Chap 19 SM PDF
Chap 19 SM PDF
Chap 19 SM PDF
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 Qh.
The percentage of the heat of combustion (heat absorbed from the high-
temperature reservoir) is the ratio of Qc to Qh. We can use the relationship
between W, Qh, and Qc ( W = Qh − Qc ) to find Qc/ Qh.
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 Qh. We
can use the relationship between W, Qh, and Qc ( W = Qh − Qc ) to express the
efficiency of the heat engine in terms of Qc and W.
1779
1780 Chapter 19
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 Qh. We
can use the relationship between W, Qh, and Qc ( W = Qh − Qc ) to express the
efficiency of the heat engine in terms of Qc and Qh.
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.
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 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.
Determine the Concept Because the efficiency of a Carnot cycle engine is given
by ε C = 1 − c , you should increase the temperature of the hot reservoir. (c ) is
T
Th
correct.
27°C and a high temperature reservoir of 127°C. Its efficiency is (a) 21%,
(b) 25%, (c) 75%, (d) 79%.
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 Pi, Vi, Ti to the
final state Pf, Vf, Tf. 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) ΔEint A > ΔEint B, (b) ΔSA > ΔSB,
(c) ΔSA < ΔSB, (d) None of the above.
V
Vi Vf
(a) Because Eint is a state function and the initial and final states are the same for
the two paths, ΔEint, A = ΔEint, B .
(b) and (c) S, like Eint, 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 ΔS A = ΔS B .
(d) (d ) is correct.
D
V
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.
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.
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.
a b
Since S = S1 + ΔS , we have: ⎛V ⎞
S = S1 + nR ln⎜⎜ ⎟⎟
⎝ V1 ⎠
S
An SV graph for the Carnot cycle
(see Figure 19-8) is shown to the 2 3
right.
1 4
V
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. Qin, 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:
S
c d
b a
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
1788 Chapter 19
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.
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 Qh Qc = Th Tc to
express the ratio of the coefficients of performance in terms of the temperatures in
the kitchen, basement, and 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
N
⎛V ⎞
located in the (open) closet is given by p = ⎜⎜ 2 ⎟⎟ where N is the number of air
⎝ V1 ⎠
molecules in your bedroom and V1 and V2 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 m3 and that the
temperature of the air is 20°C.
1.252×10 27
Substitute for N in equation (1) and ⎛1⎞ 1 27
evaluate p: p=⎜ ⎟ = 27
= 10 −1.252×10
⎝ 10 ⎠ 101.252×10
27
≈ 10 −10
γ −1
Tc ⎛V ⎞
Substitute for to obtain: ε C = 1 − ⎜⎜ h ⎟⎟
Th
⎝ Vc ⎠
Express the compression ratio r: Vc
r=
Vh
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 Qh and Qc to find an upper limit on
the COP of a household refrigerator. In (b) we can solve the definition of COP for
Qc and differentiate the resulting equation with respect to time to estimate the rate
at which heat is being drawn from the refrigerator compartment.
Qh 1
Substitute for to obtain: COPmax =
Qc Th
−1
Tc
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.
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 = 2/2N, 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
2N
or the other is t = . In (e) we can apply the ideal gas law to find the number
2(100 )
of molecules in 1.0 L of air at a pressure of 10−12 torr and an assumed temperature
of 300 K.
t=
N = 1.0 mol =6.022 ×1023 molecules: 2(100 s −1 )
23
To evaluate 26.022×10 let (6.022 ×10 )ln 2 = x ln10 ⇒ x ≈ 10
23 23
23
10 x = 26.022×10 and take the logarithm
of both sides of the equation to
obtain:
1794 Chapter 19
t=
molecules: 2(100 s −1 )
7
To evaluate 23.22×10 let (3.22 × 10 )ln 2 = x ln10 ⇒ x ≈ 10
7 7
7
10 x = 23.22×10 and take the logarithm
of both sides of the equation to
obtain:
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?
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.
Picture the Problem We can apply their definitions to find the COP of the
refrigerator and the efficiency of the heat engine.
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 Q = CV ΔT and Q = CP ΔT . We can use the 1st 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.
T1 =
P1V1
=
(1.00 atm )(24.6 L ) = 300 K
nR
(1.00 mol)⎛⎜ 8.206 ×10 − 2 L ⋅ atm ⎞⎟
⎝ mol ⋅ K ⎠
W12 = PΔV12 = 0
and
⎛ J ⎞
Q12 = CV ΔT12 = 32 RΔT12 = 32 ⎜ 8.314 ⎟ (600 K − 300 K ) = 3.74 kJ
⎝ mol ⋅ K ⎠
⎛ 101.325 J ⎞
Won = −W23 = − PΔV23 = −(2.00 atm )(49.2 L − 24.6 L )⎜ ⎟ = − 4.99 kJ
⎝ L ⋅ atm ⎠
⎛ J ⎞
Q23 = CP ΔT23 = 52 RΔT23 = 52 ⎜ 8.314 ⎟ (1200 K − 600 K ) = 12.5 kJ
⎝ mol ⋅ K ⎠
W34 = PΔV34 = 0
and
⎛ J ⎞
Q34 = ΔEint, 34 = CV ΔT34 = 32 RΔT34 = 32 ⎜ 8.314 ⎟ (600 K − 1200 K ) = − 7.48 kJ
⎝ mol ⋅ K ⎠
⎛ 101.325 J ⎞
Won = −W41 = − PΔV41 = −(1.00 atm )(24.6 L − 49.2 L )⎜ ⎟ = 2.49 kJ
⎝ L ⋅ atm ⎠
and
⎛ J ⎞
Q41 = CP ΔT41 = 52 RΔT41 = 52 ⎜ 8.314 ⎟ (300 K − 600 K ) = − 6.24 kJ
⎝ mol ⋅ K ⎠
For easy reference, the results of the preceding calculations are summarized in the
following table:
Process Won , kJ Qin , kJ ΔEint (= Qin + Won ) , 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
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.
0 V(L)
0 10.0 20.0
γ
The pressures and volumes at the end γ ⎛V ⎞
γ
points of the adiabatic expansion are P1V1 = P2V2 ⇒ P1 = ⎜⎜ 2 ⎟⎟ P2
⎝ V1 ⎠
related according to:
1.4
Substitute numerical values and ⎛ 20.0 L ⎞
evaluate P1: P1 = ⎜ ⎟ (1.00 atm) = 2.639 atm
⎝ 10.0 L ⎠
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.
P (atm)
4
the numerals 1, 2, 3, and 4 represent 1 1
D
the four steps through which the gas B
3 2 400 K
is taken. 0.5
C 300 K
0
0 10 20 30 40 50 60
V (L)
VB V 1
Noting the = 2 and D = , substitute and simplify to obtain:
VA VC 2
⎛1⎞
Th ln (2 ) + Tc ln⎜ ⎟
ε= ⎝ 2 ⎠ = Th ln (2) − Tc ln (2) = Th − Tc
Th ln (2) + V (Th − Tc ) Th ln (2) + V (Th − Tc ) Th + (Th − Tc )
C C CV
nR nR nR ln (2)
400 K − 300 K
ε= = 13.1%
J
21.0
400 K + K (400 K − 300 K )
⎛ J ⎞
(1.00 mol)⎜ 8.314 ⎟ ln (2)
⎝ mol ⋅ K ⎠
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.
(b) Find the heat entering the system for the constant-volume process from 1 → 2:
⎛ J ⎞
Q12 = C V ΔT12 = 32 RΔT12 = 32 ⎜ 8.314 ⎟ (601 K − 301 K ) = 3.74 kJ
⎝ mol ⋅ K ⎠
Find the heat entering or leaving the system for the isothermal process from
2 → 3:
⎛V ⎞ ⎛ J ⎞ ⎛ 50.0 L ⎞
Q23 = nRT2 ln⎜⎜ 3 ⎟⎟ = (1.00 mol)⎜ 8.314 ⎟ (601 K )ln⎜⎜ ⎟⎟ = 3.46 kJ
⎝ V2 ⎠ ⎝ mol ⋅ K ⎠ ⎝ 25.0 L ⎠
Find the heat leaving the system during the isobaric compression from 3 → 1:
⎛ J ⎞
Q31 = C P ΔT31 = 52 RΔT31 = 52 ⎜ 8.314 ⎟ (301 K − 601 K ) = − 6.24 kJ
⎝ mol ⋅ K ⎠
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 Qin.
Noting that heat enters the system Qin = Q12 + Q23 = C V ΔT12 + C P ΔT23
between states 1 and 2 and states 2 = 52 nRΔT12 + 72 nRΔT23
= ( 52 ΔT12 + 72 ΔT23 )nR
and 3, express Qin:
⎛ L ⋅ atm ⎞
Qin = [52 (600 K − 200 K ) + 72 (1800 K − 600 K )]⎜ 0.50 ⎟ = 2600 atm ⋅ L
⎝ K ⎠
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 S
2
ΔV = 0
(2)
3
(3) Th
Th
Tc
1
(1) (4)
4 ΔV = 0
Tc
V T
1806 Chapter 19
⎛T ⎞
= nC V ln⎜⎜ f ⎟⎟
⎝ Ti ⎠
⎛V ⎞ ⎛T ⎞ ⎛V ⎞ ⎛T ⎞
ΔS cycle = nR ln⎜⎜ 2 ⎟⎟ + CV ln⎜⎜ c ⎟⎟ − nR ln⎜⎜ 2 ⎟⎟ − CV ln⎜⎜ c ⎟⎟ = 0
⎝ V1 ⎠ ⎝ Th ⎠ ⎝ V1 ⎠ ⎝ Th ⎠
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.
Use T = 5
9
(tF − 32) + 273 to obtain: Tbody = 310 K and Troom = 294 K
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 Va, Vb and Vc.
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.
γ −1 γ −1
Because Va = Vd: ⎛⎛ V ⎞ T ⎛V ⎞ ⎞
⎜⎜ c ⎟⎟ − b ⎜⎜ b ⎟⎟ ⎟
⎜ ⎜⎝ Va ⎠ Tc ⎝ Va ⎠ ⎟
ε = 1− ⎝ ⎠
⎛ Tb ⎞
γ ⎜⎜1 − ⎟
⎝ Tc ⎟⎠
γ −1 γ −1 γ −1 γ −1
⎛ Vc ⎞ ⎛ Vb
V ⎞ Vc ⎛ Vc ⎞ ⎛ Vb
V ⎞
⎜⎜ ⎟⎟ ⎜⎜
− b ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜
− b ⎟⎟
ε = 1− ⎝ a ⎠ ⎝ Va ⎠ = 1− ⎝ a ⎠ ⎝ Va ⎠
V Vc Va V Vc
⋅
⎛ V ⎞ Vc ⎛V V ⎞
γ ⎜⎜1 − b ⎟⎟ γ ⎜⎜ c − b ⎟⎟
⎝ Vc ⎠ Va ⎝ Va Va ⎠
γ γ
⎛ Vc ⎞ ⎛ Vb ⎞
⎜⎜ ⎟⎟ − ⎜⎜ ⎟⎟
⎝ Va ⎠ ⎝ Va ⎠ Vcγ − Vbγ
= 1− = 1 − γ −1
⎛ Vc Vb ⎞ γVa (Vc − Vb )
γ ⎜⎜ − ⎟⎟
⎝ Va Va ⎠
The Second Law of Thermodynamics 1809
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.
1810 Chapter 19
Carnot Cycles
Picture the Problem We can find the efficiency of the Carnot engine using
ε = 1 − Tc / Th and the work done per cycle from ε = W / Qh . 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.
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 W = ε CQh , where
εC is the Carnot efficiency.
The Second Law of Thermodynamics 1811
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 ε2, the efficiency of this engine, is greater than
30%, then Qh2, the heat removed from the hot reservoir by this engine, is
140 J/(1 − ε2) > 200 J, and the work done by this engine is W = ε2Qh2 > 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.
than 20%, the two engines working together would violate the refrigerator
statement of the second law.
Picture the Problem We can use the definition of efficiency to find the efficiency
of the Carnot engine operating between the two reservoirs.
(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.
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 W = ε CQh and we can
use the conservation of energy to find the heat rejected to the low-temperature
reservoir.
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
Q = C V ΔT and Q = C P ΔT 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.
1814 Chapter 19
1
Apply an equation for an adiabatic ⎛ P ⎞γ
process to relate the pressures and P1V1γ = P3V3γ ⇒ V3 = V1 ⎜⎜ 1 ⎟⎟
⎝ P3 ⎠
volumes at points 2 and 3:
1
Noting that V1 = 22.4 L, evaluate V3: ⎛ 1.55 atm ⎞ 1.4
V3 = (22.4 L )⎜⎜ ⎟⎟ = 30.6 L
⎝ 1atm ⎠
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.
⎛ 1 ⎞⎛ kJ ⎞
Qc (1.00 h ) = ⎜ − 1⎟ ⎜ 200 ⎟ (3600 s ) = 1.68 GJ
⎝ 0.300 ⎠ ⎝ s ⎠
*Heat Pumps
Picture the Problem We can use the definition of the COPHP 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
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 Tc and Th we can write the amount of heat
removed from the refrigerator as a function of Tc, Th, P, and Δt.
⎛ 273 K ⎞ ⎛ 60 s ⎞
Qc = ⎜ ⎟ (370 W )⎜1.00 min × ⎟ = 303 kJ = 0.30 MJ
⎝ 293 K − 273 K ⎠ ⎝ min ⎠
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 Tc and Th we can write the amount of heat
removed from the refrigerator as a function of Tc, Th, P, and Δt.
⎛ 273 K ⎞ ⎛ 60 s ⎞
Qc = ⎜ ⎟ (370 W )⎜1.00 min × ⎟ = 173 kJ = 0.17 MJ
⎝ 308 K − 273 K ⎠ ⎝ min ⎠
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.
1820 Chapter 19
⎛ kg ⎞ ⎛ J ⎞⎛ 5 C° ⎞
2⎜1.293 3 ⎟ (5.00 m × 3.50 m × 2.50 m )⎜⎜1005 ⎟⎟ ⎜ 5 F° × ⎟
⎝ m ⎠ ⎝ kg ⋅ C° ⎠ ⎝ 9 F° ⎠
Δt = = 56 s
⎛ 317 K ⎞
⎜ ⎟ (750 W )
⎝ 317 K − 275 K ⎠
Entropy Changes
Picture the Problem Because the water absorbed heat in the vaporization process
Qabsorbed
by H 2 O
its change in entropy is positive and given by ΔS H 2 O = . See Table 18-2
T
for the latent heat of vaporization of water.
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.
⎛ g ⎞⎛ J⎞
− (1.00 mol)⎜18.015 ⎟ ⎜⎜ 333.5 ⎟⎟
⎝ mol ⎠ ⎝ g⎠ J
ΔS H 2O = = − 22.0
273 K K
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.
Express ΔS cooling : ⎛T ⎞
ΔS cooling = mC p ln⎜⎜ f ⎟⎟
⎝ Ti ⎠
⎡ 3 J
⎢ 333.5 ×10 kg ⎛ J ⎞ ⎛ 263 K ⎞
ΔS u = (0.0500 kg ) ⎢− + ⎜⎜ 2100 ⎟ ln⎜ ⎟
⎢ 273 K ⎝ kg ⋅ K ⎟⎠ ⎜⎝ 273 K ⎟⎠
⎢⎣
J ⎛ J ⎞ ⎤
333.5 ×10 3 + ⎜⎜ 2100 ⎟⎟ (273 K − 263 K ) ⎥
kg ⎝ kg ⋅ K ⎠ ⎥ = 2.40 J/K
+
263 K ⎥
⎥
⎦
and, because ΔSu > 0, the entropy of the universe increases.
Picture the Problem We can use the definition of entropy change and the 1st law
of thermodynamics to express ΔS for the ideal gas as a function of its initial and
final volumes.
⎛ J ⎞ ⎛ 40.0 L ⎞ J
ΔS gas = −(2.00 mol)⎜ 8.314 ⎟ ln⎜⎜ ⎟⎟ = 11.5
⎝ mol ⋅ K ⎠ ⎝ 80.0 L ⎠ K
Remarks: The entropy change of the environment of the gas is −11.5 J/K.
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 T3 from the entropy changes during the 1st two
processes and the heat released during the third.
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
Vi to Vf is the same as ΔS for an isothermal process from Vi to Vf. We can use the
definition of entropy change and the 1st law of thermodynamics to express ΔS for
the ideal gas as a function of its initial and final volumes.
⎛ J ⎞ ⎛ 40.0 L ⎞ J
ΔS gas = −(2.00 mol)⎜ 8.314 ⎟ ln⎜⎜ ⎟⎟ = 11.5
⎝ mol ⋅ K ⎠ ⎝ 80.0 L ⎠ K
1826 Chapter 19
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.
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 ΔS u > 0 .
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).
or
Qmelting + Qwarming − Qcooling = 0
ice water water
Substitute to relate the masses of the ice and water to their temperatures,
specific heats, and the final temperature of the water:
Using the expression for the entropy ΔSice = ΔS melting ice + ΔS warming water
change for a constant-pressure ⎛T ⎞
mLf
process, express the entropy change = + mcP ln⎜⎜ f ⎟⎟
of the melting ice and warming ice-
Tf ⎝ Ti ⎠
water:
1828 Chapter 19
⎛ kJ ⎞ ⎛ 283 K ⎞ J
ΔS water = (0.100 kg )⎜⎜ 4.18 ⎟⎟ ln⎜⎜ ⎟⎟ = −115
⎝ kg ⋅ K ⎠ ⎝ 373 K ⎠ K
Remarks: The result that ΔSu > 0 tells us that this process is irreversible.
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.
or
Qcopper + Qwarming = 0
block water
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 Tf of the water:
⎛ kJ ⎞ ⎛ 275.26 K ⎞ J
ΔS Cu = (1.00 kg )⎜⎜ 0.386 ⎟⎟ln⎜⎜ ⎟⎟ = − 117
⎝ kg ⋅ K ⎠ ⎝ 373 K ⎠ K
⎛ kJ ⎞ ⎛ 275.26 K ⎞ J
ΔS water = (4.00 kg )⎜⎜ 4.18 ⎟⎟ ln⎜⎜ ⎟⎟ = 138
⎝ kg ⋅ K ⎠ ⎝ 273 K ⎠ K
Remarks: The result that ΔSu > 0 tells us that this process is irreversible.
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.
1830 Chapter 19
⎛T ⎞ ⎛ kJ ⎞ ⎛ 283 K ⎞ J
ΔS Pb = mPb cPb ln⎜⎜ f ⎟⎟ = (2.00 kg )⎜⎜ 0.128 ⎟⎟ ln⎜⎜ ⎟⎟ = −70.69
⎝ Ti ⎠ ⎝ kg ⋅ K ⎠ ⎝ 373 K ⎠ K
kJ ⎞
(2.00 kg )⎛⎜⎜ 0.128
Substitute numerical values and
⎟ (90 K )
evaluate ΔSw: ⎝ kg ⋅ K ⎟⎠
ΔS w =
283 K
= 81.41 J/K
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.
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.
1832 Chapter 19
(a) Relate the entropy change of the ΔS u = ΔS gas during + ΔS gas during
free expansion isothermal compresion
universe to the entropy changes of
the gas during 1 complete cycle: or, because ΔSgas during = 0,
isothermal compression
Q
ΔS u = ΔS gas during =
free expansion T
⎛ J ⎞ ⎛ 12.3 L ⎞ J J
ΔS u = −(1.00 mol)⎜ 8.314 ⎟ln⎜⎜ ⎟⎟ = 5.763 = 5.76
⎝ mol ⋅ K ⎠ ⎝ 24.6 L ⎠ K K
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
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.
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.
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.
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.
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 dQ dt = cΔTρ dV dt .
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.
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.
dQc dQh dW
Because = − ,a
dt dt dt dQc
= 150 W − 15 W = 135 W
reasonable value for dQc/dt is: dt
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.
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.
Process (1) produces more waste heat. Process (2) is more wasteful of available
work.
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.
1γ
Apply an equation for an adiabatic γ γ ⎛P⎞
process to relate the pressures and P1V1 = P3V3 ⇒ V3 = V1 ⎜⎜ 1 ⎟⎟
⎝ P3 ⎠
volumes at 1 and 3:
1 1.67
Substitute numerical values and ⎛ 16 atm ⎞
evaluate V3: V3 = (1.0 L )⎜⎜ ⎟⎟ = 2.294 L
⎝ 4.0 atm ⎠
= 2.3 L
γ −1
Apply an equation for an adiabatic γ −1 γ −1 ⎛V ⎞
process (γ =1.67) to relate the T3V3 = T1V1 ⇒ T3 = T1 ⎜⎜ 1 ⎟⎟
⎝ V3 ⎠
temperatures and volumes at 1 and 3:
The Second Law of Thermodynamics 1841
1.67 −1
Substitute numerical values and ⎛ 1.0 L ⎞
evaluate T3: T3 = (600 K )⎜⎜ ⎟⎟ = 344 K
⎝ 2.294 L ⎠
= 3.4 ×10 2 K
(c) Express the work done each W = W12 + W23 + W31 (1)
cycle:
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 Tc to the work done by and
the heat input to the real heat engine.
⎛ ⎛ 101.325 J ⎞ ⎞
⎜ 2 ⎜ 4.00 atm ⋅ L × ⎟⎟
⎜ ⎝ atm ⋅ L ⎠ ⎟
Tc = (393 K ) 1 − = 313 K
⎜ 4.00 kJ ⎟
⎜ ⎟
⎝ ⎠
Picture the Problem We can use the definitions of the COP and εC to show that
their relationship is ε C × COPC = TC Th .
W T ⎛ T ⎞ Tc
Because ε C = = 1− c : 1 − ⎜⎜1 − c ⎟⎟
Qh Th 1− ε C
= ⎝ ⎠ = Th
Th
COPc =
εC εC εC
and
Tc
ε C × COPc =
Th
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.
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.
1
(d) Apply an equation for an ⎛ T ⎞ γ −1
adiabatic process (γ = 1.4) to find the TBVBγ −1 = TCVCγ −1 ⇒ VC = VB ⎜⎜ B ⎟⎟
⎝ TC ⎠
volume of the gas at C:
1
Substitute numerical values and ⎛ 1200 K ⎞ 1.4 −1
evaluate VC: VC = (39.38 L )⎜⎜ ⎟⎟ = 222.77 L
⎝ 600 K ⎠
= 223 L
⎛ J ⎞
WBC = − 52 (2.00 mol)⎜ 8.314 ⎟ (600 K − 1200 K ) = 2.494 ×10 J
4
⎝ mol ⋅ K ⎠
= 24.9 kJ
The work done by the gas during the isothermal compression CA is:
⎛V ⎞ ⎛ 19.69 L ⎞
⎟⎟ = (2.00 mol)⎛⎜ 8.314
J ⎞
WCA = nRTC ln⎜⎜ A ⎟ (600 K ) ln⎜⎜ ⎟⎟
⎝ VC ⎠ ⎝ mol ⋅ K ⎠ ⎝ 222.77 L ⎠
= −24.20 kJ = − 24.2 kJ
1846 Chapter 19
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.
1γ 1 1.4
Use the equation of state for an ⎛P ⎞ ⎛ 2.50 atm ⎞
adiabatic process and γ = 1.4 to VC = VB ⎜⎜ B ⎟⎟ = (39.39 L )⎜⎜ ⎟⎟
⎝ PC ⎠ ⎝ 1.00 atm ⎠
find the volume occupied by the
= 75.78 L
gas at C:
(c) The work done by the gas in W = WAB + WBC + WCD + WDA
one cycle is given by:
⎛V ⎞ ⎛ J ⎞ ⎛ 2V ⎞
WAB = nRTA ln⎜⎜ B ⎟⎟ = (2.00 mol)⎜ 8.314 ⎟ (600 K ) ln⎜⎜ A ⎟⎟ = 6.915 kJ
⎝ VA ⎠ ⎝ mol ⋅ K ⎠ ⎝ VA ⎠
⎛ J ⎞
WBC = −C V ΔTBC = − 52 nRΔTBC = − 52 (2.00 mol)⎜ 8.314 ⎟ (462 K − 600 K )
⎝ mol ⋅ K ⎠
= 5.737 kJ
101.325 J
WCD = PC (VD − VC ) = (1.00 atm )(19.7 L − 75.78 L ) = −56.09 atm ⋅ L ×
atm ⋅ L
= −5.680 kJ
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.
⎛ J ⎞
WBC = − 32 (2.00 mol)⎜ 8.314 ⎟ (600 K − 1200 K ) = 14.97 kJ
⎝ mol ⋅ K ⎠
= 15.0 kJ
The work done by the gas during the isothermal compression CA is:
⎛V ⎞ ⎛ 19.69 L ⎞
⎟⎟ = (2.00 mol)⎛⎜ 8.314
J ⎞
WCA = nRTC ln⎜⎜ A ⎟ (600 K ) ln⎜⎜ ⎟⎟
⎝ VC ⎠ ⎝ mol ⋅ K ⎠ ⎝ 111.4 L ⎠
= −17.29 kJ − 17.3 kJ
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.
1γ 35
Use the equation of state for an ⎛P ⎞ ⎛ 2.50 atm ⎞
adiabatic process and γ = 5/3 to VC = VB ⎜⎜ B ⎟⎟ = (39.39 L )⎜⎜ ⎟⎟
⎝ PC ⎠ ⎝ 1.00 atm ⎠
find the volume occupied by the
= 68.26 L
gas at C:
(c) The work done by the gas in one W = WAB + WBC + WCD + WDA (2)
cycle is given by:
⎛V ⎞ ⎛ J ⎞ ⎛ 2V ⎞
WAB = nRTA ln⎜⎜ B ⎟⎟ = (2.00 mol)⎜ 8.314 ⎟ (600 K ) ln⎜⎜ A ⎟⎟ = 6.915 kJ
⎝ VA ⎠ ⎝ mol ⋅ K ⎠ ⎝ VA ⎠
101.325 J
WCD = PC (VD − VC ) = (1.00 atm )(19.7 L − 68.26 L ) = −48.56 atm ⋅ L ×
atm ⋅ L
= −4.920 kJ
Picture the Problem We can express the efficiency of the Otto cycle using the
result from Example 19-2. We can apply the relation TV γ −1 = constant 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.
γ −1
Apply the relation TV γ −1 = constant ⎛V ⎞
to the adiabatic process a→b to Tb = Ta ⎜⎜ a ⎟⎟
⎝ Vb ⎠
obtain:
γ −1
Apply the relation TV γ −1 = constant ⎛V ⎞
to the adiabatic process c→d to Tc = Td ⎜⎜ d ⎟⎟
⎝ Vc ⎠
obtain:
γ −1 γ −1
Subtract the first of these equations ⎛V ⎞ ⎛V ⎞
from the second to obtain: Tc − Tb = Td ⎜⎜ d ⎟⎟ − Ta ⎜⎜ a ⎟⎟
⎝ Vc ⎠ ⎝ Vb ⎠
γ −1 γ −1
In the Otto cycle, Va = Vd and ⎛V ⎞ ⎛V ⎞
Vc = Vb. Substitute to obtain: Tc − Tb = Td ⎜⎜ a ⎟⎟ − Ta ⎜⎜ a ⎟⎟
⎝ Vb ⎠ ⎝ Vb ⎠
γ −1
⎛V ⎞
= (Td − Ta )⎜⎜ a ⎟⎟
⎝ Vb ⎠
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.
=
(T3 − T2 ) + (T1 − T4 )
(T3 − T2 )
(T − T )
= 1− 4 1
(T3 − T2 )
γ −1
Let the pressure for the transition
T1γ T2γ ⎛P ⎞ γ
from state 1 to state 2 be Plow and the = ⇒ T1 = ⎜ low ⎟ T2
γ −1
Plow γ −1
Phigh ⎜P ⎟
pressure for the transition from state ⎝ high ⎠
3 to state 4 be Phigh. Then for the
adiabatic transition from state 1 to
state 2:
γ −1
Similarly, for the adiabatic transition
⎛P ⎞ γ
from state 3 to state 4: T4 = ⎜ low ⎟ T3
⎜P ⎟
⎝ high ⎠
γ −1 γ −1
Subtract T1 from T4 and simplify to
⎛P ⎞ γ ⎛P ⎞ γ
obtain: T4 − T1 = ⎜ low ⎟ T3 − ⎜ low ⎟ T2
⎜P ⎟ ⎜P ⎟
⎝ high ⎠ ⎝ high ⎠
γ −1
⎛P ⎞ γ
= ⎜ low
⎜P
⎟
⎟
(T3 − T2 )
⎝ high ⎠
The Second Law of Thermodynamics 1855
γ −1
Dividing both sides of the equation
T4 − T1 ⎛⎜ Plow ⎞
⎟
γ
by T3 − T2 yields: =
T3 − T2 ⎜⎝ Phigh ⎟
⎠
γ −1 1−γ
Substitute in the result of Part (b) and
⎛P ⎞ γ
⎛ Phigh ⎞ γ
simplify to obtain: ε = 1 − ⎜ low ⎟ = 1 − ⎜⎜ ⎟⎟
⎜P ⎟
⎝ high ⎠ ⎝ Plow ⎠
1−γ
= 1 − (r ) γ
Phigh
where r =
Plow
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 T1 and
expands at constant pressure until its temperature T4. Then the gas is adiabatically
compressed, until its temperature is T3. And then it is compressed at constant
pressure until its temperature T2. Finally, it adiabatically expands until it returns
to its initial state at temperature T1. (a) Sketch this cycle on a PV diagram.
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.
1856 Chapter 19
=
(T4 − T1 )
− (T4 − T1 ) − (T2 − T3 )
T4 − T1
=
T3 − T2 − T4 + T1
γ −1
For the adiabatic transition from state
T3γ T4γ ⎛P ⎞ γ
4 to state 3: γ −1
= γ −1
⇒ T3 = ⎜⎜ 3 ⎟⎟ T4
P3 P4 ⎝ P4 ⎠
1.67 −1
Substitute numerical values and T3 = (5) 1.67 (248 K ) = 473 K
evaluate T3:
γ −1
Similarly, for the adiabatic transition
⎛P ⎞ γ 1.67 −1
from state 2 to state 1: T2 = ⎜⎜ 2 ⎟⎟ T1 = (5) 1.67 (198 K )
⎝ P1 ⎠
= 378 K
(COPB )T4
⎛ 10 −3 m 3 ⎞
5
2
(60 s )
−1
(101.325 kPa )⎜ 75 mL ×
⎜
L
⎟⎟(248 K − 198 K )
dW
= ⎝ ⎠ = 207 W
dt (1.11)(248 K )
= 0.21 kW
$0.15 4.0 h
Monthly Cost = × 0.207 kW × × 30 d ≈ $4
kWh d
γ −1
For an adiabatic process: T2 ⎛ V1 ⎞
=⎜ ⎟
T1 ⎜⎝ V2 ⎟⎠
The Second Law of Thermodynamics 1859
T2
Substitute for and simplify to obtain:
T1
γ −1
⎡ ⎛ V1 ⎞ ⎤
γ −1 ⎢ CV ln⎜⎜ ⎟⎟ ⎥
⎛ V1 ⎞ ⎛ V2 ⎞ ⎛ V2 ⎞ ⎢ ⎝ V2 ⎠ ⎥
ΔS = CV ln⎜⎜ ⎟⎟ + nR ln⎜⎜ ⎟⎟ = ln⎜⎜ ⎟⎟ ⎢nR + ⎥
⎝ V2 ⎠ ⎝ V1 ⎠ ⎝ V1 ⎠ ⎢ V
ln 2 ⎥
⎢⎣ V1 ⎥⎦
⎡ ⎛ ⎞⎤
⎢ (γ − 1)CV ln⎜⎜ V1 ⎟⎟ ⎥
⎛V ⎞
= ln⎜⎜ 2 ⎟⎟ ⎢nR + ⎝ V2 ⎠ ⎥ = ln⎛⎜ V2 ⎞⎟ [nR − (γ − 1)C ]
⎜V ⎟
⎝ V1 ⎠ ⎢ ⎥ V
V1 ⎝ 1⎠
⎢ − ln ⎥
⎢⎣ V2 ⎥⎦
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?
(b) In this case, heat Qh is taken from the hot reservoir and no heat is rejected to
the cold reservoir; that is, Qc = 0, then the entropy change of the universe is
ΔSu = −Qh/Th + 0, which is negative. Again, the entropy of the universe would
decrease.
1860 Chapter 19
(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
ΔSu ≥ 0 is more restrictive. The heat-engine and refrigerator statements in
conjunction with the Carnot efficiency are equivalent to ΔSu ≥ 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 ε1 and ε2,
respectively. Show that the net efficiency of the combination is given by
ε net = ε 1 + ε 2 − ε 1ε 2 .
Picture the Problem We can express the net efficiency of the two engines in
terms of W1, W2, and Qh and then use ε1 = W1/Qh and ε2 = W2/Qm to eliminate W1,
W2, Qh, and Qm.
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 Th and Tm and Engine 2
operates between Tm and Tc, where Th > Tm > Tc. Show that the net efficiency of
T
the combination is given by ε net = 1 − c . (Note that this result means that two
Th
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 W1, W2, and Qh and then use ε1 = W1/Qh and ε2 = W2/Qm to eliminate W1,
W2, Qh, and Qm. Finally, we can substitute the expressions for the efficiencies of
the ideal reversible engines to obtain ε net = 1 − Tc Th .
Qm ε net = ε1 + (1 − ε1 )ε 2
Substitute for to obtain:
Qh
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 30330 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.