698 C H A P T E R 2 2 • Heat Engines, Entropy, and the Second Law of Thermodynamics

ferred to the environment. Show that the Clausius state- 26. A heat pump, shown in Figure P22.26, is essentially an air
ment of the second law of thermodynamics is violated. conditioner installed backward. It extracts energy from
(c) Find the energy input and work output of engine S as it colder air outside and deposits it in a warmer room. Sup-
puts out exhaust energy of 100 J. (d) Let engine S operate pose that the ratio of the actual energy entering the room
as in (c) and contribute 150 J of its work output to running to the work done by the device’s motor is 10.0% of the the-
the Carnot engine in reverse. Find the total energy the fire- oretical maximum ratio. Determine the energy entering
box puts out as both engines operate together, the total the room per joule of work done by the motor, given that
work output, and the total energy transferred to the envi- the inside temperature is 20.0°C and the outside tempera-
ronment. Show that the Kelvin–Planck statement of the sec- ture is " 5.00°C.
ond law is violated. Thus our assumption about the effi-
ciency of engine S must be false. (e) Let the engines
operate together through one cycle as in part (d). Find the
change in entropy of the Universe. Show that the entropy
statement of the second law is violated.
22. At point A in a Carnot cycle, 2.34 mol of a monatomic
ideal gas has a pressure of 1 400 kPa, a volume of 10.0 L,
Qc Heat Qh
and a temperature of 720 K. It expands isothermally to pump
point B, and then expands adiabatically to point C where
its volume is 24.0 L. An isothermal compression brings it Outside Inside
to point D, where its volume is 15.0 L. An adiabatic process Tc Th
returns the gas to point A. (a) Determine all the unknown
pressures, volumes and temperatures as you fill in the
following table:

Figure P22.26

P V T
A 1 400 kPa 10.0 L 720 K 27. How much work does an ideal Carnot refrigerator
B require to remove 1.00 J of energy from helium at 4.00 K
and reject this energy to a room-temperature (293-K)
C 24.0 L environment?
D 15.0 L 28. A refrigerator maintains a temperature of 0°C in the cold
compartment with a room temperature of 25.0°C. It
removes energy from the cold compartment at the rate of
(b) Find the energy added by heat, the work done by the 8 000 kJ/h. (a) What minimum power is required to
engine, and the change in internal energy for each of the operate the refrigerator? (b) The refrigerator exhausts
steps A : B, B : C, C : D, and D : A. (c) Calculate the energy into the room at what rate?
efficiency Wnet /Q h . Show that it is equal to 1 " TC /TA , 29. If a 35.0%-efficient Carnot heat engine (Fig. 22.2) is run in
the Carnot efficiency. reverse so as to form a refrigerator (Fig. 22.5), what would
23. What is the coefficient of performance of a refrigerator be this refrigerator’s coefficient of performance?
that operates with Carnot efficiency between temperatures 30. Two Carnot engines have the same efficiency. One engine
" 3.00°C and & 27.0°C? runs in reverse as a heat pump, and the other runs in reverse
24. What is the maximum possible coefficient of performance as a refrigerator. The coefficient of performance of the heat
of a heat pump that brings energy from outdoors at pump is 1.50 times the coefficient of performance of the
" 3.00°C into a 22.0°C house? Note that the work done to refrigerator. Find (a) the coefficient of performance of the
run the heat pump is also available to warm up the house. refrigerator, (b) the coefficient of performance of the heat
pump, and (c) the efficiency of each heat engine.
25. An ideal refrigerator or ideal heat pump is equivalent to a
Carnot engine running in reverse. That is, energy Q c is
taken in from a cold reservoir and energy Q h is rejected to Section 22.5 Gasoline and Diesel Engines
a hot reservoir. (a) Show that the work that must be sup-
31. In a cylinder of an automobile engine, just after combus-
plied to run the refrigerator or heat pump is
tion, the gas is confined to a volume of 50.0 cm3 and has
Th " Tc an initial pressure of 3.00 ' 106 Pa. The piston moves out-
W! Qc
Tc ward to a final volume of 300 cm3, and the gas expands
without energy loss by heat. (a) If * ! 1.40 for the gas,
(b) Show that the coefficient of performance of the ideal what is the final pressure? (b) How much work is done by
refrigerator is the gas in expanding?
Tc 32. A gasoline engine has a compression ratio of 6.00 and
COP !
Th " Tc uses a gas for which * ! 1.40. (a) What is the efficiency

of the engine if it operates in an idealized Otto cycle?
(b) What If ? If the actual efficiency is 15.0%, what
fraction of the fuel is wasted as a result of friction and
energy losses by heat that could by avoided in a re-
versible engine? (Assume complete combustion of the
air–fuel mixture.)
33. A 1.60-L gasoline engine with a compression ratio of 6.20
has a useful power output of 102 hp. Assuming the en-
gine operates in an idealized Otto cycle, find the energy
taken in and the energy exhausted each second. Assume
the fuel–air mixture behaves like an ideal gas with
* ! 1.40.
34. The compression ratio of an Otto cycle, as shown in Figure
22.13, is VA/VB ! 8.00. At the beginning A of the compres-
sion process, 500 cm3 of gas is at 100 kPa and 20.0°C. At
the beginning of the adiabatic expansion the temperature
is TC ! 750°C. Model the working fluid as an ideal gas
with E int ! nCVT ! 2.50nRT and * ! 1.40. (a) Fill in the
table below to follow the states of the gas:
T (K) P (kPa) V (cm 3) E int
A 293 100 500
B brakes to a stop. The brakes cool off to the temperature of
C 1 023
D What is the total entropy change?
A
(b) Fill in the table below to follow the processes:
Q (input) W (output) %E int
A:B
B:C
C:D
D:A
ABCDA
(c) Identify the energy input Q h , the energy exhaust Q c ,
and the net output work Weng. (d) Calculate the thermal
efficiency. (e) Find the number of crankshaft revolutions
per minute required for a one-cylinder engine to have
an output power of 1.00 kW ! 1.34 hp. Note that the
thermodynamic cycle involves four piston strokes.
Section 22.6 Entropy
35. An ice tray contains 500 g of liquid water at 0°C. Calculate
the change in entropy of the water as it freezes slowly and
completely at 0°C.
36. At a pressure of 1 atm, liquid helium boils at 4.20 K . The
latent heat of vaporization is 20.5 kJ/kg. Determine the
entropy change (per kilogram) of the helium resulting
from vaporization.
37. Calculate the change in entropy of 250 g of water heated
slowly from 20.0°C to 80.0°C. (Suggestion: Note that
dQ ! mc dT.)
Problems 699
38. In making raspberry jelly, 900 g of raspberry juice is com-
bined with 930 g of sugar. The mixture starts at room tem-
perature, 23.0°C, and is slowly heated on a stove until it
reaches 220°F. It is then poured into heated jars and al-
lowed to cool. Assume that the juice has the same specific
heat as water. The specific heat of sucrose is 0.299 cal/g ( °C.
Consider the heating process. (a) Which of the following
terms describe(s) this process: adiabatic, isobaric, isother-
mal, isovolumetric, cyclic, reversible, isentropic? (b) How
much energy does the mixture absorb? (c) What is the mini-
mum change in entropy of the jelly while it is heated?
39. What change in entropy occurs when a 27.9-g ice cube at
" 12°C is transformed into steam at 115°C?
Section 22.7 Entropy Changes in Irreversible
Processes
40. The temperature at the surface of the Sun is approxi-
mately 5 700 K , and the temperature at the surface of the
Earth is approximately 290 K. What entropy change occurs
when 1 000 J of energy is transferred by radiation from the
Sun to the Earth?
41. A 1 500-kg car is moving at 20.0 m/s. The driver
the surrounding air, which is nearly constant at 20.0°C.
42. A 1.00-kg iron horseshoe is taken from a forge at 900°C
and dropped into 4.00 kg of water at 10.0°C. Assuming
that no energy is lost by heat to the surroundings, deter-
mine the total entropy change of the horseshoe-plus-water
system.
43. How fast are you personally making the entropy of the
Universe increase right now? Compute an order-of-magni-
tude estimate, stating what quantities you take as data and
the values you measure or estimate for them.
44. A rigid tank of small mass contains 40.0 g of argon, initially
at 200°C and 100 kPa. The tank is placed into a reservoir
at 0°C and allowed to cool to thermal equilibrium. (a) Cal-
culate the volume of the tank. (b) Calculate the change in
internal energy of the argon. (c) Calculate the energy
transferred by heat. (d) Calculate the change in entropy of
the argon. (e) Calculate the change in entropy of the con-
stant-temperature bath.
45. A 1.00-mol sample of H2 gas is contained in the left-hand
side of the container shown in Figure P22.45, which has
equal volumes left and right. The right-hand side is evacu-
ated. When the valve is opened, the gas streams into the
right-hand side. What is the final entropy change of the
gas? Does the temperature of the gas change?
Valve
H2 Vacuum
Figure P22.45
644 Heat Engines, Entropy, and the Second Law of Thermodynamics

Section 22.5 Gasoline and Diesel Engines

γ γ
P22.31 (a) i i = Pf V f
PV

FV I F 50.0 cm I
γ

= P G J = e3.00 × 10 PajG
3 1.40

H 300 cm JK
i 6
Pf = 244 kPa
HV K i
f
3

Vi

z FG V IJ
i
γ
(b) W = PdV
Vi
P = Pi
HVK
Integrating,

F 1 IJ PV LM1 − FG V IJ γ −1 OP L F 50.0 cm I OP
m jM1 − G
3 0. 400

W =G
PQ = a2.50fe3.00 × 10 Paje5.00 × 10 MN H 300 cm JK PQ
i 6 −5 3
H γ − 1 K MN H V K i i
f
3

= 192 J

P22.32 Compression ratio = 6.00 , γ = 1.40

(a) Efficiency of an Otto-engine e = 1 −

FG V IJ
2
γ −1

HV K1

e=1−G
F 1 IJ 0 . 400

H 6.00 K = 51. 2% .

(b) If actual efficiency e ′ = 15.0% losses in system are e − e ′ = 36.2% .

1 1 1
P22.33 eOtto = 1 − =1− =1−
bV V g
1 2
γ −1
a6.20fb7 5−1g a6.20f 0. 400

eOtto = 0.518
We have assumed the fuel-air mixture to behave like a diatomic gas.
Weng Weng t
Now e = =
Qh Qh t
Q h Weng t 746 W 1 hp
= = 102 hp
t e 0.518
Qh
= 146 kW
t
Q h = Weng + Q c
Qc Q h Weng
= −
t t t
Qc F 746 W I =
t
= 146 × 10 3 W − 102 hp GH 1 hp JK 70.8 kW
 Chapter 22 645
P22.34 (a), (b) The quantity of gas is

n=
PA VA
=
e
100 × 10 3 Pa 500 × 10 −6 m 3 je
= 0.020 5 mol
j
RTA b
8.314 J mol ⋅ K 293 K ga f
5 5 5
Eint, A =
2 2 2
e
nRTA = PA VA = 100 × 10 3 Pa 500 × 10 −6 m 3 = 125 J je j
In process AB, PB = PA
FG V IJ = e100 × 10 Paja8.00f
A
γ
3 1.40
= 1.84 × 10 6 Pa
HV K
B

TB =
PBVB
=
e
1.84 × 10 6 Pa 500 × 10 −6 m3 8.00 je
= 673 K
j
nR b
0.020 5 mol 8.314 J mol ⋅ K gb g
Eint, B =
5
2
5
b
nRTB = 0.020 5 mol 8.314 J mol ⋅ K 673 K = 287 J
2
gb ga f
so ∆Eint, AB = 287 J − 125 J = 162 J = Q − Wout = 0 − Wout W AB = −162 J

Process BC takes us to:

PC =
nRTC
=
b gb
0.020 5 mol 8.314 J mol ⋅ K 1 023 K
= 2.79 × 10 6 Pa
gb g
VC 62.5 × 10 −6 m 3
5 5
b
Eint, C = nRTC = 0.020 5 mol 8.314 J mol ⋅ K 1 023 K = 436 J
2 2
gb gb g
Eint, BC = 436 J − 287 J = 149 J = Q − Wout = Q − 0

QBC = 149 J

In process CD:

FG V IJ = e2.79 × 10 PajFG 1 IJ = 1.52 × 10 Pa

C
γ
6
1.40
5
PD = PC
HV KD
H 8.00 K
TD =
P VD D
=
e1.52 × 10 Paje500 × 10 m j = 445 K
5 −6 3

nR b0.020 5 molgb8.314 J mol ⋅ K g

= nRT = b0.020 5 molgb8.314 J mol ⋅ K ga 445 K f =
5 5
Eint, D D 190 J
2 2
∆Eint, CD = 190 J − 436 J = −246 J = Q − Wout = 0 − Wout

WCD = 246 J

and ∆Eint, DA = Eint, A − Eint, D = 125 J − 190 J = −65.0 J = Q − Wout = Q − 0

QDA = −65.0 J

continued on next page

646 Heat Engines, Entropy, and the Second Law of Thermodynamics

For the entire cycle, ∆Eint, net = 162 J + 149 − 246 − 65.0 = 0 . The net work is

Weng = −162 J + 0 + 246 J + 0 = 84.3 J

Q net = 0 + 149 J + 0 − 65.0 J = 84.3 J

The tables look like:

State T(K) P(kPa) V(cm3 ) Eint (J)

A 293 100 500 125
B 673 1 840 62.5 287
C 1 023 2 790 62.5 436
D 445 152 500 190
A 293 100 500 125

Process Q(J) output W(J) ∆Eint (J)

AB 0 –162 162
BC 149 0 149
CD 0 246 –246
DA –65.0 0 –65.0
ABCDA 84.3 84.3 0

(c) The input energy is Q h = 149 J , the waste is Q c = 65.0 J , and Weng = 84.3 J .

Weng 84.3 J
(d) The efficiency is: e = = = 0.565 .
Qh 149 J

f
(e) Let f represent the angular speed of the crankshaft. Then is the frequency at which we
2
obtain work in the amount of 84.3 J/cycle:

FG f IJ b84.3 J cycleg
1 000 J s =
H 2K
2 000 J s
f= = 23.7 rev s = 1.42 × 10 3 rev min
84.3 J cycle

Section 22.6 Entropy

P22.35 For a freezing process,

∆S =
b ge 5
∆Q − 0.500 kg 3.33 × 10 J kg
=
j
= −610 J K .
T 273 K