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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 ≈

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