temperatures T
c
and T
h
to
the volumes V
c
and V
h
for a quasi-
static adiabatic compression from V
c

to V
h
:

1
h h
1
c c
− −
=
γ γ
V T V T ⇒
1
c
h
1
c
1
h
h
c











= =
γ
γ
γ
V
V
V
V
T
T

Substitute for
h
c
T
T
to obtain:

1
c
h
C
1









− =
γ
ε
V
V

Express the compression ratio r:

h
c
V
V
r =

Substituting for r yields:
1 C
1
1

− =
γ
ε
r


Substitute numerical values for r and
γ (1.4 for diatomic gases) and
evaluate ε
C
:
( )
% 56
0 . 8
1
1
1 4 . 1
C
≈ − =

ε

24 •• You are working as an appliance salesperson during the summer. One
day, your physics professor comes into your store to buy a new refrigerator.
Wanting to buy the most efficient refrigerator possible, she asks you about the
efficiencies of the available models. She decides to return the next day to buy the
most efficient refrigerator. To make the sale, you need to provide her with the
following estimates: (a) the highest COP possible for a household refrigerator,
and (b) and the highest rate possible for the heat to be released by the refrigerator
if the refrigerator uses 600 W of electrical power.
The Second Law of Thermodynamics


1791
Picture the Problem If we assume that the temperature on the inside of the
refrigerator is 0°C (273 K) and the room temperature to be 20°C (293 K), then the
refrigerator must be able to maintain a temperature difference of 20 K. We can
use the definition of the COP of a refrigerator and the relationship between the
temperatures of the hot and cold reservoir and Q
h
and Q
c
to find an upper limit on
the COP of a household refrigerator. In (b) we can solve the definition of COP for
Q
c
and differentiate the resulting equation with respect to time to estimate the rate
at which heat is being drawn from the refrigerator compartment.

(a) Using its definition, express the
COP of a household refrigerator:

W
Q
c
COP = (1)
Apply conservation of energy to
the refrigerator to obtain:

h c
Q Q W = + ⇒
c h
Q Q W − =
Substitute for W and simplify to
obtain:
1
1
COP
c
h
c h
c

=

=
Q
Q
Q Q
Q


Assume, for the sake of finding the
upper limit on the COP, that the
refrigerator is a Carnot refrigerator
and relate the temperatures of the hot
and cold reservoirs to
h
Q and Q
c
:

c
h
c
h
T
T
Q
Q
=
Substitute for
c
h
Q
Q
to obtain:
1
1
COP
c
h
max

=
T
T


Substitute numerical values and
evaluate COP
max
:
14 65 . 13
1
K 273
K 293
1
COP
max
≈ =

=

(b) Solve equation (1) for Q
c
: ( ) COP
c
W Q = (2)

Differentiate equation (2) with
respect to time to obtain:

( )
dt
dW
dt
dQ
COP
c
=

Substitute numerical values and
evaluate
dt
dQ
c
:
( )( ) kW 2 . 8 J/s 600 13.65
c
= =
dt
dQ


Chapter 19


1792
25 •• [SSM] The average temperature of the surface of the Sun is about
5400 K, the average temperature of the surface of Earth is about 290 K. The solar
constant (the intensity of sunlight reaching Earth’s atmosphere) is about
1.37 kW/m
2
. (a) Estimate the total power of the sunlight hitting Earth.
(b) Estimate the net rate at which Earth’s entropy is increasing due to this solar
radiation.

Picture the Problem We can use the definition of intensity to find the total power
of sunlight hitting Earth and the definition of the change in entropy to find the
changes in the entropy of Earth and the Sun resulting from the radiation from the
Sun.

(a) Using its definition, express the
intensity of the Sun’s radiation on
Earth in terms of the power P
delivered to Earth and Earth’s cross
sectional area A:

A
P
I =
Solve for P and substitute for A to
obtain:

2
R I IA P π = =
where R is the radius of Earth.
Substitute numerical values and
evaluate P:
( )( )
W 10 75 . 1 W 10 746 . 1
m 10 37 . 6 kW/m 37 . 1
17 17
2
6 2
× = × =
× = π P


(b) Express the rate at which Earth’s
entropy S
Earth
changes due to the
flow of solar radiation:

Earth
Earth
T
P
dt
dS
=

Substitute numerical values and
evaluate
dt
dS
Earth
:
s J/K 10 02 . 6
K 290
W 10 746 . 1
14
17
Earth
⋅ × =
×
=
dt
dS


26 •• A 1.0-L box contains N molecules of an ideal gas, and the positions of
the molecules are observed 100 times per second. Calculate the average time it
should take before we observe all N molecules in the left half of the box if N is
equal to (a) 10, (b) 100, (c) 1000, and (d) 1.0 mole. (e) The best vacuums that
have been created to date have pressures of about 10
–12
torr. If a vacuum chamber
has the same volume as the box, how long will a physicist have to wait before all
of the gas molecules in the vacuum chamber occupy only the left half of it?
Compare that to the expected lifetime of the universe, which is about 10
10
years.

Picture the Problem If you had one molecule in a box, it would have a 50%
chance of being on one side or the other. We don’t care which side the molecules
are on as long as they all are on one side, so with one molecule you have a 100%
The Second Law of Thermodynamics


1793
chance of it being on one side or the other. With two molecules, there are four
possible combinations (both on one side, both on the other, one on one side and
one on the other, and the reverse), so there is a 25% (1 in 4) chance of them both
being on a particular side, or a 50% chance of them both being on either side.
Extending this logic, the probability of N molecules all being on one side of the
box is P = 2/2
N
, which means that, if the molecules shuffle 100 times a second,
the time it would take them to cover all the combinations and all get on one side
or the other is
( ) 100 2
2
N
t = . In (e) we can apply the ideal gas law to find the number
of molecules in 1.0 L of air at a pressure of 10
−12
torr and an assumed temperature
of 300 K.

(a) Evaluate t for N = 10 molecules:

( )
s 5 s 12 . 5
s 100 2
2
1
10
≈ = =

t

(b) Evaluate t for N = 100 molecules:

( )
y 10 2
s 10 3.156
y 1
s 10 34 . 6
s 100 2
2
20
7
27
1
100
× ≈
×
× × =
=

t


(c) Evaluate t for N = 1000 molecules:

( )
1
1000
s 100 2
2

= t

To evaluate
1000
2 let
1000
2 10 =
x
and
take the logarithm of both sides of
the equation to obtain:

( ) 10 ln 2 ln 1000 x = ⇒ 301 = x
Substitute to obtain:

( )
y 10 2
s 10 3.156
y 1
s 10 5 . 0
s 100 2
10
291
7
299
1
301
× ≈
×
× × =
=

t


(d) Evaluate t for
N = 1.0 mol =6.022 ×10
23
molecules:

( )
1
10 022 . 6
s 100 2
2
23

×
= t

To evaluate
23
10 022 . 6
2
×
let
23
10 022 . 6
2 10
×
=
x
and take the logarithm
of both sides of the equation to
obtain:
( ) 10 ln 2 ln 10 022 . 6
23
x = × ⇒
23
10 ≈ x
Chapter 19


1794
Substituting for x yields:
( )
y 10
s 10 3.156
y 1
s 100 2
10
23
23
10
7 1
10







×


t


(e) Solve the ideal gas law for the
number of molecules N in the gas:

kT
PV
N =

Assuming the gas to be at room
temperature (300 K), substitute
numerical values and evaluate N:
( )( )( )
( )( )
molecules 10 22 . 3
K 300 J/K 10 381 . 1
L 0 . 1 Pa/torr 32 . 133 torr 10
7
23
12
× =
×
=


N


Evaluate t for N = 3.22×10
7

molecules:

( )
1
10 22 . 3
s 100 2
2
7

×
= t

To evaluate
7
10 22 . 3
2
×
let
7
10 22 . 3
2 10
×
=
x
and take the logarithm
of both sides of the equation to
obtain:

( ) 10 ln 2 ln 10 22 . 3
7
x = × ⇒
7
10 ≈ x
Substituting for x yields:

( )
y 10
s 10 3.156
y 1
s 100 2
10
7
7
10
7 1
10

×
× =

t


Express the ratio of this waiting time
to the lifetime of the universe t
universe
:
7
7
10
10
10
universe
10
y 10
y 10
≈ =
t
t

or
universe
10
7
10 t t ≈

Heat Engines and Refrigerators

27 • [SSM] A heat engine with 20.0% efficiency does 0.100 kJ of work
during each cycle. (a) How much heat is absorbed from the hot reservoir during
each cycle? (b) How much heat is released to the cold reservoir during each
cycle?






The Second Law of Thermodynamics


1795
Picture the Problem (a) The efficiency of the engine is defined to be
h
Q W = ε where W is the work done per cycle and Q
h
is the heat absorbed from
the hot reservoir during each cycle. (b) Because, from conservation of energy,
c h
Q W Q + = , we can express the efficiency of the engine in terms of the heat Q
c

released to the cold reservoir during each cycle.

(a) Q
h
absorbed from the hot reservoir
during each cycle is given by:

J 500
0.200
J 100
h
= = =
ε
W
Q

(b) Use
c h
Q W Q + = to obtain:
J 400 J 100 J 500
h c
= − = − = W Q Q

28 • A heat engine absorbs 0.400 kJ of heat from the hot reservoir and does
0.120 kJ of work during each cycle. (a) What is its efficiency? (b) How much heat
is released to the cold reservoir during each cycle?

Picture the Problem (a) The efficiency of the engine is defined to be
h
Q W = ε where W is the work done per cycle and Q
h
is the heat absorbed from
the hot reservoir during each cycle. (b) We can apply conservation of energy to
the engine to obtain
c h
Q W Q + = and solve this equation for the heat Q
c
released
to the cold reservoir during each cycle.

(a) The efficiency of the heat engine
is given by:
% 30
J 400
J 120
h
= = =
Q
W
ε

(b) Apply conservation of energy to
the engine to obtain:

c h
Q W Q + = ⇒ W Q Q − =
h c

Substitute numerical values and
evaluate Q
c
:
J 280 J 120 J 400
c
= − = Q

29 • A heat engine absorbs 100 J of heat from the hot reservoir and releases
60 J of heat to the cold reservoir during each cycle. (a) What is its efficiency? (b)
If each cycle takes 0.50 s, find the power output of this engine.

Picture the Problem We can use its definition to find the efficiency of the engine
and the definition of power to find its power output.

(a) The efficiency of the heat engine
is given by:

h
c
h
c h
h
Q
1
Q
Q
Q Q
Q
W
− =

= = ε

Chapter 19


1796
Substitute numerical values and
evaluate ε:
% 40
J 100
J 60
1 = − = ε

(b) The power output P of this
engine is the rate at which it does
work:

dt
dQ
Q
dt
d
dt
dW
P
h
h
ε ε = = =
Substitute numerical values and
evaluate P:
( ) W 80
s 0.500
J 100
0.40 =








= P

30 • A refrigerator absorbs 5.0 kJ of heat from a cold reservoir and releases
8.0 kJ to a hot reservoir. (a) Find the coefficient of performance of the
refrigerator. (b) The refrigerator is reversible. If it is run backward as a heat
engine between the same two reservoirs, what is its efficiency?

Picture the Problem We can apply their definitions to find the COP of the
refrigerator and the efficiency of the heat engine.

(a) The COP of a refrigerator is
defined to be:

W
Q
c
COP =
Apply conservation of energy to
relate the work done per cycle to
Q
h
and Q
c
:

c h
Q Q W − =
Substitute for W to obtain:

c h
c
COP
Q Q
Q

=

Substitute numerical values and
evaluate COP:
7 . 1
kJ 5.0 kJ 0 . 8
kJ 5.0
COP =

=

(b) The efficiency of a heat pump
is defined to be:
h
Q
W
= ε

Apply conservation of energy to the
heat pump to obtain:

h
c
h
c h
1
Q
Q
Q
Q Q
− =

= ε
Substitute numerical values and
evaluate ε :
% 38
kJ 8.0
kJ 0 . 5
1 = − = ε

The Second Law of Thermodynamics


1797
31 •• [SSM] The working substance of an engine is 1.00 mol of a
monatomic ideal gas. The cycle begins at P
1
= 1.00 atm and V
1
= 24.6 L. The gas
is heated at constant volume to P
2
= 2.00 atm. It then expands at constant pressure
until its volume is 49.2 L. The gas is then cooled at constant volume until its
pressure is again 1.00 atm. It is then compressed at constant pressure to its
original state. All the steps are quasi-static and reversible. (a) Show this cycle on
a PV diagram. For each step of the cycle, find the work done by the gas, the heat
absorbed by the gas, and the change in the internal energy of the gas. (b) Find the
efficiency of the cycle.

Picture the Problem To find the heat added during each step we need to find the
temperatures in states 1, 2, 3, and 4. We can then find the work done on the gas
during each process from the area under each straight-line segment and the heat
that enters the system from T C Q Δ =
V
and .
P
T C Q Δ = We can use the 1
st
law of
thermodynamics to find the change in internal energy for each step of the cycle.
Finally, we can find the efficiency of the cycle from the work done each cycle
and the heat that enters the system each cycle.

(a) The cycle is shown to the right:


Apply the ideal-gas law to state 1 to find T
1
:

( )( )
( )
K 300
K mol
atm L
10 8.206 mol 1.00
L 24.6 atm 1.00
2
1 1
1
=








×
= =

nR
V P
T

The pressure doubles while the
volume remains constant between
states 1 and 2. Hence:

K T T 600 2
1 2
= =
The volume doubles while the
pressure remains constant between
states 2 and 3. Hence:

K T T 1200 2
2 3
= =
Chapter 19


1798
The pressure is halved while the
volume remains constant
between states 3 and 4. Hence:

K T T 600
3 2
1
4
= =
For path 1→2:

0 Δ
12 12
= = V P W
and
( ) kJ 74 . 3 K 300 K 600
K mol
J
8.314 Δ Δ
2
3
12 2
3
12 V 12
= − ⎟






= = = T R T C Q

The change in the internal energy of
the system as it goes from state 1 to
state 2 is given by the 1
st
law of
thermodynamics:

on in int
Δ W Q E + =
Because 0
12
= W :
kJ 74 . 3 Δ
12 12 int,
= = Q E

For path 2→3:

( )( ) kJ 99 . 4
atm L
J 101.325
L 24.6 L 49.2 atm 2.00 Δ
23 23 on
− = ⎟






− − = − = − = V P W W

( ) kJ 5 . 12 K 600 K 1200
K mol
J
8.314 Δ Δ
2
5
23 2
5
23 P 23
= − ⎟






= = = T R T C Q

Apply
on in int
Δ W Q E + = to obtain:

kJ 5 . 7 kJ 99 . 4 kJ 5 . 12 Δ
23 int,
= − = E
For path 3→4:

0
34 34
= Δ = V P W
and
( ) kJ 48 . 7 K 00 2 1 K 600
K mol
J
8.314 Δ Δ Δ
2
3
34 2
3
34 V 34 int, 34
− = − ⎟






= = = = T R T C E Q

Apply
on in int
Δ W Q E + = to obtain:

kJ 48 . 7 0 kJ 48 . 7 Δ
34 int,
− = + − = E
The Second Law of Thermodynamics


1799

For path 4→1:

( )( ) kJ 49 . 2
atm L
J 101.325
L 2 . 9 4 L 24.6 atm 1.00 Δ
41 41 on
= ⎟






− − = − = − = V P W W
and
( ) kJ 24 . 6 K 600 K 00 3
K mol
J
8.314 Δ Δ
2
5
41 2
5
41 P 41
− = − ⎟






= = = T R T C Q

Apply
on in int
Δ W Q E + = to obtain:

kJ 75 . 3 kJ 49 . 2 kJ 24 . 6 Δ
41 int,
− = + − = E

For easy reference, the results of the preceding calculations are summarized in the
following table:
Process
on
W , kJ
in
Q , kJ ( )
on in int
Δ W Q E + = , kJ
1→2 0 3.74 3.74
2→3 −4.99 12.5 7.5
3→4 0 −7.48 −7.48
4→1 2.49 −6.24 −3.75

(b) The efficiency of the cycle is
given by:
( )
23 12
41 23
in
by
Q Q
W W
Q
W
+
− + −
= = ε

Substitute numerical values and
evaluate ε:
% 15
kJ 5 . 12 kJ 3.74
kJ 2.49 kJ 4.99

+

= ε

Remarks: Note that the work done per cycle is the area bounded by the
rectangular path. Note also that, as expected because the system returns to its
initial state, the sum of the changes in the internal energy for the cycle is zero.

32 •• The working substance of an engine is 1.00 mol of a diatomic ideal
gas. The engine operates in a cycle consisting of three steps: (1) an adiabatic
expansion from an initial volume of 10.0 L to a pressure of 1.00 atm and a
volume of 20.0 L, (2) a compression at constant pressure to its original volume of
10.0 L, and (3) heating at constant volume to its original pressure. Find the
efficiency of this cycle.

Chapter 19


1800
Picture the Problem The three steps
in the process are shown on the PV
diagram. We can find the efficiency of
the cycle by finding the work done by
the gas and the heat that enters the
system per cycle.
V(L)
2
3
1
P (atm)
2.639
2
1
0
0 10.0
20.0


The pressures and volumes at the end
points of the adiabatic expansion are
related according to:

γ γ
2 2 1 1
V P V P = ⇒
2
1
2
1
P
V
V
P
γ








=
Substitute numerical values and
evaluate P
1
:
( ) atm 639 . 2 atm 00 . 1
L 0 . 10
L 0 . 20
4 . 1
1
= ⎟





= P

Express the efficiency of the cycle:

h
Q
W
= ε (1)

No heat enters or leaves the system
during the adiabatic expansion:

0
12
= Q
Find the heat entering or leaving
the system during the isobaric
compression:

( )( )
L atm 35.0
L 20.0 L 10.0 atm 1.00
Δ Δ Δ
2
7
23 2
7
23 2
7
23 P 23
⋅ − =
− =
= = = V P T R T C Q


Find the heat entering or leaving
the system during the constant-
volume process:

( )( )
L atm 0 . 41
L 10.0 atm 1.00 atm 2.639
Δ Δ Δ
2
5
31 2
5
31 2
5
31 V 31
⋅ =
− =
= = = PV T R T C Q


Apply the 1
st
law of thermodynamics
to the cycle ( 0
cycle int,
= ΔE ) to obtain:
L atm 6.0
L atm 41.0 L atm 35.0 0
Δ
31 23 12
in in int on
⋅ =
⋅ + ⋅ − =
+ + =
− = − =
Q Q Q
Q Q E W


Substitute numerical values in
equation (1) and evaluate ε :
% 15
L atm 41
L atm 6.0
=


= ε

The Second Law of Thermodynamics


1801
33 •• An engine using 1.00 mol of an ideal gas initially at a volume of
24.6 L and a temperature of 400 K performs a cycle consisting of four steps: (1)
an isothermal expansion at 400 K to twice its initial volume, (2) cooling at
constant volume to a temperature of 300 K (3) an isothermal compression to its
original volume, and (4) heating at constant volume to its original temperature of
400 K. Assume that C
v
= 21.0 J/K. Sketch the cycle on a PV diagram and find its
efficiency.

Picture the Problem We can find the efficiency of the cycle by finding the work
done by the gas and the heat that enters the system per cycle.

The PV diagram of the cycle is
shown to the right. A, B, C, and D
identify the four states of the gas and
the numerals 1, 2, 3, and 4 represent
the four steps through which the gas
is taken.
0 10 20 30 40 50 60
2
1
1.5
0
0.5
400 K
300 K
P

(
a
t
m
)
V (L)
1
2
3
4
A
B
C
D


Express the efficiency of the cycle:

4 h, 3 h, 2 h, 1 h,
4 3 2 1
h
Q Q Q Q
W W W W
Q
W
+ + +
+ + +
= = ε

Because steps 2 and 4 are constant-
volume processes, W
2
= W
4
= 0:

4 h, 3 h, 2 h, 1 h,
3 1
h
0 0
Q Q Q Q
W W
Q
W
+ + +
+ + +
= = ε
Because the internal energy of the
gas increases in step 4 while no work
is done, and because the internal
energy does not change during step 1
while work is done by the gas, heat
enters the system only during these
processes:

4 h, 1 h,
3 1
h
Q Q
W W
Q
W
+
+
= = ε (1)
The work done during the isothermal
expansion (1) is given by:









=
A
B
1
ln
V
V
nRT W
The work done during the isothermal
compression (3) is given by:









=
C
D
c 3
ln
V
V
nRT W
Chapter 19


1802
Because there is no change in the
internal energy of the system during
step 1, the heat that enters the system
during this isothermal expansion is
given by:









= =
A
B
h 1 1
ln
V
V
nRT W Q
The heat that enters the system
during the constant-volume step 4 is
given by:

( )
c h V V 4
Δ T T C T C Q − = =
Substituting in equation (1) yields:
( )
c h V
A
B
h
C
D
c
A
B
h
ln
ln ln
T T C
V
V
nRT
V
V
nRT
V
V
nRT
− +
















+








= ε

Noting the 2
A
B
=
V
V
and
2
1
C
D
=
V
V
, substitute and simplify to obtain:

( )
( ) ( )
( ) ( )
( ) ( )
( )
( )
c h
V
h
c h
c h
V
h
c h
c h
V
h
c h
2 ln
2 ln
2 ln 2 ln
2 ln
2
1
ln 2 ln
T T
nR
C
T
T T
T T
nR
C
T
T T
T T
nR
C
T
T T
− +

=
− +

=
− +






+
= ε

Substitute numerical values and evaluate ε:

( ) ( )
( )
% 1 . 13
K 300 K 400
2 ln
K mol
J
314 . 8 mol 00 . 1
K
J
0 . 21
K 400
K 300 K 400
=








+

= ε

34 •• Figure 19-15 shows the cycle followed by 1.00 mol of an ideal
monatomic gas initially at a volume of 25.0 L. All the processes are quasi-static.
Determine (a) the temperature of each numbered state of the cycle, (b) the heat
transfer for each part of the cycle, and (c) the efficiency of the cycle.

Picture the Problem We can use the ideal-gas law to find the temperatures of
each state of the gas and the heat capacities at constant volume and constant
pressure to find the heat flow for the constant-volume and isobaric processes.
Because the change in internal energy is zero for the isothermal process, we can
use the expression for the work done on or by a gas during an isothermal process
The Second Law of Thermodynamics


1803
to find the heat flow during such a process. Finally, we can find the efficiency of
the cycle from its definition.

(a) Use the ideal-gas law to find the
temperature at point 1:

( )( )
( )
K 301
K mol
J
8.314 mol 1.00
L 25.0 kPa 100
1 1
1
=







= =
nR
V P
T


Use the ideal-gas law to find the
temperatures at points 2 and 3:
( )( )
( )
K 601
K mol
J
8.314 mol 1.00
L 25.0 kPa 200
2 2
3 2
=







=
= =
nR
V P
T T


(b) Find the heat entering the system for the constant-volume process from 1 → 2:

( ) kJ 3.74 K 301 K 601
K mol
J
8.314 Δ Δ
2
3
12 2
3
12 V 12
= − ⎟






= = = T R T C Q

Find the heat entering or leaving the system for the isothermal process from
2 → 3:

( ) ( ) kJ 46 . 3
L 0 . 5 2
L 0 . 0 5
ln K 01 6
K mol
J
8.314 mol 1.00 ln
2
3
2 23
=















=








=
V
V
nRT Q

Find the heat leaving the system during the isobaric compression from 3 → 1:

( ) kJ 24 . 6 K 601 K 301
K mol
J
8.314 Δ Δ
2
5
31 2
5
31 P 31
− = − ⎟






= = = T R T C Q

(c) Express the efficiency of the
cycle:

23 12 in
Q Q
W
Q
W
+
= = ε (1)

Apply the 1
st
law of thermodynamics
to the cycle:

kJ 0.96
kJ 6.24 kJ 3.46 kJ .74 3
31 23 12
=
− + =
+ + = =

Q Q Q Q W

because, for the cycle, 0 Δ
int
= E .
Chapter 19


1804
Substitute numerical values in equation
(1) and evaluate ε :
% 13
kJ 3.46 kJ 3.74
kJ 0.96
=
+
= ε

35 •• An ideal diatomic gas follows the cycle shown in Figure 19-16. The
temperature of state 1 is 200 K. Determine (a) the temperatures of the other three
numbered states of the cycle and (b) the efficiency of the cycle.

Picture the Problem We can use the ideal-gas law to find the temperatures of
each state of the gas. We can find the efficiency of the cycle from its definition;
using the area enclosed by the cycle to find the work done per cycle and the heat
entering the system between states 1 and 2 and 2 and 3 to determine Q
in
.

(a) Use the ideal-gas law for a fixed
amount of gas to find the
temperature in state 2 to the
temperature in state 1:

2
2 2
1
1 1
T
V P
T
V P
= ⇒
1
2
1
1 1
2 2
1 2
P
P
T
V P
V P
T T = =

Substitute numerical values and
evaluate T
2
:

( )
( )
( )
K 600
atm 1.0
atm 3.0
K 200
2
= = T

Apply the ideal-gas law for a fixed
amount of gas to states 2 and 3 to
obtain:

2
3
2
2 2
3 3
2 3
V
V
T
V P
V P
T T = =

Substitute numerical values and
evaluate T
3
:

( )
( )
( )
K 1800
L 100
L 300
K 600
3
= = T
Apply the ideal-gas law for a fixed
amount of gas to states 3 and 4 to
obtain:

3
4
3
3 3
4 4
3 4
P
P
T
V P
V P
T T = =

Substitute numerical values and
evaluate T
4
:

( )
( )
( )
K 600
atm 3.0
atm 1.0
K 1800
4
= = T
(b) The efficiency of the cycle is:
in
Q
W
= ε (1)

Use the area of the rectangle to
find the work done each cycle:

( )( )
L atm 400
atm 1.0 atm 3.0 L 100 L 300
Δ Δ
⋅ =
− − =
= V P W


The Second Law of Thermodynamics


1805
Apply the ideal-gas law to state 1
to find the product of n and R:
( )( )
atm/K L 0.50
K 200
L 100 atm 1.0
1
1 1
⋅ =
= =
T
V P
nR


Noting that heat enters the system
between states 1 and 2 and states 2
and 3, express Q
in
:
( )nR T T
T nR T nR
T C T C Q Q Q
23 2
7
12 2
5
23 2
7
12 2
5
23 P 12 V 23 12 in
Δ + Δ =
Δ + Δ =
Δ + Δ = + =


Substitute numerical values and evaluate Q
in
:

( ) [ ( )] L atm 2600
K
atm L
50 . 0 K 600 K 1800 K 200 K 600
2
7
2
5
in
⋅ =





⎛ ⋅
− + − = Q

Substitute numerical values in
equation (1) and evaluate ε :
% 15
L atm 2600
L atm 400
=


= ε

36 ••• Recently, an old design for a heat engine, known as the Stirling engine
has been promoted as a means of producing power from solar energy. The cycle
of a Stirling engine is as follows: (1) isothermal compression of the working gas
(2) heating of the gas at constant volume, (3) an isothermal expansion of the gas,
and (4) cooling of the gas at constant volume. (a) Sketch PV and ST diagrams for
the Stirling cycle. (b) Find the entropy change of the gas for each step of the cycle
and show that the sum of these entropy changes is equal to zero.

Picture the Problem (a) The PV and ST cycles are shown below. (b) We can
show that the entropy change during one Stirling cycle is zero by adding up the
entropy changes for the four processes.

P
V
T
T
c
h
(1)
(2)
(3)
(4)
1
2
3
4
S
T
T
h
c
T
V = 0
V = 0
Δ
Δ


Chapter 19


1806

(b) The change in entropy for one
Stirling cycle is the sum of the
entropy changes during the cycle:

41 34 23 12 cycle
Δ Δ Δ Δ Δ S S S S S + + + = (1)
Express the entropy change for the
isothermal process from state 1 to
state 2:









=
1
2
12
ln Δ
V
V
nR S
Similarly, the entropy change for the
isothermal process from state 3 to
state 4 is:









=
3
4
34
ln Δ
V
V
nR S
or, because V
2
= V
3
and V
1
= V
4
,








− =








=
1
2
2
1
34
ln ln Δ
V
V
nR
V
V
nR S

The change in entropy for a constant-
volume process is given by:








=
= =
∫ ∫
i
f
V
V
isochoric
ln
Δ
f
i
T
T
nC
T
dT nC
T
dQ
S
T
T


For the constant-volume process
from state 2 to state 3:









=
h
c
V 23
ln Δ
T
T
C S
For the constant-volume process
from state 4 to state 1:








− =








=
h
c
V
c
h
V 41
ln ln Δ
T
T
C
T
T
C S

Substituting in equation (1) yields:

0 ln ln ln ln Δ
h
c
V
1
2
h
c
V
1
2
cycle
=


























+








=
T
T
C
V
V
nR
T
T
C
V
V
nR S

37 •• ″As far as we know, Nature has never evolved a heat engine″—Steven
Vogel, Life’s Devices, Princeton University Press (1988). (a) Calculate the
efficiency of a heat engine operating between body temperature (98.6ºF) and a
typical outdoor temperature (70ºF), and compare this to the human body’s
efficiency for converting chemical energy into work (approximately 20%). Does
this efficiency comparison contradict the second law of thermodynamics?
(b) From the result of Part (a), and a general knowledge of the conditions under
which most warm-blooded organisms exist, give a reason why no warm-blooded
organisms have evolved heat engines to increase their internal energies.
The Second Law of Thermodynamics


1807
Picture the Problem We can use the efficiency of a Carnot engine operating
between reservoirs at body temperature and typical outdoor temperatures to find
an upper limit on the efficiency of an engine operating between these
temperatures.

(a) Express the maximum efficiency
of an engine operating between body
temperature and 70°F:

h
c
C
1
T
T
− = ε
Use ( ) 273 32
F 9
5
+ − = t T to obtain: K 310
body
= T and K 294
room
= T

Substitute numerical values and
evaluate
C
ε :

% 16 . 5
K 310
K 294
1
C
= − = ε

The fact that this efficiency is considerably less than the actual efficiency of a
human body does not contradict the second law of thermodynamics. The
application of the second law to chemical reactions such as the ones that supply
the body with energy have not been discussed in the text but we can note that we
don’t get our energy from heat swapping between our body and the environment.
Rather, we eat food to get the energy that we need.

(b) Most warm-blooded animals survive under roughly the same conditions as
humans. To make a heat engine work with appreciable efficiency, internal body
temperatures would have to be maintained at an unreasonably high level.

38 ••• The diesel cycle shown in Figure 19-17 approximates the behavior of a
diesel engine. Process ab is an adiabatic compression, process bc is an expansion
at constant pressure, process cd is an adiabatic expansion, and process da is
cooling at constant volume. Find the efficiency of this cycle in terms of the
volumes V
a
, V
b
and V
c
.

Picture the Problem The working fluid will be modeled as an ideal gas and the
process will be modeled as quasistatic. To find the efficiency of the diesel cycle
we can find the heat that enters the system and the heat that leaves the system and
use the expression that gives the efficiency in terms of these quantities. Note that
no heat enters or leaves the system during the adiabatic processes ab and cd. Heat
enters the system during the isobaric process bc and leaves the system during the
isovolumetric process da.

Express the efficiency of the cycle in
terms of Q
c
and Q
h
:

h
c
h
c h
h
1
Q
Q
Q
Q Q
Q
W
− =

= = ε

Express Q for the isobaric warming
process bc:
( )
b c bc
T T C Q Q − = =
P h

Chapter 19


1808
Because C
V
is independent of T,
Q
da
(the constant-volume cooling
process) is given by:

( )
a d da
T T C Q Q − = =
V c

Substitute for Q
h
and Q
c
and
simplify using
V P
C C = γ to obtain:
( )
( )
( )
( )
b c
a d
b c
a d
T T
T T
T T C
T T C


− =


− =
γ
ε 1 1
P
V


Using an equation for a quasistatic
adiabatic process, relate the
temperatures T
a
and T
b
to the
volumes V
a
and V
b
:

1 1 − −
=
γ γ
b b a a
V T V T ⇒
1
1


=
γ
γ
a
b
b a
V
V
T T (1)
Proceeding similarly, relate the
temperatures T
c
and T
d
to the
volumes V
c
and V
d
:

1 1 − −
=
γ γ
d d c c
V T V T ⇒
1
1


=
γ
γ
d
c
c d
V
V
T T (2)
Use equations (1) and (2) to eliminate
T
a
and T
d
:

( )
b c
a
b
b
d
c
c
T T
V
V
T
V
V
T










− =




γ
ε
γ
γ
γ
γ
1
1
1
1
1

Because V
a
= V
d
:



































− =
− −
c
b
a
b
c
b
a
c
T
T
V
V
T
T
V
V
1
1
1 1
γ
ε
γ γ


Noting that P
b
= P
c
, apply the ideal-
gas law to relate T
b
and T
c
:

c
b
c
b
V
V
T
T
=

Substitute for the ratio of T
b
to T
c
and simplify to obtain:

( )
b c a
b c
a
b
a
c
a
b
a
c
a
b
a
c
a
b
c
b
a
c
a
c
a
c
c
b
a
b
c
b
a
c
V V V
V V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V
V


− =


























− =


























− = ⋅


























− =

− − − −
1
1 1 1 1
1 1
1
1
1
γ
γ γ
γ γ
γ γ γ γ
γ
γ
γ γ
ε

The Second Law of Thermodynamics


1809
Second Law of Thermodynamics

39 •• [SSM] A refrigerator absorbs 500 J of heat from a cold reservoir and
releases 800 J to a hot reservoir. Assume that the heat-engine statement of the
second law of thermodynamics is false, and show how a perfect engine working
with this refrigerator can violate the refrigerator statement of the second law of
thermodynamics.

Determine the Concept The following diagram shows an ordinary refrigerator
that uses 300 J of work to remove 500 J of heat from a cold reservoir and releases
800 J of heat to a hot reservoir (see (a) in the diagram). Suppose the heat-engine
statement of the second law is false. Then a ″perfect″ heat engine could remove
energy from the hot reservoir and convert it completely into work with 100
percent efficiency. We could use this perfect heat engine to remove 300 J of
energy from the hot reservoir and do 300 J of work on the ordinary refrigerator
(see (b) in the diagram). Then, the combination of the perfect heat engine and the
ordinary refrigerator would be a perfect refrigerator; transferring 500 J of heat
from the cold reservoir to the hot reservoir without requiring any work (see (c) in
the diagram).This violates the refrigerator statement of the second law.






⇓ ⇓
500 J
Cold reservoir at temperature T
c
Hot reservoir at temperature T
h
800 J
300 J 300 J
300 J
Ordinary
refrigerator
Perfect
refrigerator
500 J
500 J
a b c ( ) ( ) ( )
Perfect
heat
engine


40 •• If two curves that represent quasi-static adiabatic processes could
intersect on a PV diagram, a cycle could be completed by an isothermal path
between the two adiabatic curves shown in Figure 19-18. Show that such a cycle
violates the second law of thermodynamics.

Determine the Concept The work done by the system is the area enclosed by the
cycle, where we assume that we start with the isothermal expansion. It is only in
this expansion that heat is extracted from a reservoir. There is no heat transfer in
the adiabatic expansion or compression. Thus, we would completely convert heat
to mechanical energy, without exhausting any heat to a cold reservoir, in violation
of the second law of thermodynamics.
Chapter 19


1810
Carnot Cycles

41 • [SSM] A Carnot engine works between two heat reservoirs at
temperatures T
h
= 300 K and T
c
= 200 K. (a) What is its efficiency? (b) If it
absorbs 100 J of heat from the hot reservoir during each cycle, how much work
does it do each cycle? (c) How much heat does it release during each cycle?
(d) What is the COP of this engine when it works as a refrigerator between the
same two reservoirs?

Picture the Problem We can find the efficiency of the Carnot engine using
h c
/ 1 T T − = ε and the work done per cycle from . /
h
Q W = ε We can apply
conservation of energy to find the heat rejected each cycle from the heat absorbed
and the work done each cycle. We can find the COP of the engine working as a
refrigerator from its definition.

(a) The efficiency of the Carnot
engine depends on the temperatures
of the hot and cold reservoirs:

% 3 . 33
K 300
K 200
1 1
h
c
C
= − = − =
T
T
ε

(b) Using the definition of efficiency,
relate the work done each cycle to the
heat absorbed from the hot reservoir:

( )( ) J 33.3 J 100 0.333
h C
= = = Q W ε

(c) Apply conservation of energy to
relate the heat given off each cycle
to the heat absorbed and the work
done:

J 67
J 66.7 J 33.3 J 100
h c
=
= − = − = W Q Q

(d) Using its definition, express and
evaluate the refrigerator’s coefficient
of performance:
0 . 2
J 33.3
J 66.7
COP
c
= = =
W
Q


42 • An engine absorbs 250 J of heat per cycle from a reservoir at 300 K
and releases 200 J of heat per cycle to a reservoir at 200 K. (a) What is its
efficiency? (b) How much additional work per cycle could be done if the engine
were reversible?

Picture the Problem We can find the efficiency of the engine from its definition
and the additional work done if the engine were reversible from ,
h C
Q W ε = where
ε
C
is the Carnot efficiency.

The Second Law of Thermodynamics


1811
(a) Express the efficiency of the
engine in terms of the heat absorbed
from the high-temperature reservoir
and the heat exhausted to the low-
temperature reservoir:

% 0 . 20
J 250
J 200
1
1
h
c
h
c h
h
= − =
− =

= =
Q
Q
Q
Q Q
Q
W
ε


(b) Express the additional work done
if the engine is reversible:

( ) a
W W W
Part Carnot
− = Δ (1)
Relate the work done by a reversible
engine to its Carnot efficiency:

h
h
c
h C
1 Q
T
T
Q W








− = = ε

Substitute numerical values and
evaluate W:
( ) J 3 . 83 J 250
K 300
K 200
1 =








− = W

Substitute numerical values in
equation (1) and evaluate ΔW:
J 33 J 50 J 3.3 8 Δ = − = W

43 •• A reversible engine working between two reservoirs at temperatures T
h

and T
c
has an efficiency of 30%. Working as a heat engine, it releases 140 J per
cycle of heat to the cold reservoir. A second engine working between the same
two reservoirs also releases 140 J per cycle to the cold reservoir. Show that if the
second engine has an efficiency greater than 30%, the two engines working
together would violate the heat-engine statement of the second law.

Determine the Concept Let the first engine be run as a refrigerator. Then it will
remove 140 J from the cold reservoir, deliver 200 J to the hot reservoir, and
require 60 J of energy to operate. Now take the second engine and run it between
the same reservoirs, and let it eject 140 J into the cold reservoir, thus replacing the
heat removed by the refrigerator. If ε
2
, the efficiency of this engine, is greater than
30%, then Q
h2
, the heat removed from the hot reservoir by this engine, is
140 J/(1 − ε
2
) > 200 J, and the work done by this engine is W = ε
2
Q
h2
> 60 J. The
end result of all this is that the second engine can run the refrigerator, replacing
the heat taken from the cold reservoir, and do additional mechanical work. The
two systems working together then convert heat into mechanical energy without
rejecting any heat to a cold reservoir, in violation of the second law.

44 •• A reversible engine working between two reservoirs at temperatures T
h

and T
c
has an efficiency of 20%. Working as a heat engine, it does 100 J of work
per cycle. A second engine working between the same two reservoirs also does
100 J of work per cycle. Show that if the efficiency of the second engine is greater
Chapter 19


1812
than 20%, the two engines working together would violate the refrigerator
statement of the second law.

Determine the Concept If the reversible engine is run as a refrigerator, it will
require 100 J of mechanical energy to take 400 J of heat from the cold reservoir
and deliver 500 J to the hot reservoir. Now let the second engine, with ε
2
> 0.2,
operate between the same two heat reservoirs and use it to drive the refrigerator.
Because ε
2
> 0.2, this engine will remove less than 500 J from the hot reservoir in
the process of doing 100 J of work. The net result is then that no net work is done
by the two systems working together, but a finite amount of heat is transferred
from the cold reservoir to the hot reservoir, in violation of the refrigerator
statement of the second law.

45 •• A Carnot engine works between two heat reservoirs as a refrigerator.
During each cycle, 100 J of heat are absorbed and 150 J are released to the hot
reservoir. (a) What is the efficiency of the Carnot engine when it works as a heat
engine between the same two reservoirs? (b) Show that no other engine working
as a refrigerator between the same two reservoirs can have a COP greater than
2.00.

Picture the Problem We can use the definition of efficiency to find the efficiency
of the Carnot engine operating between the two reservoirs.

(a) The efficiency of the Carnot
engine is given by:

% 33
J 150
J 50
h
C
= = =
Q
W
ε

(b) If the COP > 2, then 50 J of work will remove more than 100 J of heat from
the cold reservoir and put more than 150 J of heat into the hot reservoir. So
running the engine described in Part (a) to operate the refrigerator with a COP > 2
will result in the transfer of heat from the cold to the hot reservoir without doing
any net mechanical work in violation of the second law.

46 •• A Carnot engine works between two heat reservoirs at temperatures
T
h
= 300 K and T
c
= 77.0 K. (a) What is its efficiency? (b) If it absorbs 100 J of
heat from the hot reservoir during each cycle, how much work does it do?
(c) How much heat does it release to the low-temperature reservoir during each
cycle? (d) What is the coefficient of performance of this engine when it works as a
refrigerator between these two reservoirs?





The Second Law of Thermodynamics


1813
Picture the Problem We can use the definitions of the efficiency of a Carnot
engine and the coefficient of performance of a refrigerator to find these quantities.
The work done each cycle by the Carnot engine is given by
h C
Q W ε = and we can
use the conservation of energy to find the heat rejected to the low-temperature
reservoir.

(a) The efficiency of a Carnot engine
depends on the temperatures of the
hot and cold reservoirs:

74.3%
K 300
K 77.0
1 1
h
c
C
= − = − =
T
T
ε

(b) Express the work done each
cycle in terms of the efficiency of
the engine and the heat absorbed
from the high-temperature reservoir:

( )( ) J 3 . 74 J 100 743 . 0
h C
= = = Q W ε

(c) Apply conservation of energy to
obtain:

J 26 J 74.3 J 00 1
h c
= − = − = W Q Q

(d) Using its definition, express and
evaluate the refrigerator’s coefficient
of performance:
35 . 0
J 74.3
J 26
COP
c
= = =
W
Q


47 •• [SSM] In the cycle shown in Figure 19-19, 1.00 mol of an ideal
diatomic gas is initially at a pressure of 1.00 atm and a temperature of 0.0ºC. The
gas is heated at constant volume to T
2
= 150ºC and is then expanded adiabatically
until its pressure is again 1.00 atm. It is then compressed at constant pressure back
to its original state. Find (a) the temperature after the adiabatic expansion,
(b) the heat absorbed or released by the system during each step, (c) the efficiency
of this cycle, and (d) the efficiency of a Carnot cycle operating between the
temperature extremes of this cycle.

Picture the Problem We can use the ideal-gas law for a fixed amount of gas and
the equations of state for an adiabatic process to find the temperatures, volumes,
and pressures at the end points of each process in the given cycle. We can use
T Q Δ =
V
C and T Q Δ =
P
C to find the heat entering and leaving during the
constant-volume and isobaric processes and the first law of thermodynamics to
find the work done each cycle. Once we’ve calculated these quantities, we can
use its definition to find the efficiency of the cycle and the definition of the
Carnot efficiency to find the efficiency of a Carnot engine operating between the
extreme temperatures.

Chapter 19


1814
(a) Apply the ideal-gas law for a
fixed amount of gas to relate the
temperature at point 3 to the
temperature at point 1:

3
3 3
1
1 1
T
V P
T
V P
=
or, because P
1
= P
3
,
1
3
1 3
V
V
T T = (1)

Apply the ideal-gas law for a fixed
amount of gas to relate the pressure
at point 2 to the temperatures at
points 1 and 2 and the pressure at 1:
2
2 2
1
1 1
T
V P
T
V P
= ⇒
1 2
2 1 1
2
T V
T V P
P =


Because V
1
= V
2
:

( ) atm 1.55
K 273
K 423
atm 1.00
1
2
1 2
= = =
T
T
P P

Apply an equation for an adiabatic
process to relate the pressures and
volumes at points 2 and 3:

γ γ
3 3 1 1
V P V P = ⇒
γ
1
3
1
1 3








=
P
P
V V
Noting that V
1
= 22.4 L, evaluate V
3
:
( ) L 30.6
atm 1
atm 1.55
L 22.4
1.4
1
3
=








= V

Substitute numerical values in
equation (1) and evaluate T
3
and t
3
:

( ) K 373
L 22.4
L 30.6
K 273
3
= = T
and
C 100 273
3 3
° = − = T t

(b) Process 1→2 takes place at
constant volume (note that γ = 1.4
corresponds to a diatomic gas and
that C
P
– C
V
= R):

( )
kJ 3.12
K 273 K 423
K mol
J
8.314
Δ Δ C
2
5
12 2
5
12 V 12
=
− ⎟






=
= = T R T Q


Process 2→3 takes place adiabatically:

0
23
= Q
Process 3→1 is isobaric (note that
C
P
= C
V
+ R):

( )
kJ 2.91
K 373 K 73 2
K mol
J
8.314
Δ Δ C
2
7
12 2
7
31 P 31
− =
− ⎟






=
= = T R T Q


The Second Law of Thermodynamics


1815
(c) The efficiency of the cycle is
given by:

in
Q
W
= ε (2)
Apply the first law of thermodynamics
to the cycle:

on in int
Δ W Q E + =
or, because 0
cycle int,
= ΔE (the system
begins and ends in the same state) and
in gas by the on
Q W W = − = .

Evaluating W yields:

kJ 0.21 kJ 2.91 0 kJ 3.12
31 23 12
= − + =
+ + = =

Q Q Q Q W


Substitute numerical values in
equation (2) and evaluate ε :
% 7 . 6
kJ 3.12
kJ 0.21
= = ε

(d) Express and evaluate the
efficiency of a Carnot cycle
operating between 423 K and
273 K:
35.5%
K 23 4
K 73 2
1 1
h
c
C
= − = − =
T
T
ε

48 •• You are part of a team that is completing a mechanical-engineering
project. Your team built a steam engine that takes in superheated steam at 270ºC
and discharges condensed steam from its cylinder at 50.0ºC. Your team has
measured its efficiency to be 30.0%. (a) How does this efficiency compare with
the maximum possible efficiency for your engine? (b) If the useful power output
of the engine is known to be 200 kW, how much heat does the engine release to
its surroundings in 1.00 h?

Picture the Problem We can find the maximum efficiency of the steam engine
by calculating the Carnot efficiency of an engine operating between the given
temperatures. We can apply the definition of efficiency to find the heat
discharged to the engine’s surroundings in 1.00 h.

(a) The efficiency of the steam
engine as a percentage of the
maximum possible efficiency is
given by:

max max
engine steam
300 . 0
ε ε
ε
=
The efficiency of a Carnot engine
operating between temperatures F
c

and T
h
is:

% 52 . 40
K 543
K 323
1 1
h
c
max
= − = − =
T
T
ε

Chapter 19


1816
Substituting for ε
max
yields:
% 05 . 74
4052 . 0
300 . 0
max
engine steam
= =
ε
ε

or
max engine steam
740 . 0 ε ε =

(b) Relate the heat Q
c
discharged to
the engine’s surroundings to Q
h
and
the efficiency of the engine:

h
c h
h
Q
Q Q
Q
W −
= = ε ⇒ ( )
h c
1 Q Q ε − =

Using its definition, relate the
efficiency of the engine to the heat
intake of the engine and the work it
does each cycle:

ε ε
t P W
Q
Δ
= =
h

Substitute for Q
h
in the expression
for
c
Q and simplify to obtain:
( ) t P
t P
Q Δ 1
1 Δ
1
c






− = − =
ε ε
ε

Substitute numerical values and evaluate ( ) h 00 . 1
c
Q :

( ) ( ) GJ 68 . 1 s 3600
s
kJ
200 1
300 . 0
1
h 00 . 1
c
=












− = Q

*Heat Pumps

49 • [SSM] As an engineer, you are designing a heat pump that is capable
of delivering heat at the rate of 20 kW to a house. The house is located where, in
January, the average outside temperature is –10ºC. The temperature of the air in
the air handler inside the house is to be 40ºC. (a) What is maximum possible
COP for a heat pump operating between these temperatures? (b) What must the
minimum power of the electric motor driving the heat pump be? (c) In reality, the
COP of the heat pump will be only 60 percent of the ideal value. What is the
minimum power of the electric motor when the COP is 60 percent of the ideal
value?

Picture the Problem We can use the definition of the COP
HP
and the Carnot
efficiency of an engine to express the maximum efficiency of the refrigerator in
terms of the reservoir temperatures. We can apply the definition of power to find
the minimum power needed to run the heat pump.

The Second Law of Thermodynamics


1817
(a) Express the COP
HP
in terms of T
h

and T
c
:
c h
h
h
c
h
c
h
h h
HP
1
1
1
1
COP
T T
T
T
T
Q
Q
Q Q
Q
W
Q
c

=

=

=

= =


Substitute numerical values and
evaluate COP
HP
:
3 . 6
26 . 6
K 263 K 313
K 13 3
COP
HP
=
=

=


(b) The COP
HP
is also given by:

motor
out
HP
COP
P
P
= ⇒
HP
out
motor
COP
P
P =

Substitute numerical values and
evaluate P
motor
:
kW 2 . 3
6.26
kW 20
motor
= = P

(c) The minimum power of the
electric motor is given by:
( )
max HP,
c
HP
c
min
COP ε ε
dt
dQ
dt
dQ
P = =
where
HP
ε is the efficiency of the heat
pump.

Substitute numerical values and
evaluate P
min
: ( )( )
kW 3 . 5
6.26 60 . 0
kW 20
min
= = P

50 • A refrigerator is rated at 370 W. (a) What is the maximum amount of
heat it can absorb from the food compartment in 1.00 min if the food-
compartment temperature of the refrigerator is 0.0ºC and it releases heat into a
room at 20.0ºC? (b) If the COP of the refrigerator is 70% of that of a reversible
refrigerator, how much heat can it absorb from the food compartment in 1.00 min
under these conditions?

Picture the Problem We can use the definition of the COP to relate the heat
removed from the refrigerator to its power rating and operating time. By
expressing the COP in terms of T
c
and T
h
we can write the amount of heat
removed from the refrigerator as a function of T
c
, T
h
, P, and Δt.

(a) Express the amount of heat the
refrigerator can remove in a given
period of time as a function of its
COP:
( )
( ) t P
W Q
Δ =
=
COP
COP
c


Chapter 19


1818
Express the COP in terms of T
h
and
T
c
and simplify to obtain:
c h
c
h
c
h
h
h
c c
1
1
1
1
1 1
COP
T T
T
T
T
Q
W Q
Q
Q
W
Q

=


= − =

=

= = =
ε ε
ε
ε ε


Substituting for COP yields:
t P
T T
T
Q Δ
c h
c
c









=

Substitute numerical values and evaluate Q
c
:

( ) MJ 30 . 0 kJ 303
min
s 60
min 00 . 1 W 370
K 273 K 293
K 273
c
= = ⎟





× ⎟






= Q

(b) If the COP is 70% of the
efficiency of an ideal pump:
( )( ) MJ 1 0.2 kJ 303 70 . 0
c
= =
'
Q

51 • A refrigerator is rated at 370 W. (a) What is the maximum amount of
heat it can absorb for the food compartment in 1.00 min if the temperature in the
compartment is 0.0ºC and it releases heat into a room at 35ºC? (b) If the COP of
the refrigerator is 70% of that of a reversible pump, how much heat can it absorb
from the food compartment in 1.00 min? Is the COP for the refrigerator greater
when the temperature of the room is 35ºC or 20ºC? Explain.

Picture the Problem We can use the definition of the COP to relate the heat
removed from the refrigerator to its power rating and operating time. By
expressing the COP in terms of T
c
and T
h
we can write the amount of heat
removed from the refrigerator as a function of T
c
, T
h
, P, and Δt.

(a) Express the amount of heat the
refrigerator can remove in a given
period of time as a function of its
COP:

( )
( ) t P
W Q
Δ =
=
COP
COP
c


The Second Law of Thermodynamics


1819
Express the COP in terms of T
h

and T
c
and simplify to obtain:
c h
c
h
c
h
h
h
c c
1
1
1
1
1 1
COP
T T
T
T
T
Q
W Q
Q
Q
W
Q

= −

=
− =

=

= = =
ε ε
ε
ε ε


Substituting for COP yields:
t P
T T
T
Q Δ
c h
c
c









=

Substitute numerical values and evaluate Q
c
:

( ) MJ 7 1 . 0 kJ 73 1
min
s 60
min 00 . 1 W 370
K 273 K 08 3
K 73 2
c
= =






×







= Q

(b) If the COP is 70% of the
efficiency of an ideal pump:

( )( ) MJ 12 . 0 kJ 73 1 70 . 0
c
= =
'
Q

Because the temperature difference increases when the room is warmer, the COP
decreases.

52 ••• You are installing a heat pump, whose COP is half the COP of a
reversible heat pump. You will use the pump on chilly winter nights to increase
the air temperature in your bedroom. Your bedroom’s dimensions are 5.00 m ×
3.50 m × 2.50 m. The air temperature should increase from 63°F

to 68°F. The
outside temperature is 35°F

, and the temperature at the air handler in the room is
112°F. If the pump’s electric power consumption is 750 W, how long will you
have to wait in order for the room’s air to warm (take the specific heat of air to be
1.005 kJ/(kg·°C)? Assume you have good window draperies and good wall
insulation so that you can neglect the release of heat through windows, walls,
ceilings and floors. Also assume that the heat capacity of the floor, ceiling, walls
and furniture are negligible.

Picture the Problem We can use the definition of the coefficient of performance
of a heat pump and the relationship between the work done per cycle and the
pump’s power consumption to find your waiting time.





Chapter 19


1820
The coefficient of performance of the
heat pump is defined as:

t P
Q
W
Q
Δ
COP
h h
HP
= = ⇒
( )P
Q
t
HP
h
COP
Δ =
where Q
h
is the heat required to raise
the temperature of your bedroom, P is
the power consumption of the heat
pump, and Δt is the time required to
warm the bedroom.

We’re given that the coefficient of
performance of the heat pump is half
the coefficient of performance of an
ideal heat pump:










=
= =
c h
h
2
1
max 2
1 h
HP
COP COP
T T
T
W
Q


Substituting for
HP
COP yields:

P
T T
T
Q
t









=
c h
h
h
2
Δ

The heat required to warm the room
is related to the volume of the room,
the density of air, and the desired
increase in temperature:

T Vc T mc Q Δ Δ
h
ρ = =
where ρ is the density of air and c is its
specific heat capacity.

Substitute for Q
h
to obtain:
P
T T
T
T Vc
t









=
c h
h
Δ 2
Δ
ρ


Substitute numerical values and evaluate Δt:

( )
( )
s 56
W 750
K 275 K 317
K 317
F 9
C 5
F 5
C kg
J
1005 m 2.50 m 3.50 m 00 . 5
m
kg
293 . 1 2
Δ
3
=













°
°
× °








° ⋅
× ×






= t

Entropy Changes

53 • [SSM] You inadvertently leave a pan of water boiling away on the
hot stove. You return just in time to see the last drop converted into steam. The
pan originally held 1.00 L of boiling water. What is the change in entropy of the
water associated with its change of state from liquid to gas?



The Second Law of Thermodynamics


1821
Picture the Problem Because the water absorbed heat in the vaporization process
its change in entropy is positive and given by
T
Q
S
O H by
absorbed
O H
2
2
Δ = . See Table 18-2
for the latent heat of vaporization of water.

The change in entropy of the water is
given by:
T
Q
S
O H by
absorbed
O H
2
2
Δ =

The heat absorbed by the water as it
vaporizes is the product of its mass
and latent heat of vaporization:

v v
O H by
absorbed
2
VL mL Q ρ = =
Substituting for
O H by
absorbed
2
Q yields:
T
VL
S
v
O H
2
Δ
ρ
=

Substitute numerical values and
evaluate
O H
2
ΔS :
( )
K
kJ
05 . 6
K 373
kg
kJ
2257 L 00 . 1
L
kg
00 . 1
Δ
O H
2
=














= S


54 • What is the change in entropy of 1.00 mol of liquid water at 0.0ºC that
freezes to ice at 0.0°C?

Picture the Problem We can use the definition of entropy change to find the
change in entropy of the liquid water as it freezes. Because heat is removed from
liquid water when it freezes, the change in entropy of the liquid water is negative.
See Appendix C for the molar mass of water and Table 18-2 for the latent heat of
fusion of water.

The change in entropy of the water is
given by::

T
Q
S
O H from
removed
O H
2
2
Δ =

The heat removed from the water as
it freezes is the product of its mass
and latent heat of fusion:

f
O H from
removed
2
mL Q − =
or, because
O H
2
nM m = ,
f O H
O H from
removed
2
2
L nM Q − =

Chapter 19


1822

Substitute numerical values and evaluate
O H
2
ΔS :

( )
K
J
22.0
K 273
g
J
333.5
mol
g
18.015 mol 00 . 1
Δ
O H
2
− =















= S

55 •• Consider the freezing of 50.0 g of water once it is placed in the freezer
compartment of a refrigerator. Assume the walls of the freezer are maintained at
–10ºC. The water, initially liquid at 0.0ºC, is frozen into ice and cooled to –10ºC.
Show that even though the entropy of the water decreases, the net entropy of the
universe increases.

Picture the Problem The change in the entropy of the universe resulting from the
freezing of this water and the cooling of the ice formed is the sum of the entropy
changes of the water-ice and the freezer. Note that, while the entropy of the water
decreases, the entropy of the freezer increases.

The change in entropy of the
universe resulting from this freezing
and cooling process is given by:

freezer water u
S S S Δ + Δ = Δ (1)
Express
water
S Δ :

cooling freezing water
S S S Δ + Δ = Δ (2)
Express
freezing
S Δ :
freezing
freezing
freezing
T
Q
S

= Δ (3)
where the minus sign is a consequence
of the fact that energy is leaving the
water as it freezes.

Relate
freezing
Q to the latent heat of
fusion and the mass of the water:

f freezing
mL Q =
Substitute in equation (3) to obtain:

freezing
f
freezing
T
mL
S

= Δ

Express
cooling
S Δ :








= Δ
i
f
p cooling
ln
T
T
mC S

Substitute in equation (2) to obtain:









+

= Δ
i
f
p
freezing
f
water
ln
T
T
mC
T
mL
S
The Second Law of Thermodynamics


1823
Noting that the freezer gains heat
(at 263 K) from the freezing
water and cooling ice, express
freezer
S Δ :

freezer
p
freezer
f
freezer
ice cooling
freezer
ice
freezer
T
T mC
T
mL
T
Q
T
Q
S
Δ
+ =
Δ
+
Δ
= Δ


Substitute for
water
S Δ and
freezer
S Δ in equation (1):








⎡ Δ +
+








+

=
Δ
+ +








+

= Δ
freezer
p f
i
f
p
freezing
f
freezer
p
freezer
f
i
f
p
freezing
f
u
ln
ln
T
T C L
T
T
C
T
L
m
T
T mC
T
mL
T
T
mC
T
mL
S


Substitute numerical values and evaluate ΔS
u
:

( )
( )
J/K 40 . 2
K 263
K 263 K 273
K kg
J
2100
kg
J
10 5 . 333
K 273
K 263
ln
K kg
J
2100
K 273
kg
J
10 5 . 333
kg 0500 . 0 Δ
3
3
u
=
















+ ×
+























+
×
− = S

and, because ΔS
u
> 0, the entropy of the universe increases.

56 • In this problem, 2.00 mol of an ideal gas at 400 K expand quasi-
statically and isothermally from an initial volume of 40.0 L to a final volume of
80.0 L. (a) What is the entropy change of the gas? (b) What is the entropy change
of the universe for this process?

Picture the Problem We can use the definition of entropy change and the 1
st
law
of thermodynamics to express ΔS for the ideal gas as a function of its initial and
final volumes.

(a) The entropy change of the gas is
given by:

T
Q
S =
gas
Δ (1)
Chapter 19


1824

Apply the first law of thermodynamics
to the isothermal process to express Q
in terms of W
on
:
on int
Δ W E Q − =
or, because ΔE
int
= 0 for an isothermal
expansion of a gas,
on
W Q − =

The work done on the gas is given
by:








=
f
i
on
ln
V
V
nRT W ⇒








− =
f
i
ln
V
V
nRT Q

Substitute for Q in equation (1) to
obtain:








− =
f
i
gas
ln Δ
V
V
nR S

Substitute numerical values and evaluate ΔS:

( )
K
J
11.5
L 80.0
L 40.0
ln
K mol
J
8.314 mol 2.00 Δ
gas
=















− = S

(b) Because the process is reversible:
0
u
= ΔS

Remarks: The entropy change of the environment of the gas is −11.5 J/K.

57 •• [SSM] A system completes a cycle consisting of six quasi-static
steps, during which the total work done by the system is 100 J. During step 1 the
system absorbs 300 J of heat from a reservoir at 300 K, during step 3 the system
absorbs 200 J of heat from a reservoir at 400 K, and during step 5 it absorbs heat
from a reservoir at temperature T
3
. (During steps 2, 4 and 6 the system undergoes
adiabatic processes in which the temperature of the system changes from one
reservoir’s temperature to that of the next.) (a) What is the entropy change of the
system for the complete cycle? (b) If the cycle is reversible, what is the
temperature T
3
?

Picture the Problem We can use the fact that the system returns to its original
state to find the entropy change for the complete cycle. Because the entropy
change for the complete cycle is the sum of the entropy changes for each process,
we can find the temperature T
3
from the entropy changes during the 1st two
processes and the heat released during the third.

(a) Because S is a state function of
the system, and because the system’s
final state is identical to its initial
state:
0 Δ
cycle complete 1
system
= S
The Second Law of Thermodynamics


1825
(b) Relate the entropy changes for
each of the three heat reservoirs and
the system for one complete cycle of
the system:

0 Δ Δ Δ Δ
system 3 2 1
= + + + S S S S
or
0 0
3
3
2
2
1
1
= + + +
T
Q
T
Q
T
Q

Substitute numerical values. Heat is
rejected by the two high-temperature
reservoirs and absorbed by the cold
reservoir:

0
J 400
K 400
J 200
K 300
J 300
3
= +

+

T


Solving for T
3
yields:
K 267
3
= T

58 •• In this problem, 2.00 mol of an ideal gas initially has a temperature of
400 K and a volume of 40.0 L. The gas undergoes a free adiabatic expansion to
twice its initial volume. What is (a) the entropy change of the gas and (b) the
entropy change of the universe?

Picture the Problem The initial and final temperatures are the same for a free
expansion of an ideal gas. Thus, the entropy change ΔS for a free expansion from
V
i
to V
f
is the same as ΔS for an isothermal process from V
i
to V
f
. We can use the
definition of entropy change and the 1
st
law of thermodynamics to express ΔS for
the ideal gas as a function of its initial and final volumes.

(a) The entropy change of the gas is
given by:

T
Q
S =
gas
Δ (1)
Apply the first law of thermodynamics
to the isothermal process to express Q:
on int
Δ W E Q − =
or, because ΔE
int
= 0 for a free
expansion of a gas,
on
W Q − =

The work done on the gas is given
by:









=
f
i
on
ln
V
V
nRT W ⇒








− =
f
i
ln
V
V
nRT Q
Substitute for Q in equation (1) to
obtain:








− =
f
i
gas
ln Δ
V
V
nR S

Substitute numerical values and evaluate ΔS:

( )
K
J
11.5
L 80.0
L 40.0
ln
K mol
J
8.314 mol 2.00 Δ
gas
=















− = S
Chapter 19


1826
(b) The change in entropy of the
universe is the sum of the entropy
changes of the gas and the
surroundings:

gs surroundin gas u
Δ Δ Δ S S S + =
For the change in entropy of the
surroundings we use the fact that,
during the free expansion, the
surroundings are unaffected:

0
0
Δ
rev
gs surroundin
= = =
T T
Q
S

The change in entropy of the universe
is the change in entropy of the gas:
K
J
5 . 11 Δ
u
= S

59 •• A 200-kg block of ice at 0.0ºC is placed in a large lake. The
temperature of the lake is just slightly higher than 0.0ºC, and the ice melts very
slowly. (a) What is the entropy change of the ice? (b) What is the entropy change
of the lake? (c) What is the entropy change of the universe (the ice plus the lake)?

Picture the Problem Because the ice gains heat as it melts, its entropy change is
positive and can be calculated from its definition. Because the temperature of the
lake is just slightly greater than 0°C and the mass of water is so much greater than
that of the block of ice, the absolute value of the entropy change of the lake will
be approximately equal to the entropy change of the ice as it melts.

(a) The entropy change of the ice is
given by:

T
mL
S
f
ice
Δ =
Substitute numerical values and
evaluate
ice
ΔS :
( )
K
kJ
244
K 273
kg
kJ
333.5 kg 200
Δ
ice
=








= S

(b) Relate the entropy change of the
lake to the entropy change of the ice:

K
kJ
244 Δ Δ
ice lake
− = − ≈ S S

(c) The entropy change of the
universe due to this melting process
is the sum of the entropy changes of
the ice and the lake:

lake ice u
Δ Δ Δ S S S + =
The Second Law of Thermodynamics


1827

Because the temperature of the lake is slightly greater than that of the ice, the
magnitude of the entropy change of the lake is less than 244 kJ/K and the entropy
change of the universe is just slightly greater than zero. The melting of the ice is
an irreversible process and 0
u
> ΔS .

60 •• A 100-g piece of ice at 0.0ºC is placed in an insulated calorimeter with
negligible heat capacity containing 100 g of water at 100ºC. (a) What is the final
temperature of the water once thermal equilibrium is established? (b) Find the
entropy change of the universe for this process.

Picture the Problem We can use conservation of energy to find the equilibrium
temperature of the water and apply the equations for the entropy change during a
melting process and for constant-pressure processes to find the entropy change of
the universe (the entropy change of the piece of ice plus the entropy change of the
water in the insulated container).

(a) Apply conservation of energy
to obtain:

0
i
i
=

Q
or
0
water
cooling
water
warming
ice
melting
= − + Q Q Q

Substitute to relate the masses of the ice and water to their temperatures,
specific heats, and the final temperature of the water:

( ) ( )
( ) ( ) 0 C 100
C kg
kJ
18 . 4 g 100
C kg
kJ
18 . 4 g 100
kg
kJ
5 . 33 3 g 100
= − °








° ⋅









° ⋅
+








t
t


Solving for t yields:
C 1 . 10 ° = t

(b) The entropy change of the
universe is the sum of the entropy
changes of the ice and the water:

water ice u
S S S Δ + Δ = Δ
Using the expression for the entropy
change for a constant-pressure
process, express the entropy change
of the melting ice and warming ice-
water:








+ =
Δ + Δ = Δ
i
f
P
f
f
water warming ice melting ice
ln
T
T
mc
T
mL
S S S

Chapter 19


1828
Substitute numerical values to obtain:

( )
( )
K
J
137
K 273
K 283
ln
K kg
kJ
4.18 kg 0.100
K 273
kg
kJ
333.5 kg 0.100
Δ
ice
=

















+








= S

Find the entropy change of the cooling water:

( )
K
J
115
K 373
K 283
ln
K kg
kJ
4.18 kg 0.100 Δ
water
− =

















= S

Substitute for ΔS
ice
and ΔS
water
and
evaluate the entropy change of the
universe:
K
J
22
K
J
115
K
J
37 1 Δ
u
= − = S


Remarks: The result that ΔS
u
> 0 tells us that this process is irreversible.

61 •• [SSM] A 1.00-kg block of copper at 100ºC is placed in an insulated
calorimeter of negligible heat capacity containing 4.00 L of liquid water at 0.0ºC.
Find the entropy change of (a) the copper block, (b) the water, and (c) the
universe.

Picture the Problem We can use conservation of energy to find the equilibrium
temperature of the water and apply the equations for the entropy change during a
constant pressure process to find the entropy changes of the copper block, the
water, and the universe.

(a) Use the equation for the entropy
change during a constant-pressure
process to express the entropy
change of the copper block:









= Δ
i
f
Cu Cu Cu
ln
T
T
c m S (1)
Apply conservation of energy to
obtain:

0
i
i
=

Q
or
0
water
warming
block
copper
= +Q Q

The Second Law of Thermodynamics


1829

Substitute to relate the masses of the block and water to their temperatures,
specific heats, and the final temperature T
f
of the water:

( ) ( )
( ) ( ) 0 K 273
K kg
kJ
4.18
L
kg
1.00 L 4.00
K 373
K kg
kJ
0.386 kg 1.00
f
f
= −















+










T
T


Solve for T
f
to obtain: K 275.26
f
= T

Substitute numerical values in equation (1) and evaluate
Cu
ΔS :

( )
K
J
117
K 373
K 275.26
ln
K kg
kJ
0.386 kg 1.00 Δ
Cu
− =

















= S

(b) The entropy change of the
water is given by:









= Δ
i
f
water water water
ln
T
T
c m S
Substitute numerical values and evaluate
water
ΔS :

( )
K
J
138
K 273
K 26 . 275
ln
K kg
kJ
18 . 4 kg 00 . 4 Δ
water
=

















= S

(c) Substitute for
Cu
ΔS and
water
ΔS
and evaluate the entropy change of
the universe:
K
J
1 2
K
J
138
K
J
117 Δ Δ Δ
water Cu u
=
+ − = + = S S S


Remarks: The result that ΔS
u
> 0 tells us that this process is irreversible.

62 •• If a 2.00-kg piece of lead at 100ºC is dropped into a lake at 10ºC, find
the entropy change of the universe.

Picture the Problem Because the mass of the water in the lake is so much
greater than the mass of the piece of lead, the temperature of the lake will
increase only slightly and we can reasonably assume that its final temperature is
10°C. We can apply the equation for the entropy change during a constant
pressure process to find the entropy changes of the piece of lead, the water in the
lake, and the universe.
Chapter 19


1830
Express the entropy change of the
universe in terms of the entropy
changes of the lead and the water in
the lake:

w Pb u
S S S Δ + Δ = Δ (1)
Using the equation for the entropy change during a constant-pressure
process, express and evaluate the entropy change of the lead:

( )
K
J
69 . 70
K 373
K 283
ln
K kg
kJ
0.128 kg 2.00 ln Δ
i
f
Pb Pb Pb
− =

















=








=
T
T
c m S

The entropy change of the water in
the lake is given by:
w
Pb Pb Pb
w
Pb
w
w
w
Δ
Δ
T
T c m
T
Q
T
Q
S = = =

Substitute numerical values and
evaluate ΔS
w
:
( ) ( )
J/K 41 . 81
K 283
K 90
K kg
kJ
0.128 kg 2.00
Δ
w
=









= S

Substitute numerical values in
equation (1) and evaluate ΔS
u
:
K
J
11
K
J
81.41
K
J
70.69 Δ
u
= + − = S

Entropy and ″Lost″ Work

63 •• [SSM] A a reservoir at 300 K absorbs 500 J of heat from a second
reservoir at 400 K. (a) What is the change in entropy of the universe, and (b) how
much work is lost during the process?

Picture the Problem We can find the entropy change of the universe from the
entropy changes of the high- and low-temperature reservoirs. The maximum
amount of the 500 J of heat that could be converted into work can be found from
the maximum efficiency of an engine operating between the two reservoirs.

(a) The entropy change of the
universe is the sum of the
entropy changes of the two
reservoirs:








− − =
+ − = Δ + Δ = Δ
c h
c h
c h u
1 1
T T
Q
T
Q
T
Q
S S S


The Second Law of Thermodynamics


1831
Substitute numerical values and
evaluate ΔS
u
:
( )
J/K 0.42
K 300
1
K 400
1
J 500 Δ
u
=








− − = S


(b) Relate the heat that could have
been converted into work to the
maximum efficiency of an engine
operating between the two
reservoirs:

h max
Q W ε =
The maximum efficiency of an
engine operating between the two
reservoir temperatures is the
efficiency of a Carnot device
operating between the reservoir
temperatures:

h
c
C max
1
T
T
− = = ε ε
Substitute for ε
max
to obtain:
h
h
c
1 Q
T
T
W








− =

Substitute numerical values and
evaluate W:
( ) J 125 J 500
K 400
K 300
1 =








− = W

64 •• In this problem, 1.00 mol of an ideal gas at 300 K undergoes a free
adiabatic expansion from V
1
= 12.3 L to V
2
= 24.6 L. It is then compressed
isothermally and reversibly back to its original state. (a) What is the entropy
change of the universe for the complete cycle? (b) How much work is lost in this
cycle? (c) Show that the work lost is TΔS
u
.

Picture the Problem Although no energy is lost by the gas in the adiabatic free
expansion, the process is irreversible and the entropy of the gas (and the universe)
increases. In the isothermal reversible process that returns the gas to its original
state, the gas releases energy to the surroundings. However, because the process is
reversible, the entropy change of the universe is zero. Consequently, the net
entropy change is the negative of that of the gas in the isothermal compression.

Chapter 19


1832

(a) Relate the entropy change of the
universe to the entropy changes of
the gas during 1 complete cycle:

compresion isothermal
during gas
expansion free
during gas u
Δ Δ Δ S S S + =
or, because 0 Δ
n compressio isothermal
during gas
= S ,
T
Q
S S = =
expansion free
during gas u
Δ Δ

The work done by the gas during its
isothermal compression is given by:









− = − = − =
i
f
on by
ln
V
V
nRT Q W W
Substituting for Q in the expression
for
u
ΔS and simplifying yields:









− =
i
f
u
ln Δ
V
V
nR S (1)
Substitute numerical values and evaluate ΔS
u
:

( )
K
J
5.76
K
J
763 . 5
L 6 . 24
L 3 . 12
ln
K mol
J
8.314 mol 1.00 Δ
u
= =















− = S

(b) Use Equation 19-22 to find the
amount of energy that becomes
unavailable for doing work during
this process:

( )
kJ 1.73
K
J
5.763 K 300 Δ
u lost
=






= = S T W

(c) No work is done in the free
expansion. In the adiabatic
compression, the work done on the
gas is:

u
i
f
i
f
f
i
i f gas, on i f gas, by
ln ln
ln
S T
V
V
nR T
V
V
nRT
V
V
nRT W W
Δ =
















=








=








− = − =
→ →

General Problems

65 • A heat engine with an output of 200 W has an efficiency of 30%. It
operates at 10.0 cycles/s. (a) How much work is done by the engine during each
cycle? (b) How much heat is absorbed from the hot reservoir and how much is
released to the cold reservoir during each cycle?

Picture the Problem We can use the definition of power to find the work done
each cycle and the definition of efficiency to find the heat that is absorbed each
cycle. Application of the first law of thermodynamics will yield the heat given off
each cycle.
The Second Law of Thermodynamics


1833

(a) Use the definition of power to
relate the work done in each cycle to
the frequency of each cycle:

f
P
t P W = = Δ
cycle

where f is the frequency of the engine.

Substitute numerical values and
evaluate W
cycle
:
J 20.0
s 10.0
W 200
1
cycle
= =

W

(b) Express the heat absorbed in each
cycle in terms of the work done and
the efficiency of the engine:

J 67
0.30
J 20.0
cycle
cycle h,
= = =
ε
W
Q

Apply the 1
st
law of thermodynamics
to find the heat given off in each
cycle:
J 47
J 20 J 67
cycle h, cycle c,
=
− = − = W Q Q


66 • During each cycle, a heat engine operating between two heat
reservoirs absorbs 150 J from the reservoir at 100ºC and releases 125 J to the
reservoir at 20ºC. (a) What is the efficiency of this engine? (b) What is the ratio
of its efficiency to that of a Carnot engine working between the same reservoirs?
(This ratio is called the second law efficiency.)

Picture the Problem We can use their definitions to find the efficiency of the
engine and that of a Carnot engine operating between the same reservoirs.

(a) The efficiency of the engine
is given by:
h
c
h
c h
h
1
Q Q
Q Q Q
Q
W
− =

= = ε

Substitute numerical values and
evaluate ε:
% 7 . 16 % 67 . 16
J 150
J 125
1 = = − = ε

(b) Find the efficiency of a Carnot
engine operating between the same
reservoirs:

% 45 . 21
K 373
K 293
1 1
h
c
C
= − = − =
T
T
ε

Express the ratio of the two
efficiencies:
777 . 0
% 45 . 21
% 67 . 16
C
= =
ε
ε


67 • [SSM] An engine absorbs 200 kJ of heat per cycle from a reservoir
at 500 K and releases heat to a reservoir at 200 K. Its efficiency is 85 percent of
that of a Carnot engine working between the same reservoirs. (a) What is the
Chapter 19


1834
efficiency of this engine? (b) How much work is done in each cycle? (c) How
much heat is released to the low-temperature reservoir during each cycle?

Picture the Problem We can use the definition of efficiency to find the work
done by the engine during each cycle and the first law of thermodynamics to find
the heat released to the low-temperature reservoir during each cycle.

(a) Express the efficiency of the
engine in terms of the efficiency of a
Carnot engine working between the
same reservoirs:









− = =
h
c
C
1 85 . 0 85 . 0
T
T
ε ε

Substitute numerical values and
evaluate ε :
% 51 510 . 0
K 500
K 200
1 85 . 0 = =








− = ε

(b) Use the definition of efficiency to
find the work done in each cycle:

( )( )
MJ 0.10
kJ 102 kJ 200 .510 0
h
=
= = = Q W ε


(c) Apply the first law of
thermodynamics to the cycle to obtain:
kJ 8 9
kJ 02 1 kJ 00 2
cycle h, cycle c,
=
− = − = W Q Q


68 • Estimate the change in entropy of the universe associated with an
Olympic diver diving into the water from the 10-m platform.

Picture the Problem Assume that the mass of the diver is 75 kg and that the
temperature of the water in the pool is 25°C. The energy added to the water in the
pool is the change in the gravitational potential energy of the diver during the
dive.

The change in entropy of the
universe associated with a dive is
given by:

water
water to added
water u
Δ Δ
T
Q
S S = =
where
water to added
Q is the energy entering
the water as a result of the kinetic
energy of the diver as he enters the
water.

The energy added to the water is the
change in the gravitational potential
energy of the diver:

water
u
Δ
T
mgh
S =
The Second Law of Thermodynamics


1835
Substitute numerical values and
evaluate
u
ΔS :
( )( )( )
( )
K
J
25
K 273 25
m 10 m/s 81 . 9 kg 75
Δ
2
u

+
= S


69 • To maintain the temperature inside a house at 20ºC, the electric power
consumption of the electric baseboard heaters is 30.0 kW on a day when the
outside temperature is –7ºC. At what rate does this house contribute to the
increase in the entropy of the universe?

Picture the Problem The change in entropy of the universe is the change in
entropy of the house plus the change in entropy of the environment. We can find
the change in entropy of the house by exploiting the given information that the
temperature inside the house is maintained at a constant temperature. We can find
the change in entropy of the surrounding by dividing the heat added by the
temperature.

Entropy is a state function, and the
state of the house does not change.
Therefore the entropy of the house
does not change:

gs surroundin house u
Δ Δ Δ S S S + =
or, because 0 Δ
house
= S ,
gs surroundin u
Δ Δ S S =
Heat is absorbed by the surroundings
at the same rate R that energy is
delivered to the house:

gs surroundin gs surroundin
gs surroundin
Δ
Δ
T
t R
T
Q
S = =
Substitute for ΔS
surroundings
yields:

gs surroundin
u
Δ
Δ
T
t R
S = ⇒
gs surroundin
u
Δ
Δ
T
R
t
S
=

Substitute numerical values and
evaluate ΔS
u
/Δt:
K
W
13 1
K 266
kW 30.0
Δ
Δ
u
= =
t
S


70 •• Calvin Cliffs Nuclear Power Plant, located on the Hobbes River,
generates 1.00 GW of power. In this plant, liquid sodium circulates between the
reactor core and a heat exchanger located in the superheated steam that drives the
turbine. Heat is absorbed by the liquid sodium in the core, and released by the
liquid sodium (and into the superheated steam) in the heat exchanger. The
temperature of the superheated steam is 500 K. Heat is released into the river, and
the water in the river flows by at a temperature of 25ºC. (a) What is the highest
efficiency that this plant can have? (b) How much heat is released into the river
every second? (c) How much heat must be released by the core to supply
Chapter 19


1836
1.00 GW of electrical power? (d) Assume that new environmental laws have been
passed to preserve the unique wildlife of the river. Because of these laws, the
plant is not allowed to heat the river by more than 0.50ºC. What is the minimum
flow rate that the water in the Hobbes River must have?

Picture the Problem We can use the expression for the Carnot efficiency of the
plant to find the highest efficiency this plant can have. We can then use this
efficiency to find the power that must be supplied to the plant to generate
1.00 GW of power and, from this value, the power that is wasted. The rate at
which heat is being released to the river is related to the requisite flow rate of the
river by . dt dV T c dt dQ ρ Δ =

(a) The Carnot efficiency of a plant
operating between temperatures T
c

and T
h
is given by:

h
c
C max
1
T
T
− = = ε ε
Substitute numerical values and
evaluate ε
C
:

404 . 0
K 500
K 298
1
max
= − = ε

(c) The power that must be supplied,
at 40.4% efficiency, to produce an
output of 1.00 GW is given by:
GW 48 . 2
0.404
GW 00 . 1
max
output
supplied
=
= =
ε
P
P


(b) Relate the wasted power to the
power generated and the power
supplied:

generated supplied wasted
P P P − =
Substitute numerical values and
evaluate
wasted
P :

GW 48 . 1
GW 00 . 1 GW 48 . 2
wasted
=
− = P


(d) Express the rate at which heat is
being dumped into the river:

( )
dt
dV
T c
V
dt
d
T c
dt
dm
T c
dt
dQ
ρ
ρ
Δ =
Δ = Δ =


Solve for the flow rate dV/dt of the
river:

ρ T c
dt dQ
dt
dV
Δ
=
The Second Law of Thermodynamics


1837
Substitute numerical values (see
Table 19-1 for the specific heat of
water) and evaluate dV/dt:

( )
L/s 10 1 . 7
m
kg
10 K 50 . 0
kg
J
4180
s
J
10 48 . 1
5
3
3
9
× =














×
=
dt
dV


71 •• An inventor comes to you to explain his new invention. It is a novel
heat engine using water vapor as the working substance. He claims that the water
vapor absorbs heat at 100°C, does work at the rate of 125 W, and releases heat to
the air at the rate of only 25.0 W, when the air temperature is 25°C. (a) Explain
to him why he cannot be correct. (b) After careful analysis of the data in his
prospectus folder, you decide he has made an error in the measurement of his
exhausted-heat value. What is the minimum rate of exhausting heat that would
make you consider believing him?

Picture the Problem We can use the inventor’s data to calculate the thermal
efficiency of his steam engine and then compare this value to the efficiency of a
Carnot engine operating between the same temperatures.

(a) The Carnot efficiency of an
engine operating between these
temperatures is:

% 1 . 20
K 373
K 298
1 1
h
c
C
= − = − =
T
T
ε

The thermal efficiency of the
inventor’s device, in terms of the rate
at which it expels heat to the air and
does work is:
% 3 . 83
W 0 . 25 W 125
W 125
c h
=
+
=
+
= =
dt
dQ
dt
dW
dt
dW
dt
dQ
dt
dW
ε


You should explain to him that, because the efficiency he claims for his invention
is greater than the efficiency of a Carnot engine operating between the same two
temperatures, his data is not consistent with what is known about the
thermodynamics of engines. He must have made a mistake in his analysis of his
data−or he is a con man looking for suckers to swindle.

(b) The maximum efficiency of a steam engine that has ever been achieved is
about 50% of the Carnot efficiency of an engine operating between the same
temperatures.

Setting the efficiency of his steam
engine equal to half the Carnot
efficiency of the engine yields:

dt
dQ
dt
dW
dt
dW
dt
dQ
dt
dW
c h
C 2
1
+
= = ε
Chapter 19


1838
Solve for dQ
c
/dt to obtain:

dt
dW
dt
dQ








− = 1
2
C
c
ε


Assuming that the inventor has
measured the work done per cycle
by his invention correctly:

( ) W 1100 W 125 1
201 . 0
2
c
≈ ⎟





− =
dt
dQ

a value totally inconsistent with the
inventor’s claims for his engine.

Ignoring his claim that 125.0 W of
work are done per cycle, let’s
assume that his device does take in
energy at the rate of 150 W each
cycle and find how much work it
would do with an efficiency half that
of a Carnot engine:

dt
dQ
dt
dW
h
C 2
1
= ε ⇒
dt
dQ
dt
dW
h
C 2
1
ε =


Substituting numerical values yields:
( )( ) W 15 W 150 201 . 0
2
1
≈ =
dt
dW


Because
dt
dW
dt
dQ
dt
dQ
− =
h c
, a
reasonable value for dQ
c
/dt is:

W 135 W 15 W 150
c
= − =
dt
dQ


72 •• The cycle represented in Figure 19-12 (next to Problem 19-14) is for
1.00 mol of an ideal monatomic gas. The temperatures at points A and B are 300
and 750 K, respectively. What is the efficiency of the cyclic process ABCDA?

Picture the Problem Because the cycle represented in Figure 19-12 is a Carnot
cycle, its efficiency is that of a Carnot engine operating between the temperatures
of its isotherms.

The Carnot efficiency of the cycle is
given by:

h
c
C
1
T
T
− = ε
Substitute numerical values and
evaluate ε
C
:
% 0 . 60
K 750
K 300
1
C
= − = ε

73 •• [SSM] (a) Which of these two processes is more wasteful? (1) A
block moving with 500 J of kinetic energy being slowed to rest by sliding
(kinetic) friction when the temperature of the environment is 300 K, or (2) A
reservoir at 400 K releasing 1.00 kJ of heat to a reservoir at 300 K? Explain your
choice. Hint: How much of the 1.00 kJ of heat could be converted into work by an
ideal cyclic process? (b) What is the change in entropy of the universe for each
process?
The Second Law of Thermodynamics


1839
Picture the Problem All 500 J of mechanical energy are lost, i.e., transformed
into heat in process (1). For process (2), we can find the heat that would be
converted to work by a Carnot engine operating between the given temperatures
and subtract that amount of work from 1.00 kJ to find the energy that is lost. In
Part (b) we can use its definition to find the change in entropy for each process.

(a) For process (2):
in C recovered max , 2
Q W W ε = =

The efficiency of a Carnot engine
operating between temperatures
T
h
and T
c
is given by:

h
c
C
1
T
T
− = ε
and hence
in
h
c
recovered
1 Q
T
T
W








− =

Substitute for
C
ε to obtain:

( ) J 250 kJ 1.00
K 400
K 300
1
recovered
=






− = W
or
750 J are lost.

Process (1) produces more waste heat. Process (2) is more wasteful of available
work.

(b) Find the change in entropy of the
universe for process (1):

J/K 1.67
K 300
J 500 Δ
Δ
1
= = =
T
Q
S

Express the change in entropy of
the universe for process (2):









− Δ =
Δ
+
Δ
− = Δ + Δ = Δ
h c
c h
c h 2
1 1
T T
Q
T
Q
T
Q
S S S


Substitute numerical values and
evaluate ΔS
2
:
( )
J/K 833 . 0
K 400
1
K 300
1
kJ 1.00 Δ
2
=








− = S


74 •• Helium, a monatomic gas, is initially at a pressure of 16 atm, a volume
of 1.0 L, and a temperature of 600 K. It is quasi-statically expanded at constant
temperature until its volume is 4.0 L and is then quasi-statically compressed at
constant pressure until its volume and temperature are such that a quasi-static
adiabatic compression will return the gas to its original state. (a) Sketch this
Chapter 19


1840
cycle on a PV diagram. (b) Find the volume and temperature after the
compression at constant pressure. (c) Find the work done during each step of the
cycle. (d) Find the efficiency of the cycle.

Picture the Problem Denote the three states of the gas as 1, 2, and 3 with 1 being
the initial state. We can use the ideal-gas law and the equation of state for an
adiabatic process to find the temperatures, volumes, and pressures at points 1, 2,
and 3. To find the work done during each cycle, we can use the equations for the
work done during isothermal, isobaric, and adiabatic processes. Finally, we find
the efficiency of the cycle from the work done each cycle and the heat that enters
the system during the isothermal expansion.

(a) The PV diagram of the cycle is
shown to the right.



(b) Apply the ideal-gas law to the
isothermal expansion 1→2 to find
P
2
:

( ) atm 4.0
L 4.0
L 1.0
atm 16
2
1
1 2
=








= =
V
V
P P

Apply an equation for an adiabatic
process to relate the pressures and
volumes at 1 and 3:

γ γ
3 3 1 1
V P V P = ⇒
γ 1
3
1
1 3








=
P
P
V V

Substitute numerical values and
evaluate V
3
:
( )
L 2.3
L 2.294
atm 4.0
atm 16
L 1.0
1.67 1
3
=
=








= V


Apply an equation for an adiabatic
process (γ =1.67) to relate the
temperatures and volumes at 1 and 3:

1
1 1
1
3 3
− −
=
γ γ
V T V T ⇒
1
3
1
1 3









=
γ
V
V
T T

The Second Law of Thermodynamics


1841
Substitute numerical values and
evaluate T
3
:
( )
K 10 3.4
K 344
L 2.294
L 1.0
K 600
2
1 1.67
3
× =
=








=

T


(c) Express the work done each
cycle:

31 23 12
W W W W + + = (1)
For the process 1→2:
( )( )
L atm 22.18
L 1.0
L 4.0
ln L 1.0 atm 16
ln ln
1
2
1 1
1
2
1 12
⋅ =








=








=








=
V
V
V P
V
V
nRT W


For the process 2→3:
( )( )
L atm 824 . 6
L 4.00 L 2.294 atm 4.0
Δ
23 2 23
⋅ − =
− =
= V P W


For the process 3→1:

( ) ( )
( )( ) ( )( ) [ ]
L atm 0.24 1
L 2.294 atm 4.0 L 1.0 atm 16
Δ
2
3
3 3 1 1 2
3
3 1 2
3
31 V 31
⋅ − =
− − =
− − = − − = − = V P V P T T nR T C W


Substitute numerical values in
equation (1) and evaluate W:

L atm 5 L atm 5.116
L atm 10.24
L atm 6.824 L atm 18 . 22
⋅ = ⋅ =
⋅ −
⋅ − ⋅ = W


(d) Use its definition to express
the efficiency of the cycle:

12 12 in
W
W
Q
W
Q
W
= = = ε

Substitute numerical values and
evaluate ε:
% 20
L atm 22.18
L atm 5.116



= ε

75 •• [SSM] A heat engine that does the work of blowing up a balloon at a
pressure of 1.00 atm absorbs 4.00 kJ from a reservoir at 120ºC. The volume of the
balloon increases by 4.00 L, and heat is released to a reservoir at a temperature T
c
,
where T
c
< 120ºC. If the efficiency of the heat engine is 50% of the efficiency of a
Carnot engine working between the same two reservoirs, find the temperature T
c
.
Chapter 19


1842
Picture the Problem We can express the temperature of the cold reservoir as a
function of the Carnot efficiency of an ideal engine and, given that the efficiency
of the heat engine is half that of a Carnot engine, relate T
c
to the work done by and
the heat input to the real heat engine.

Using its definition, relate the
efficiency of a Carnot engine
working between the same reservoirs
to the temperature of the cold
reservoir:

h
c
C
1
T
T
− = ε ⇒ ( )
C h c
1 ε − = T T
Relate the efficiency of the heat
engine to that of a Carnot engine
working between the same
temperatures:

C 2
1
in
ε ε = =
Q
W

in
C
2
Q
W
= ε

Substitute for
C
ε to obtain:









− =
in
h c
2
1
Q
W
T T

The work done by the gas in
expanding the balloon is:

( )( )
L atm 4.00
L 4.00 atm 1.00 Δ
⋅ =
= = V P W


Substitute numerical values and evaluate T
c
:

( ) K 313
kJ 4.00
L atm
J 101.325
L atm 4.00 2
1 K 393
c
=



















× ⋅
− = T

76 •• Show that the coefficient of performance of a Carnot engine run as a
refrigerator is related to the efficiency of a Carnot engine operating between the
same two temperatures by
C C c h
COP ε × = T T .

Picture the Problem We can use the definitions of the COP and ε
C
to show that
their relationship is
h C C C
COP T T = × ε .

Using the definition of the COP,
relate the heat removed from the cold
reservoir to the work done each
cycle:

W
Q
c
COP =
The Second Law of Thermodynamics


1843
Apply energy conservation to relate
Q
c
, Q
h
, and W:

W Q Q − =
h c

Substitute for Q
c
to obtain:
W
W Q −
=
h
COP

Divide the numerator and
denominator by Q
h
and simplify to
obtain:
h
h h
1
COP
Q
W
Q
W
W
W Q

=

=

Because
h
c
h
C
1
T
T
Q
W
− = = ε :
C
h
c
C
h
c
C
C
c
1 1
1
COP
ε ε ε
ε T
T
T
T
=








− −
=

=
and
h
c
c C
COP
T
T
= × ε

77 •• A freezer has a temperature T
c
= –23ºC. The air in the kitchen has a
temperature T
h
= 27ºC. The freezer is not perfectly insulated and some heat leaks
through the walls of the freezer at a rate of 50 W. Find the power of the motor that
is needed to maintain the temperature in the freezer.

Picture the Problem We can use the definition of the COP to express the work
the motor must do to maintain the temperature of the freezer in terms of the rate at
which heat flows into the freezer. Differentiation of this expression with respect
to time will yield an expression for the power of the motor that is needed to
maintain the temperature in the freezer.

Using the definition of the COP,
relate the heat that must be removed
from the freezer to the work done by
the motor:

W
Q
c
COP = ⇒
COP
c
Q
W =
Differentiate this expression with
respect to time to express the power
of the motor:

COP
c
dt dQ
dt
dW
P = =

Express the maximum COP of the
motor:

T
T
Δ
=
c
max
COP

Chapter 19


1844
Substitute for COP
max
to obtain:
c
c
T
T
dt
dQ
P
Δ
=

Substitute numerical values and
evaluate P:
( ) W 10
K 250
K 50
W 50 =








= P

78 •• In a heat engine, 2.00 mol of a diatomic gas are taken through the
cycle ABCA as shown in Figure 19-20. (The PV diagram is not drawn to scale.)
At A the pressure and temperature are 5.00 atm and 600 K. The volume at B is
twice the volume at A. The segment BC is an adiabatic expansion and the
segment CA is an isothermal compression. (a) What is the volume of the gas at
A? (b) What are the volume and temperature of the gas at B? (c) What is the
temperature of the gas at C? (d) What is the volume of the gas at C? (e) How
much work is done by the gas in each of the three segments of the cycle? (f) How
much heat is absorbed or released by the gas in each segment of this cycle?

Picture the Problem We can use the ideal-gas law to find the unknown
temperatures, pressures, and volumes at points A, B, and C and then find the work
done by the gas and the efficiency of the cycle by using the expressions for the
work done on or by the gas and the heat that enters the system for the constant-
pressure, adiabatic, and isothermal processes of the cycle.

(a) Apply the ideal-gas law to find
the volume of the gas at A:

( ) ( )
L 19.7
L 69 . 19
m 10
L 1
m 10 969 . 1
atm
kPa 101.325
atm 5.00
K 600
K mol
J
8.314 mol 2.00
3 3
3 2
A
A
A
=
= × × =
×







=
=


P
nRT
V

(b) We’re given that
A B
2V V = .
Hence:

( ) L 39.4 L 38 . 39 L 19.69 2
B
= = = V

Apply the ideal-gas law to this
constant-pressure process to
obtain:

( )
K 1200
2
K 600
A
A
A
B
A B
=
= =
V
V
V
V
T T


The Second Law of Thermodynamics


1845

(c) Because the process C→A is
isothermal:

K 600
A C
= = T T

(d) Apply an equation for an
adiabatic process (γ = 1.4) to find the
volume of the gas at C:

1
C C
1
B B
− −
=
γ γ
V T V T ⇒
1
1
C
B
B C









=
γ
T
T
V V


Substitute numerical values and
evaluate V
C
:
( )
L 223
L 77 . 222
K 600
K 1200
L 39.38
1 1.4
1
C
=
=








=

V


(e) The work done by the gas
during the constant-pressure
process AB is given by:

( ) ( )
A A
A A A A B A AB
2
V P
V V P V V P W
=
− = − =

Substitute numerical values and
evaluate W
AB
:
( )( )
kJ 9.98 J 10 9754 . 9
L atm
J 101.325
L atm 98.45
L 19.69 atm 5.00
3
AB
= × =

× ⋅ =
= W


Apply the first law of thermodynamics
to express the work done on the gas
during the adiabatic expansion BC:

BC 2
5
BC V BC int,
BC int, BC in, BC int, BC
0
T nR
T nc E
E Q E W
Δ − =
Δ − = Δ =
− Δ = − Δ =


Substitute numerical values and evaluate W
BC
:

( ) ( )
kJ 24.9
J 10 494 . 2 K 1200 K 600
K mol
J
8.314 mol 2.00
4
2
5
BC
=
× = − ⎟






− = W


The work done by the gas during the isothermal compression CA is:

( ) ( )
kJ 2 . 24 kJ 20 . 24
L 222.77
L 19.69
ln K 600
K mol
J
8.314 mol 2.00 ln
C
A
C CA
− = − =















=








=
V
V
nRT W


Chapter 19


1846

(f) The heat absorbed during the constant-pressure expansion AB is:

( ) ( )
kJ 9 . 34 kJ 92 . 34
K 600 K 1200
K mol
J
8.314 mol 2.00 Δ Δ
2
7
B A 2
7
B A P AB
= =
− ⎟






= = =
− −
T nR T nc Q


The heat absorbed during the
adiabatic expansion BC is:

0
BC
= Q
Use the first law of thermodynamics
to find the heat absorbed during the
isothermal compression CA:

kJ 2 . 24
CA CA int, CA CA
− =
= Δ + = W E W Q

because 0
CA int,
= ΔE for an isothermal
process.

79 •• [SSM] In a heat engine, 2.00 mol of a diatomic gas are carried
through the cycle ABCDA shown in Figure 19-21. (The PV diagram is not drawn
to scale.) The segment AB represents an isothermal expansion, the segment BC an
adiabatic expansion. The pressure and temperature at A are 5.00 atm and 600 K.
The volume at B is twice the volume at A. The pressure at D is 1.00 atm.
(a) What is the pressure at B? (b) What is the temperature at C? (c) Find the total
work done by the gas in one cycle.

Picture the Problem We can use the ideal-gas law to find the unknown
temperatures, pressures, and volumes at points B, C, and D. We can then find the
work done by the gas and the efficiency of the cycle by using the expressions for
the work done on or by the gas and the heat that enters the system for the various
thermodynamic processes of the cycle.

(a) Apply the ideal-gas law for a
fixed amount of gas to the
isothermal process AB to find the
pressure at B:
( )
kPa 253
kPa 253.3
atm 1
kPa 101.325
atm 2.50
2
atm 00 . 5
A
A
B
A
A B
=
= × =
= =
V
V
V
V
P P


(b) Apply the ideal-gas law for a
fixed amount of gas to the
adiabatic process BC to express the
temperature at C:

B B
C C
B C
V P
V P
T T = (1)
The Second Law of Thermodynamics


1847
Use the ideal-gas law to find the
volume of the gas at B:
( ) ( )
L 39.39
kPa 253.3
K 600
K mol
J
8.314 mol 2.00
B
B
B
=







=
=
P
nRT
V


Use the equation of state for an
adiabatic process and γ = 1.4 to
find the volume occupied by the
gas at C:
( )
L 75.78
atm 1.00
atm 2.50
L 39.39
1.4 1 1
C
B
B C
=








=








=
γ
P
P
V V

Substitute numerical values in
equation (1) and evaluate T
C
:
( )
( )( )
( )( )
K 462
L 39.39 atm 2.50
L 75.78 atm 1.00
K 600
C
=
= T


(c) The work done by the gas in
one cycle is given by:

DA CD BC AB
W W W W W + + + =

The work done during the isothermal expansion AB is:

( ) ( ) kJ 6.915
V
2V
ln K 600
K mol
J
8.314 mol 2.00 ln
A
A
A
B
A AB
=















=








=
V
V
nRT W

The work done during the adiabatic expansion BC is:

( ) ( )
kJ 5.737
K 00 6 K 62 4
K mol
J
8.314 mol 2.00 Δ Δ
2
5
BC 2
5
BC V BC
=
− ⎟






− = − = − = T nR T C W


The work done during the isobaric compression CD is:

( ) ( )( )
kJ 5.680
L atm
J 101.325
L atm 56.09 L 75.78 L 19.7 atm 1.00
C D C CD
− =

× ⋅ − = − = − = V V P W


Express and evaluate the work
done during the constant-volume
process DA:

0
DA
= W
Chapter 19


1848
Substitute numerical values and
evaluate W:
kJ 97 . 6 kJ 972 . 6
0 kJ 5.680 kJ 5.737 kJ 915 . 6
= =
+ − + = W


80 •• In a heat engine, 2.00 mol of a monatomic gas are taken through the
cycle ABCA as shown in Figure 19-20. (The PV diagram is not drawn to scale.)
At A the pressure and temperature are 5.00 atm and 600 K. The volume at B is
twice the volume at A. The segment BC is an adiabatic expansion and the
segment CA is an isothermal compression. (a) What is the volume of the gas at
A? (b) What are the volume and temperature of the gas at B? (c) What is the
temperature of the gas at C? (d) What is the volume of the gas at C? (e) How
much work is done by the gas in each of the three segments of the cycle? (f) How
much heat is absorbed by the gas in each segment of the cycle?

Picture the Problem We can use the ideal-gas law to find the unknown
temperatures, pressures, and volumes at points A, B, and C and then find the work
done by the gas and the efficiency of the cycle by using the expressions for the
work done on or by the gas and the heat that enters the system for the isobaric,
adiabatic, and isothermal processes of the cycle.

(a) Apply the ideal-gas law to find
the volume of the gas at A:

( ) ( )
L 19.7 L 19.69
atm
kPa 101.325
atm 5.00
K 600
K mol
J
8.314 mol 2.00
A
A
A
= =
×







=
=
P
nRT
V


(b) We’re given that:

( )
L 39.4
L 39 . 39 L 19.69 2 2
A B
=
= = = V V


Apply the ideal-gas law to this
isobaric process to find the
temperature at B:

( )
K 1200
2
K 600
A
A
A
B
A B
=
= =
V
V
V
V
T T


(c) Because the process CA is
isothermal:
K 600
A C
= = T T

(d) Apply an equation for an adiabatic
process (γ = 5/3) to express the
volume of the gas at C:
1
C C
1
B B
− −
=
γ γ
V T V T ⇒
1
1
C
B
B C









=
γ
T
T
V V

The Second Law of Thermodynamics


1849
Substitute numerical values and
evaluate V
C
:
( )
L 11 1 L 4 . 111
K 600
K 1200
L 39.39
2
3
C
= =








= V


(e) The work done by the gas
during the isobaric process AB is
given by:

( ) ( )
A A
A A A A B A AB
2
V P
V V P V V P W
=
− = − =


Substitute numerical values and
evaluate W
AB
:
( )( )
kJ 9.98 kJ 975 . 9
L atm
J 101.325
L atm 98.45
L 19.69 atm 5.00
AB
= =

× ⋅ =
= W


Apply the first law of thermodynamics
to express the work done by the gas
during the adiabatic expansion BC:

( )
BC 2
3
BC V BC int,
BC int,
BC in, BC int, BC
0
T nR
T nc E
E
Q E W
Δ − =
Δ − = Δ =
− Δ =
− Δ =


Substitute numerical values and evaluate W
BC
:

( ) ( )
kJ 0 . 5 1
kJ 97 . 14 K 1200 K 600
K mol
J
8.314 mol 2.00
2
3
BC
=
= − ⎟






− = W


The work done by the gas during the isothermal compression CA is:

( ) ( )
kJ 3 . 17 kJ 29 . 17
L 4 . 11 1
L 19.69
ln K 600
K mol
J
8.314 mol 2.00 ln
C
A
C CA
− − =















=








=
V
V
nRT W


(f) The heat absorbed during the isobaric expansion AB is:

( ) ( )
kJ 9 . 24
K 600 K 1200
K mol
J
8.314 mol 2.00 Δ Δ
2
5
AB 2
5
AB P AB in,
=
− ⎟






= = = T nR T nc Q


Chapter 19


1850
Express and evaluate the heat
absorbed during the adiabatic
expansion BC:

0
BC
= Q
Use the first law of thermodynamics
to express and evaluate the heat
absorbed during the isothermal
compression CA:

kJ 3 . 17
Δ
CA CA int, CA CA
− =
= + = W E W Q

because ΔE
int
= 0 for an isothermal
process.

81 •• In a heat engine, 2.00 mol of a monatomic gas are carried through the
cycle ABCDA shown in Figure 19-21. (The PV diagram is not drawn to scale.)
The segment AB represents an isothermal expansion, the segment BC an
adiabatic expansion. The pressure and temperature at A are 5.00 atm and 600 K.
The volume at B is twice the volume at A. The pressure at D is 1.00 atm.
(a) What is the pressure at B? (b) What is the temperature at C? (c) Find the total
work done by the gas in one cycle.

Picture the Problem We can use the ideal-gas law to find the unknown
temperatures, pressures, and volumes at points B, C, and D and then find the work
done by the gas and the efficiency of the cycle by using the expressions for the
work done on or by the gas and the heat that enters the system for the various
thermodynamic processes of the cycle.

(a) Apply the ideal-gas law for a
fixed amount of gas to the isothermal
process AB:
( )
kPa 253 kPa 3 . 253
atm 1
kPa 101.325
atm 2.50
2
atm 00 . 5
A
A
B
A
A B
= =
× =
= =
V
V
V
V
P P


(b) Apply the ideal-gas law for a
fixed amount of gas to the adiabatic
process BC:

B B
C C
B C
V P
V P
T T = (1)
Use the ideal-gas law to find the
volume at B:
( ) ( )
L 39.39
kPa 253.3
K 600
K mol
J
8.314 mol 2.00
B
B
B
=







=
=
P
nRT
V


The Second Law of Thermodynamics


1851
Use the equation of state for an
adiabatic process and γ = 5/3 to
find the volume occupied by the
gas at C:
( )
L 26 . 8 6
atm 1.00
atm 2.50
L 39.39
5 3 1
C
B
B C
=








=








=
γ
P
P
V V

Substitute numerical values in
equation (1) and evaluate T
C
:
( )
( )( )
( )( )
K 416 K 9 . 415
L 39.39 atm 2.50
L 26 . 8 6 atm 1.00
K 600
C
= =
= T


(c) The work done by the gas in one
cycle is given by:

DA CD BC AB
W W W W W + + + = (2)
The work done during the isothermal expansion AB is:

( ) ( ) kJ 6.915
2
ln K 600
K mol
J
8.314 mol 2.00 ln
A
A
A
B
A AB
=















=








=
V
V
V
V
nRT W

The work done during the adiabatic expansion BC is:

( ) ( )
kJ 592 . 4
K 00 6 K 9 . 15 4
K mol
J
8.314 mol 2.00
Δ Δ
2
3
BC 2
3
BC V BC
=
− ⎟






− =
− = − = T nR T C W


The work done during the isobaric compression CD is:

( ) ( )( )
kJ 920 . 4
L atm
J 101.325
L atm 56 . 8 4 L 26 . 8 6 L 19.7 atm 1.00
C D C CD
− =

× ⋅ − = − = − = V V P W


The work done during the constant-
volume process DA is:

0
DA
= W
Substitute numerical values in
equation (2) to obtain:
kJ 59 . 6
0 kJ 920 . 4 kJ 592 . 4 kJ 915 . 6
=
+ − + = W


82 •• Compare the efficiency of the Otto cycle to the efficiency of the
Carnot cycle operating between the same maximum and minimum temperatures.
(The Otto cycle is discussed in Section 19-1.)

Chapter 19


1852
Picture the Problem We can express the efficiency of the Otto cycle using the
result from Example 19-2. We can apply the relation constant
1
=
− γ
TV to the
adiabatic processes of the Otto cycle to relate the end-point temperatures to the
volumes occupied by the gas at these points and eliminate the temperatures at c
and d. We can use the ideal-gas law to find the highest temperature of the gas
during its cycle and use this temperature to express the efficiency of a Carnot
engine. Finally, we can compare the efficiencies by examining their ratio.

The efficiency of the Otto engine is
given in Example 19-2:

b
a d
T T
T T


− =
c
Otto
1 ε (1)
where the subscripts refer to the various
points of the cycle as shown in Figure
19-3.

Apply the relation constant
1
=
− γ
TV
to the adiabatic process a→b to
obtain:

1 −








=
γ
b
a
a b
V
V
T T
Apply the relation constant
1
=
− γ
TV
to the adiabatic process c→d to
obtain:

1 −








=
γ
c
d
d c
V
V
T T
Subtract the first of these equations
from the second to obtain:

1 1 − −

















= −
γ γ
b
a
a
c
d
d b c
V
V
T
V
V
T T T

In the Otto cycle, V
a
= V
d
and
V
c
= V
b
. Substitute to obtain:

( )
1
1 1

− −








− =

















= −
γ
γ γ
b
a
a d
b
a
a
b
a
d b c
V
V
T T
V
V
T
V
V
T T T


Substitute in equation (1) and
simplify to obtain:
( )
b
a
a
b
b
a
a d
a d
T
T
V
V
V
V
T T
T T
− =








− =










− =


1 1
1
1
1
Otto
γ
γ
ε

Note that, while T
a
is the lowest
temperature of the cycle, T
b
is not the
highest temperature.
The Second Law of Thermodynamics


1853
Apply the ideal-gas law to c and
b to obtain an expression for the
cycle’s highest temperature T
c
:

b
b
c
c
T
P
T
P
= ⇒
b
b
c
b c
T
P
P
T T > =

The efficiency of a Carnot engine
operating between the maximum and
minimum temperatures of the Otto
cycle is given by:

c
a
T
T
− =1
Carnot
ε
Express the ratio of the efficiency of
a Carnot engine to the efficiency of
an Otto engine operating between
the same temperatures:
1
1
1
Otto
Carnot
>


=
b
a
c
a
T
T
T
T
ε
ε
because T
c
> T
b
.
Hence,
Otto Carnot
ε ε >

83 ••• [SSM] A common practical cycle, often used in refrigeration, is the
Brayton cycle, which involves (1) an adiabatic compression, (2) an isobaric
(constant pressure) expansion,(3) an adiabatic expansion, and (4) an isobaric
compression back to the original state. Assume the system begins the adiabatic
compression at temperature T
1
, and transitions to temperatures T
2
, T
3
and T
4
after
each leg of the cycle. (a) Sketch this cycle on a PV diagram. (b) Show that the
efficiency of the overall cycle is given by ε = 1−
T
4
− T
1
( )
T
3
− T
2
( )
. (c) Show that this
efficiency, can be written as ε = 1− r
1−γ ( ) γ
, where r is the pressure ratio P
high
/P
low

of the maximum and minimum pressures in the cycle.

Picture the Problem The efficiency of the cycle is the ratio of the work done to
the heat that flows into the engine. Because the adiabatic transitions in the cycle
do not have heat flow associated with them, all we must do is consider the heat
flow in and out of the engine during the isobaric transitions.

(a) The Brayton heat engine cycle is
shown to the right. The paths 1→2
and 3→4 are adiabatic. Heat Q
h

enters the gas during the isobaric
transition from state 2 to state 3 and
heat Q
c
leaves the gas during the
isobaric transition from state 4 to
state 1.
1
2 3
4
P
V


h
Q
c
Q


Chapter 19


1854
(b) The efficiency of a heat engine is
given by:
in
c h
in
Q
Q Q
Q
W −
= = ε (1)

During the constant-pressure
expansion from state 1 to state 2 heat
enters the system:

( )
2 3 P P h 23
Δ T T nC T nC Q Q − = = =
During the constant-pressure
compression from state 3 to state 4
heat enters the system:

( )
4 1 P P c 41
Δ T T nC T nC Q Q − − = − = − =
Substituting in equation (1) and
simplifying yields:
( ) ( ) ( )
( )
( ) ( )
( )
( )
( )
2 3
1 4
2 3
4 1 2 3
2 3 P
4 1 P 2 3 P
1
T T
T T
T T
T T T T
T T nC
T T nC T T nC


− =

− + −
=

− − − −
= ε


(c) Given that, for an adiabatic
transition, constant
1
=
− γ
TV , use the
ideal-gas law to eliminate V and
obtain:

constant
1
=
− γ
γ
P
T

Let the pressure for the transition
from state 1 to state 2 be P
low
and the
pressure for the transition from state
3 to state 4 be P
high
. Then for the
adiabatic transition from state 1 to
state 2:

1
high
2
1
low
1
− −
=
γ
γ
γ
γ
P
T
P
T

2
1
high
low
1
T
P
P
T
γ
γ −








=

Similarly, for the adiabatic transition
from state 3 to state 4:

3
1
high
low
4
T
P
P
T
γ
γ −








=

Subtract T
1
from T
4
and simplify to
obtain:

( )
2 3
1
high
low
2
1
high
low
3
1
high
low
1 4
T T
P
P
T
P
P
T
P
P
T T









=

















= −

− −
γ
γ
γ
γ
γ
γ

The Second Law of Thermodynamics


1855
Dividing both sides of the equation
by T
3
− T
2
yields:

γ
γ 1
high
low
2 3
1 4









=


P
P
T T
T T


Substitute in the result of Part (b) and
simplify to obtain:
( ) γ
γ
γ
γ
γ
γ
ε



− =








− =








− =
1
1
low
high
1
high
low
1
1 1
r
P
P
P
P

where
low
high
P
P
r =

84 ••• Suppose the Brayton cycle engine (see Problem 83) is run in reverse as
a refrigerator in your kitchen. In this case, the cycle begins at temperature T
1
and
expands at constant pressure until its temperature T
4
. Then the gas is adiabatically
compressed, until its temperature is T
3
. And then it is compressed at constant
pressure until its temperature T
2
. Finally, it adiabatically expands until it returns
to its initial state at temperature T
1
. (a) Sketch this cycle on a PV diagram.
(b) Show that the coefficient of performance is COP
B
=
T
4
− T
1
( )
T
3
− T
2
− T
4
+ T
1
( )
.
(c) Suppose your ″Brayton cycle refrigerator″ is run as follows. The cylinder
containing the refrigerant (a monatomic gas) has an initial volume and pressure of
60 mL and 1.0 atm. After the expansion at constant pressure, the volume and
temperature are 75 mL and –25°C. The pressure ratio r = P
high
/P
low
for the cycle is
5.0. What is the coefficient of performance for your refrigerator? (d) To absorb
heat from the food compartment at the rate of 120 W, what is the rate at which
electrical energy must be supplied to the motor of this refrigerator? (e) Assuming
the refrigerator motor is actually running for only 4.0 h each day, how much does
it add to your monthly electric bill. Assume 15 cents per kWh of electric energy
and thirty days in a month.

Picture the Problem The efficiency of the Brayton refrigerator cycle is the ratio
of the heat that enters the system to the work done to operate the refrigerator.
Because the adiabatic transitions in the cycle do not have heat flow associated
with them, all we must do is consider the heat flow in and out of the refrigerator
during the isobaric transitions.

Chapter 19


1856
(a) The Brayton refrigerator cycle is
shown to the right. The paths 1→2
and 3→4 are adiabatic. Heat Q
c

enters the gas during the constant-
pressure transition from state 1 to
state 4 and heat Q
h
leaves the gas
during the constant-pressure
transition from state 3 to state 2.
1
2 3
4
P
V


h
Q
c
Q

(b) The coefficient of performance of
the Brayton cycle refrigerator is
given by:

W
Q
c
B
COP = (1)
where
14 32
Q Q W − =

During the constant-pressure
compression from state 3 to state 2
heat leaves the system:

( )
3 2 P P h 32
Δ T T nC T nC Q Q − − = − = − =
During the constant-pressure
expansion from state 1 to state 4 heat
enters the system:

( )
1 4 P P c 14
Δ T T nC T nC Q Q − = = =
Substituting in equation (1) and
simplifying yields:
( )
( ) ( )
( )
( ) ( )
1 4 2 3
1 4
3 2 1 4
1 4
1 4 P 3 2 P
1 4 P
B
COP
T T T T
T T
T T T T
T T
T T nC T T nC
T T nC
+ − −

=
− − − −

=
− − − −

=


(c) The COP
B
requires the
temperatures corresponding to states
1, 2, 3, and 4. We’re given that the
temperature in state 4 is:

K 248 K 273 C 25
4
= + ° − = T
For the constant-pressure transition
from state 1 to state 4, the quotient
T/V is constant:

4
4
1
1
V
T
V
T
= ⇒
4
4
1
1
T
V
V
T








=

Substitute numerical values and
evaluate T
1
:
( ) K 198 K 248
mL 75
mL 60
1
= ⎟





= T
The Second Law of Thermodynamics


1857
Given that, for an adiabatic
transition, constant
1
=
− γ
TV , use the
ideal-gas law to eliminate V and
obtain:

constant
1
=
− γ
γ
P
T

For the adiabatic transition from state
4 to state 3:

1
4
4
1
3
3
− −
=
γ
γ
γ
γ
P
T
P
T

4
1
4
3
3
T
P
P
T
γ
γ −








=

Substitute numerical values and
evaluate T
3
:

( ) ( ) K 473 K 248 5 67 . 1
1 67 . 1
3
= =

T

Similarly, for the adiabatic transition
from state 2 to state 1:

( ) ( )
K 378
K 98 1 5 67 . 1
1 67 . 1
1
1
1
2
2
=
=








=


T
P
P
T
γ
γ


Substitute numerical values in the
expression derived in Part (a) and
evaluate COP
B
:
1.1
K 198 K 248 K 378 K 473
K 198 K 248
COP
B
=
+ − −

=

(d) From the definition of COP
B
:

B
COP
c
Q
W =

The rate at which energy must be
supplied to this refrigerator is given
by:

dt
dQ
dt
dW
c
B
COP
1
=
or, if the frequency of the AC power
input is f,
B
c
COP
fQ
dt
dW
=

Express the heat Q
c
that is drawn
from the cold reservoir:

( )
1 4 P P c
Δ T T nC T nC Q − = =
Substituting for Q
c
yields:
( )
B
1 4 P
COP
T T fnC
dt
dW −
=

Use the ideal-gas law to express the
number of moles of the gas:

4
4 4
RT
V P
n =
Chapter 19


1858
Because the gas is monatomic,
R C
2
5
P
= . Substitute for n and C
P
to
obtain:

( )
( )
( )
4 B
1 4 4 4 2
5
B
1 4
4
4 4
2
5
COP
COP
T
T T V fP
T T R
RT
V P
f
dt
dW

=

=


Substitute numerical values and evaluate dW/dt:

( )( ) ( )
( )( )
kW 21 . 0
W 207
K 248 1.11
K 198 K 248
L
m 10
mL 75 kPa 325 . 101 s 60
3 3
1
2
5
=
=









×
=


dt
dW


(e) The monthly cost of operation is given by

month per days of number n consumptio daily rate
n Consumptio Power Power of Per Unit Cost Cost Monthly
× × =
× =


Substitute numerical values and evaluate the monthly cost of operation:

4 $ d 0 3
d
h 4.0
kW 207 . 0
kWh
15 . 0 $
Cost Monthly ≈ × × × =

85 ••• Using ( ) ( )
1 2 1 2 V
ln ln V V nR T T C S + = Δ (Equation 19-16) for the
entropy change of an ideal gas, show explicitly that the entropy change is zero for
a quasi-static adiabatic expansion from state (V
1
, T
1
) to state (V
2
, T
2
).

Picture the Problem We can use
V P
C C nR − = ,
V P
C C = γ , and
1 − γ
TV = a constant to show that the entropy change for a quasi-static adiabatic
expansion that proceeds from state (V
1
,T
1
) to state (V
2
,T
2
) is zero.

Express the entropy change for a
general process that proceeds from
state 1 to state 2:









+








= Δ
1
2
1
2
V
ln ln
V
V
nR
T
T
C S
For an adiabatic process:
1
2
1
1
2









=
γ
V
V
T
T


The Second Law of Thermodynamics


1859

Substitute for
1
2
T
T
and simplify to obtain:
( )
( ) [ ]
V
1
2
2
1
2
1
V
1
2
1
2
1
2
1
V
1
2
1
2
1
2
1
V
1 ln
ln
ln 1
ln
ln
ln
ln ln ln
C nR
V
V
V
V
V
V
C
nR
V
V
V
V
V
V
C
nR
V
V
V
V
nR
V
V
C S
− −








=
























+








=






















+








=








+








= Δ


γ
γ
γ
γ


Use the relationship between C
P
and
C
V
to obtain:

V P
C C nR − =
Substituting for nR and γ and
simplifying yields:
0
1 ln
V
V
p
V P
1
2
=














− − −








= Δ C
C
C
C C
V
V
S


86 ••• (a) Show that if the refrigerator statement of the second law of
thermodynamics were not true, then the entropy of the universe could decrease.
(b) Show that if the heat-engine statement of the second law were not true, then
the entropy of the universe could decrease. (c) A third statement of the second law
is that the entropy of the universe cannot decrease. Have you just proved that this
statement is equivalent to the refrigerator and heat-engine statements?

Picture the Problem
(a) Suppose the refrigerator statement of the second law is violated in the sense
that heat Q
c
is taken from the cold reservoir and an equal amount of heat is
transferred to the hot reservoir and W = 0. The entropy change of the universe is
then ΔS
u
= Q
c
/T
h
− Q
c
/T
c
. Because T
h
> T
c
, S
u
< 0, i.e., the entropy of the universe
would decrease.

(b) In this case, heat Q
h
is taken from the hot reservoir and no heat is rejected to
the cold reservoir; that is, Q
c
= 0, then the entropy change of the universe is
ΔS
u
= −Q
h
/T
h
+ 0, which is negative. Again, the entropy of the universe would
decrease.

Chapter 19


1860

(c) The heat-engine and refrigerator statements of the second law only state that
some heat must be rejected to a cold reservoir and some work must be done to
transfer heat from the cold to the hot reservoir, but these statements do not specify
the minimum amount of heat rejected or work that must be done. The statement
ΔS
u
≥ 0 is more restrictive. The heat-engine and refrigerator statements in
conjunction with the Carnot efficiency are equivalent to ΔS
u
≥ 0.

87 ••• Suppose that two heat engines are connected in series, such that the
heat released by the first engine is used as the heat absorbed by the second engine
as shown in Figure 19-22. The efficiencies of the engines are ε
1
and ε
2
,
respectively. Show that the net efficiency of the combination is given by
2 1 2 1 net
ε ε ε ε ε − + = .

Picture the Problem We can express the net efficiency of the two engines in
terms of W
1
, W
2
, and Q
h
and then use ε
1
= W
1
/Q
h
and ε
2
= W
2
/Q
m
to eliminate W
1
,
W
2
, Q
h
, and Q
m
.

Express the net efficiency of the
two heat engines connected in
series:

h
2 1
net
Q
W W +
= ε
Express the efficiencies of engines 1
and 2:
h
1
1
Q
W
= ε and
m
2
2
Q
W
= ε

Solve for W
1
and W
2
and substitute
to obtain:

2
h
m
1
h
m 2 h 1
net
ε ε
ε ε
ε
Q
Q
Q
Q Q
+ =
+
=

Express the efficiency of engine 1 in
terms of Q
m
and Q
h
:
h
m
1
1
Q
Q
− = ε ⇒
1
h
m
1 ε − =
Q
Q


Substitute for Q
m
/Q
h
and simplify to
obtain:
( )
2 1 2 1 2 1 1 net
1 ε ε ε ε ε ε ε ε − + = − + =

88 ••• Suppose that two heat engines are connected in series, such that the
heat released by the first engine is used as the heat absorbed by the second
engine, as shown in Figure 19-22. Suppose that each engine is an ideal reversible
heat engine. Engine 1 operates between temperatures T
h
and T
m
and Engine 2
operates between T
m
and T
c
, where T
h
> T
m
> T
c
. Show that the net efficiency of
the combination is given by
c
net
h
1 ε = −
T
T
. (Note that this result means that two
The Second Law of Thermodynamics


1861
reversible heat engines operating ″in series″ are equivalent to one reversible heat
engine operating between the hottest and coldest reservoirs.)

Picture the Problem We can express the net efficiency of the two engines in
terms of W
1
, W
2
, and Q
h
and then use ε
1
= W
1
/Q
h
and ε
2
= W
2
/Q
m
to eliminate W
1
,
W
2
, Q
h
, and Q
m
. Finally, we can substitute the expressions for the efficiencies of
the ideal reversible engines to obtain
h c net
1 T T − = ε .

Express the efficiencies of ideal
reversible engines 1 and 2:

h
m
1
1
T
T
− = ε (1)
and
m
c
2
1
T
T
− = ε (2)

The net efficiency of the two engines
connected in series is given by:

h
2 1
net
Q
W W +
= ε (3)
Express the efficiencies of engines 1
and 2:
h
1
1
Q
W
= ε and
m
2
2
Q
W
= ε

Solve for W
1
and W
2
and substitute
in equation (3) to obtain:

2
h
m
1
h
m 2 h 1
net
ε ε
ε ε
ε
Q
Q
Q
Q Q
+ =
+
=

Express the efficiency of engine 1 in
terms of Q
m
and Q
h
:
h
m
1
1
Q
Q
− = ε ⇒
1
h
m
1 ε − =
Q
Q


Substitute for
h
m
Q
Q
to obtain:

( )
2 1 1 net
1 ε ε ε ε − + =

Substitute for ε
1
and ε
2
and simplify
to obtain:

h
c
h
c
h
m
h
m
m
c
h
m
h
m
net
1 1
1 1
T
T
T
T
T
T
T
T
T
T
T
T
T
T
− = − + − =

















+ − = ε


89 ••• [SSM] The English mathematician and philosopher Bertrand Russell
(1872-1970) once said that if a million monkeys were given a million typewriters
and typed away at random for a million years, they would produce all of
Shakespeare’s works. Let us limit ourselves to the following fragment of
Shakespeare (Julius Caesar III:ii):

Chapter 19


1862
Friends, Romans, countrymen! Lend me your ears.
I come to bury Caesar, not to praise him.
The evil that men do lives on after them,
The good is oft interred with the bones.
So let it be with Caesar.
The noble Brutus hath told you that Caesar was ambitious,
And, if so, it were a grievous fault,
And grievously hath Caesar answered it . . .

Even with this small fragment, it will take a lot longer than a million years! By
what factor (roughly speaking) was Russell in error? Make any reasonable
assumptions you want. (You can even assume that the monkeys are immortal.)

Picture the Problem There are 26 letters and four punctuation marks (space,
comma, period, and exclamation point) used in the English language, disregarding
capitalization, so we have a grand total of 30 characters to choose from. This
fragment is 330 characters (including spaces) long; there are then 30
330
different
possible arrangements of the character set to form a fragment this long. We can
use this number of possible arrangements to express the probability that one
monkey will write out this passage and then an estimate of a monkey’s typing
speed to approximate the time required for one million monkeys to type the
passage from Shakespeare.

Assuming the monkeys type at
random, express the probability P
that one monkey will write out this
passage:

330
30
1
= P
Use the approximation
5 . 1
10 1000 30 = ≈ to obtain:
( )( )
495
495 330 5 . 1
10
10
1
10
1

= = = P

Assuming the monkeys can type at a
rate of 1 character per second, it
would take about 330 s to write a
passage of length equal to the
quotation from Shakespeare. Find
the time T required for a million
monkeys to type this particular
passage by accident:

( )( )
( )
y 10
s 10 3.16
y 1
s 10 30 . 3
10
10 s 330
484
7
491
6
495









×
× =
= T

Express the ratio of T to Russell’s
estimate:
478
6
484
Russell
10
y 10
y 10
= =
T
T

or

Russell
478
10 T T ≈