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*21.1 One mole of helium contains Avogadro's number of molecules and has a mass of 4.00 g. Let us

call m the mass of one atom, and we have

4.00 g/mol

or m= = 6.64 × 10–24 g/molecule

6.02 × 1023 molecules/mol

m = 6.64 × 10–27 kg

*21.2 We first find the pressure exerted by the gas on the wall of the container.

P= = = = = 9.13 × 105 Pa

V V V 8.00 × 10–3 m 3

21.3 F = Nm = 500(5.00 × 10–3 kg) = 0.943 N

∆t 30.0 s

–

F

P = = 1.57 N/m2 = 1.57 Pa

A

21.4 Consider the x axis to be perpendicular to the plane of the window. Then, the average force

exerted on the window by the hail stones is

F = Nm = Nm = Nm = Nm

∆t t t t

–

F 2v sin θ

P = = Nm

A At

*21.5 F = = 14.0 N

1.00 s

–

F 14.0 N

and P= = = 17.6 kPa

A 8.00 × 10–4 m 2

2 Chapter 21 Solutions

2N mv 2

21.6 Use Equation 21.2, P = , so that

3V 2

mv2 3PV

K av = = where N = nNA = 2NA

2 2N

Kav = =

2(2N A ) 2(2 mol)(6.02 × 1023 molecules/mol)

2N —

21.7 P= (KE) Equation 21.2

3V

N= = = 2.00 × 1024 molecules

2 — 2 (3.60 × 10 –22 )

(K E)

n= = = 3.32 mol

N A 6.02 × 1023 molecules/mol

Goal Solution

G: The balloon has a volume of 4.00 L and a diameter of about 20 cm, which seems like a

reasonable size for a typical helium balloon. The pressure of the balloon is only slightly more

than 1 atm, and if the temperature is anywhere close to room temperature, we can use the

estimate of 22 L/mol for an ideal gas at STP conditions. If this is valid, the balloon should

contain about 0.2 moles of helium.

O: The average kinetic energy can be used to find the temperature of the gas, which can be used

with PV=nRT to find the number of moles.

1 3

A: The gas temperature must be that implied by mv2 = kBT for a monatomic gas like He.

2 2

1

2 2 mv 2 3.6 × 10–22 J

2

T= = = 17.4 K

3 ka 3 1.38 × 10–23 J/K

Now PV = nRT gives

n= =

RT (8.315 J/mol ⋅ K)(17.4 K)

n = 3.32 mol

L: This result is more than ten times the number of moles we predicted, primarily because the

temperature of the helium is much colder than room temperature! In fact, T is only slightly

above the temperature at which the helium would liquify (4.2 K at 1 atm). We should hope

this balloon is not being held by a child; not only would the balloon sink in the air, it is cold

enough to cause frostbite!

Chapter 21 Solutions 3

3kBT

21.8 v=

m

vO MHe 4.00 1

= = =

vHe MO 32.0 8.00

1350 m/s

vO = = 477 m/s

8.00

N= = = 3.53 × 1023 atoms

kBT (1.38 × 10–23 J/K)(293 K)

— 3 3

(b) K = kBT = (1.38 × 10–23)(293) J = 6.07 × 10–21 J

2 2

1 –2 3 3kBT

(c) mv = kBT ∴ vrms = = 1.35 km/s

2 2 m

Nmv2 Nmv 2

21.10 (a) PV = nRT = K= = Etrans

3 2

3PV 3

Etrans = = (3.00 × 1.013 × 105)(5.00 × 10–3) = 2.28 kJ

2 2

(b) = = = = 6.22 × 10–21 J

2 2 2N A 2 (6.02 × 10 23)

– 3 3

21.11 (a) K = kBT = (1.38 × 10–23 J/K)(423 K) = 8.76 × 10–21 J

2 2

– 1 2

(b) K = mv rms = 8.76 × 10–21 J

2

1.75 × 10–20 J

so vrms = (1)

m

For helium,

4.00 g/mol

m= = 6.64 × 10–24 g/molecule

6.02 × 1023 molecules/mol

4 Chapter 21 Solutions

39.9 g/mol

m= = 6.63 × 10–23 g/molecule

6.02 × 1023 molecules/mol

for helium, vrms = 1.62 km/s ; and for argon, vrms = 514 m/s

1 Pa = (1 Pa)

1 N/m2 1 J J

*21.12 (a) = 1 3

1 Pa 1 N ⋅ m m

3

(b) For a monatomic ideal gas, Eint = nRT

2

For any ideal gas, the energy of molecular translation is the same,

3 3

Etrans = nRT = PV

2 2

Etrans 3

Thus, the energy per volume is = P

V 2

3

21.13 Eint = nRT

2

3 3

∆Eint = nR ∆T = (3.00 mol)(8.315 J/mol ⋅ K)(2.00 K) = 75.0 J

2 2

nRT

21.14 The piston moves to keep pressure constant. Since V = , then

P

nR ∆T

∆V = for a constant pressure process.

P

Q Q 2Q

Q = nCP ∆T = n(CV + R)∆T so ∆T = = =

n(C V + R) n(5R/2 + R) 7nR

nR 2Q 2Q 2 Q V

and ∆V = = =

P 7nR 7P 7 nRT

2 (4.40 × 10 3 J)(5.00 L)

∆V = = 2.52 L

7 (1.00 mol)(8.315 J/mol ⋅ K)(300 K)

Chapter 21 Solutions 5

∆Eint = nCV ∆T = n R ∆T

3

(c)

2

2(∆Eint) 2(209 J)

so ∆T = = = 16.8 K

3nR 3(1.00 mol)(8.315 J/mol ⋅ K)

21.17 (a) Consider heating it at constant pressure. Oxygen and nitrogen are diatomic, so

CP = 7R/2

nR ∆T = ∆T

7 7 PV

Q = nCP ∆T =

2 2 T

Q= (1.00 K) = 118 kJ

2 300 K

(b) Ug = mgy

Ug 1.18 × 105 J

m= = = 6.03 × 103 kg

gy (9.80 m/s2)2.00 m

5 5 J

*21.18 (a) CV =

2 2 mol ⋅ K 0.0289 kg kg ⋅ K kg ⋅ K

m = nM = M

PV

(b)

RT

m = 0.0289 = 0.811 kg

mol (8.315 J/mol ⋅ K)(300 K)

6 Chapter 21 Solutions

kJ

(700 K – 300 K) = 233 kJ

kg ⋅ K

(d) We now consider a constant pressure process where the internal energy of the gas is

increased and work is done.

Q = (0.811 kg)

7 kJ

0.719 (400 K) = 327 kJ

5 kg ⋅ K

*21.19 Consider 800 cm3 of (flavored) water at 90.0˚C mixing with 200 cm3 of diatomic ideal gas at

20.0˚C:

(∆T)w = – =

mwcw (ρwVw)cw

where we have anticipated that the final temperature of the mixture will be close to 90.0˚C.

7 7 J

CP,air =

2 2 mol ⋅ C° 28.9 g

(∆T)w = –

[(1.00 g/cm3)(800 cm3)](4.186 J/g ⋅ C°)

The change of temperature for the water is between 10–3 °C and 10–2 °C

In the isovolumetric process, P triples so T changes from 2Ti to 6Ti .

7 5

2 2

Q = 13.5nRTi = 13.5PV

Chapter 21 Solutions 7

2(500 J)

500 J = n(3R/2)(TB – TA) or TB = TA +

3nR

2(500 J)

TB = 300 K + = 340 K

3(1.00 mol)(8.315 J/mol ⋅ K)

5nR

Q = nCP ∆T = (TC – TB) = –500 J

2

Thus,

2(500 J) 1000 J

(a) TC = TB – = 340 K – = 316 K

5nR 5(1.00 mol)(8.315 J/mol ⋅ K)

(b) The work done by the gas during the isobaric process is

or WBC= –200 J

or W on gas = +200 J

Q = n1C1 ∆T + n2C2 ∆T

The number of molecules is N1 + N2, so the number of "moles of the mixture" is n1 + n2 and

Q = (n1 + n2)C ∆T,

n 1C 1 + n 2C 2

so C=

n1 + n2

m m

(b) Q= ∑ niCi ∆T = ∑n C ∆T

i

i=1 i = 1

m m

C= ∑ niCi /∑n i

i=1 i=1

8 Chapter 21 Solutions

3RT

21.23 The rms speed of the gas molecules is v = . Thus, to double the rms speed, the

M

temperature must increase by a factor of 4: Tf = 4Ti.

P =

P Pi Pi

= = constant or V

V Vi V i

Pi V2 = nRT or V2 = V i nRT

V i Pi

2

Vf Tf

Therefore, 2 = = 4 or Vf = 2Vi.

Vi Ti

Pi 2Vi

⌠ V dV = 3 PiVi

Vf

⌠ P dV =

W=⌡

Vi V i ⌡Vi 2

5 15 15

nRTi = PV

2 2 2 i i

15 3

Q = ∆Eint + W = P V + P V = 9PiVi

2 i i 2 i i

*21.24 (a) PiV i = PfVf so = = = 0.118

V i Pf 20.0

Tf PfVf Pf V f

(b) = = = (20.0)(0.118) = 2.35

Ti PiV i Pi V i

CP R + CV 5

Since γ = 1.40 = = , CV = R, and ∆T = 2.35Ti – Ti = 1.35Ti

CV CV 2

5 J [1.35(300 K)] = 135 J

8.315

2 mol ⋅ K

Chapter 21 Solutions 9

γ γ

*21.25 (a) PiV i = PfVf

V i γ

Pf = Pi = (5.00 atm)

12.0 1.40

= 1.39 atm

V f 30.0

(b) Ti = = = 366 K

nR (2.00 mol)(8.315 J/mol ⋅ K)

Tf = = = 253 K

nR (2.00 mol)(8.315 J/mol ⋅ K)

CP R + CV 5

γ = 1.40 = = CV = R

CV CV 2

∆Eint = nCV ∆T = (2.00 mol) (8.315 J/mol ⋅ K) (366 – 253) K = 4.66 kJ

5

2

n= =

RTi (8.315 J/mol ⋅ K)(300 K)

γ γ

(a) PiV f = PfVf

Vf = 5.15 × 10–5 m 3

Pf Pi 1/γ

= Ti

PfVf

Tf = Ti = Ti(Pi/Pf)(1/γ – 1)

P iV i Pi Pf

10 Chapter 21 Solutions

(c) The work put into the gas in compressing it is ∆Eint = nCV ∆T

5

W = (9.97 × 10–3 mol) (8.315 J/mol ⋅ K)(560 – 300) K

2

W = 53.9 J

Now imagine this energy being shared with the inner wall as the gas is held at constant

volume. The pump wall has outer diameter 25.0 mm + 2.00 mm + 2.00 mm = 29.0 mm, and

volume

53.9 J = nCV ∆T + mc ∆T

5

53.9 J = (9.97 × 10–3 mol) (8.315 J/mol ⋅ K)(Tff – 300 K)

2

Tf V i γ – 1 1 0.400

21.27 = =

Ti V f 2

Goal Solution

G: The air should cool as it expands, so we should expect Tf < 300 K.

O: The air expands adiabatically, losing no heat but dropping in temperature as it does work on

the air around it, so we assume that PVγ = constant (where γ = 1.40 for an ideal gas).

γ γ nRT1 nRT2

A: Combine P1V1 = P2V2 and P1 = with P2 =

V1 V2

γ–1 γ–1

to find T1V1 = T2V2

V 1 γ – 1

T2 = T1 = 300 K

1 (1.40 – 1)

= 227 K

V 2 2

L: The air does cool, but the rate is not linear with the change in volume (the temperature drops

only 24% while the volume doubles)

Chapter 21 Solutions 11

P

21.28 (a) The work done on the gas is

Vb Pb b Adiabatic, Qab = 0

⌠ P dV

–Wab = – ⌡

Va

Tb’ = Ta

⌠

–Wab' = –nRTa ⌡

V b'

1 dV b’

Pb’

Va V

= –nRTa ln

Vb'

= nRTa ln

Va

Pa

a

V b'

V

V

Vb = Vb’ = Va /10 Va

J

mol ⋅ K

= 28.0 kJ

(b) For the adiabatic process, we must first find the final temperature, Tb. Since air consists

primarily of diatomic molecules, we shall use

V a γ – 1

Tb = Ta = (293 K)(10.0)0.400 = 736 K

V b

Thus, the work done on the gas during the adiabatic process is

Thus, Pb' = Pa

Va'

= (1.00 atm)(10.0) = 10.0 atm

Vb'

γ γ

For the adiabatic process, we have Pb'Vb = PaVa

V a γ

Thus, Pb = Pa = (1.00 atm)(10.0)1.40 = 25.1 atm

V b

12 Chapter 21 Solutions

P

21.29 (a) See the diagram at the right.

γ γ

(b) PBVB = PCVC 3Pi B Adiabatic

γ γ

3PiVi = PiVC

VC = 2.19(4.00 L) = 8.79 L

3Pi

A C

TB = 3Ti = 3(300 K) = 900 K V (L)

Vi = 4L VC

(d) After one whole cycle, TA = Ti = 300 K

5

(e)

2

7

2

Chapter 21 Solutions 13

P

21.30 (a) See the diagram at the right.

γ γ

(b) PBVB = PCVC 3Pi B Adiabatic

γ γ

3PiVi = PiVC

TB = 3Ti Pi

A C

V (L)

(d) After one whole cycle, TA = Ti

Vi VC

5

(e)

2

7

2

14 Chapter 21 Solutions

diatomic ideal gas. We find its final absolute pressure:

50.0 cm 3

21.0 atm(50.0 cm3)7/5 = Pf(400 cm3)7/5 400 cm 3

5 5 5 Before

∴ W = –n RTf + nRTi = (–PfVf + PiVi)

2 2 2

5

=[–(1.14 atm)(400 cm3) After

2

+ (21.0 atm)(50.0 cm3)]

1.013 × 105 N/m2 10–6 m3

1 atm cm3

W = 150 J

1 1 min 60 s

The time for this stroke is = 6.00 × 10–3 s

4 2500 1 min

W 150 J

So ℘ = = = 25.0 kW

t 6.00 × 10–3 s

kBT nRT

21.32 (1) Eint = Nf =f

2 2

1 dEint 1

(2) CV = = fR

n dT 2

1

(3) CP = CV + R = (f + 2) R

2

CP (f + 2)

(4) γ= =

CV f

5 7

21.33 (a) C V' = nR = 9.95 cal/K C'P = nR = 13.9 cal/K

2 2

7 9

(b) C V' = nR = 13.9 cal/K C'P = nR = 17.9 cal/K

2 2

Chapter 21 Solutions 15

21.34 A more massive diatomic or polyatomic molecule will generally have a lower frequency of

vibration. At room temperature, vibration has more chance of being excited than in a less

massive molecule. Absorbing energy into vibration shows up in higher specific heats.

1

21.35 Rotational Kinetic Energy = Iω 2

2

Cl

1

∴Krot = Iω2 = 2.33 × 10–21 J

2

21.36 The ratio of the number at higher energy to the number at lower energy is e–∆E/kBT where ∆E is

the energy difference. Here,

and at 0°C,

Since this is much less than the excitation energy, nearly all the atoms will be in the ground

state and the number excited is

This number is much less than one, so almost all of the time no atom is excited .

At 10000°C,

21.37 Call n00 the sea-level number density of oxygen molecules, nN0 the sea-level number of nitrogen

per volume, and n0 and nN their respective densities at y = 10.0 km.

n0 n00

and = exp (–m0gy/kBT + mNgy/kBT)

nN nN0

16 Chapter 21 Solutions

(n0/nN)

So = exp [–(m0 – mN)gy/kBT]

(n00/nN0)

= exp –

(1.38 × 10–23 J/K)300 K

= 0.855

The ratio of oxygen to nitrogen molecules decreases to 85.5% of its sea-level value.

21.38 (a) = = = 1.03

V rms,37 3RT/M37 35.0 g/mol

∑nivi 1

21.39 (a) vav = = [1(2) + 2(3) + 3(5) + 4(7) + 3(9) + 2(12)] = 6.80 m/s

N 15

2

∑n iv i

(b) (v2) av = = 54.9 m2/s2

N

vmp = = = 132 m/s

m 6.64 × 10–27 kg

= 0: 4πN

m 3/2

exp –

dN v mv 2 2mv 3

Take 2v – =0

dv 2π kBT 2kBT 2kBT

and solve for vmp to get Equation 21.29. Reject the solutions v = 0 and v = ∞.

mv2

Retain only 2 – = 0.

kBT

3kBT

21.42 (a) From vrms = , we find the temperature as

m

T= = 2.01 × 10 4 K

3(1.38 × 10–23 J/mol ⋅ K)

(b) T= = 9.01 × 10 2 K

3(1.38 × 10–23 J/mol ⋅ K)

Chapter 21 Solutions 17

1 2 3

21.43 At 0°C, mvrms0 = kBT0

2 2

1 3

At the higher temperature, m(2vrms0)2 = kBT

2 2

21.44 Visualize the molecules in liquid water at 20°C jostling about randomly. One happens to get

kinetic energy corresponding to 2430 J/g, and happens to be at the surface and headed upward.

Then this molecule can break out of the liquid.

(a) 2430 J/g =

g 1 mol 6.02 × 1023 molecules

1

(b) 7.27 × 10–20 J = mv2

2

2(7.27 × 10 –20 J)

v= = 2.21 km/s

18.0 u(1.66 × 10–27 kg/1 u)

(c) If these were typical molecules in an ideal gas instead of exceptional molecules in liquid

water,

1 3

mv2 = kBT

2 2

2 7.27 × 10–20 J

T= = 3510 K

3 1.38 × 10–23 J/K

These molecules got to be fast-moving in collisions that made other molecules slow-

moving; the average molecular energy is unaffected.

PV =

N PVNA

21.45 (a) RT and N= so that

A

N RT

N= = 3.21 × 1012 molecules

(8.315)(300)

1 V 1.00 m3

(b) l= = =

nVπd 2

2 1/2 N πd 2

2 1/2 (3.21 × 10 molecules)π (3.00 × 10–10 m) 2(2)1/2

12

l = 778 km

v

(c) f = l = 6.42 × 10 –4 s–1

18 Chapter 21 Solutions

Goal Solution

G: Since high vacuum means low pressure as a result of a low molecular density, we should

expect a relatively low number of molecules, a long free path, and a low collision frequency

compared with the values found in Example 21.7 for normal air. Since the ultrahigh vacuum

is 13 orders of magnitude lower than atmospheric pressure, we might expect corresponding

values of N ~ 1012 molecules/m3, l ~ 106 m, and f ~ 0.0001/s.

O: The equation of state for an ideal gas can be used with the given information to find the

number of molecules in a specific volume. The mean free path can be found directly from

equation 21.30, and this result can be used with the average speed to find the collision

frequency.

( a ) PV =

N PVNA

A: RT and N= so that

N A RT

N= = 3.21 × 1012 molecules

(8.315 J/mol ⋅ K)(300 K)

1 V 1.00 m3

(b) l = = =

2 π d 2n v 2 N πd2 2 (3.21 × 1012 molecules)π (3.00 × 10–10 m)2

v 500 m/s

(c) f=l= = 6.42 × 10–4 s–1

7.78 × 105 m

L: The pressure and the calculated results differ from the results in Example 21.7 by about 13

orders of magnitude as we expected. This ultrahigh vacuum provides conditions that are

extremely different from normal atmosphere, and these conditions provide a “clean”

environment for a variety of experiments and manufacturing processes that would otherwise

be impossible.

v= 8RT/πM

v = 178 m/s

Chapter 21 Solutions 19

1 1

l= =

2 π d 2n V 2π(0.200 × 10–9 m)2 1/m3

l = 5.63 × 1018 m

l = 5.63 × 1012 m

1

21.47 From Equation 21.30, l =

2 π d 2n V

N P

For an ideal gas, nV = =

V kBT

kBT

Therefore, l = , as required.

2 π d 2P

P

21.48 l = [ 2 πd2nV]–1 nV =

kBT

1.013 × 105

d = 3.60 × 10–10 m nV = = 2.51 × 1025/m3

(1.38 × 10 –23)(293)

kBT

21.49 Using P = nVkBT, Equation 21.30 becomes l = (1)

2 π Pd 2

(a) l= = 9.36 × 10–8 m

2 π (1.0113 × 10 5 Pa)(3.10 × 10 –10 m) 2

(b) Equation (1) shows that P1l1 = P2l2. Taking P1l1 from (a) and with l2 = 1.00 m, we find

P2 = = 9.36 × 10–8 atm

1.00 m

20 Chapter 21 Solutions

P3 = = 302 atm

3.10 × 10–10 m

*21.50 (a) n= = = 1.31 × 103 mol

RT (8.315 J/mol ⋅ K)(293 K)

1 3 3

(c) m v2 = kBT = (1.38 × 10–23 J/K)(293 K) = 6.07 × 10–21 J/molecule

2 0 2 2

M 0.0289 kg/mol

m0 = = = 4.80 × 10–26 kg/molecule

N A 6.02 × 1023 molecules/mol

vrms = = 503 m/s

4.80 × 10–26 kg/molecule

Eint = nCVT = n R T = PV

5 5

2 2

5

Eint = (1.013 × 105 Pa)(31.5 m3) = 7.98 MJ

2

Vf = = = 0.0665 m3 = 66.5 L

Pf 100 × 103 Pa

Chapter 21 Solutions 21

(b) Tf = 400 K

Vf = Vi = = = 0.0499 m3 = 49.9 L

Pi 100 × 103 Pa

Pf = Pi

Tf

= (100 kPa)

400 K

= 133 kPa

i

T 300 K

W = ∫ P dV = 0 since V = constant

Vf = Vi

Pi

= (49.9 L)

100 kPa

= 41.6 L

Pf 120 kPa

= nRTi ln = nRTi ln

Vf dV Vf Pi

⌠

W = ∫ P dV = nRTi ⌡

Vi V i

V Pf

100 kPa

= –910 J

120 kPa

(d) Pf = 120 kPa γ= = = = = =

CV CV 3.50R 3.50R 3.50 7

Pi 1/γ

Vf = Vi = (49.9 L)

γ γ 100 kPa 7/9

PfV f = PiVi so = 43.3 L

Pf 120 kPa

Tf = Ti

P fV f

= (300 K)

120 kPa 43.3 L

= 312 K

PiVi 100 kPa 49.9 L

Q = 0 (abiabatic process)

22 Chapter 21 Solutions

21.52 (a) The average speed vav is just the weighted average of all the speeds.

v av = = 3.65v

(2 + 3 + 5 + 4 + 3 + 2 + 1)

v av = = 15.95v2

2+3+5+4+3+2+1

2

The root-mean square speed is then vrms = v av = 3.99v

(c) The most probable speed is the one that most of the particles have;

i.e., five particles have speed 3.00v

1 2

(d) PV = Nmvav

3

= 106

20 [m(15.95)v2] mv 2

Therefore, P =

3 V V

– 1 2 1

K = mvav = m(15.95v2) = 7.98mv 2

2 2

f f d V PiVi – PfVf

21.53 (a) ⌠ P dV = k⌡

PVγ = k. So, W = ⌡ ⌠ =

i i Vγ γ–1

3

Therefore, W = –∆Eint = – nR ∆T = nCV(Ti – Tf)

2

Therefore, 1/(γ – 1) = CV/R.

CV

W = (PiVi – PfVf)

R

PV

Also, for an ideal gas = nT so that W = nCV(Ti – Tf)

R

Chapter 21 Solutions 23

N v = 4π N

m 3/2

v 2e–mv2/2kBT

2 π k B T

M 0.032 kg

With N = 1.00 × 104, m = = = 5.32 × 10–26 kg

N A 6.02 × 1023

The following is a plot of this function for the range 0 ≤ v ≤ 1400 m/s.

Nv (s/m)

18

16

14

12

10

4 vmp

vav

2 vrms

0 v (m/s)

0 200 400 600 800 1000 1200 1400 1600

(b) The most probable speed occurs where Nv is a maximum.

(c) vav = = = 575 m/s

πm π (5.32 × 10 –26 )

Also, vrms = = = 624 m/s

m 5.32 × 10 –26

600

⌠ N vd v

⌡ 300

(d) The fraction of particles in the range 300 ≤ v ≤ 600 m/s is where N = 104 and

N

the integral of Nv is read from the graph as the area under the curve. This is

approximately 4400 and the fraction is 0.44 or 44% .

24 Chapter 21 Solutions

21.55 The pressure of the gas in the lungs of the diver will be the same as the absolute pressure of the

water at this depth of 50.0 meters. This is:

1.00 atm

or = 5.84 atm

1.013 × 105 Pa

If the partial pressure due to the oxygen in the gas mixture is to be 1.00 atmosphere or less (or

approximately one-sixth of the total pressure), oxygen molecules should make up only about

one-sixth of the total number of molecules. This will be true if 1.00 mole of oxygen is used for

every 5.00 moles of helium. The ratio by weight is therefore,

= = 0.625

(1.00 mol O2)g (32.0 g)g

m 1.20 kg

*21.56 n= = = 41.5 mol

M 0.0289 kg/mol

(a) Vi = = = 0.514 m3

Pi 200 × 103 Pa

Vf = Vi

Pf 2

= (0.514 m3)

Pf Vf 400 2

(b) = so = 2.06 m3

Pi Vi Pi 200

(c) Tf = = = 2.38 × 10 3 K

nR (41.5 mol)(8.315 J/mol ⋅ K)

Vf

Pi 3/2 2 Pi 3/2

⌠ V1/2dV = 2V

Vf Vf

(d) ⌠ P dV = C ⌡

W=⌡ = (V

3/2

– Vi )

Vi Vi 1/2

Vi 3 3 V 1/2 f

Vi i

W= [(2.06 m3)3/2 – (0.514 m)3/2] = 4.80 × 105 J

3 0.514 m

∆Eint = nCV ∆T = (41.5 mol) (8.315 J/mol ⋅ K) (2.38 × 103 – 298) K

5

(e)

2

Chapter 21 Solutions 25

21.57 (a) Since pressure increases as volume decreases (and vice versa) ,

dV 1 d V

<0 and – >0

dP V dP

nRT 1 d nRT

(b) For an ideal gas, V = and κ1 = –

P V dP P

nRT 1 1

κ1 = – – =

V P 2 P

κ2 = – = (1/γ)+1 = 1/ γ+1 =

V dP P V γ P γP γP

1 1

(d) κ1 = = = 0.500 atm–1

P (2.00 atm)

CP

γ= and for a monatomic ideal gas, γ = 5/3, so that

CV

1 1

κ2 = = = 0.300 atm–1

γ P (5/3)(2.00 atm)

B dP

*21.58 (a) The speed of sound is v = where B = –V .

ρ dV

1

According to Problem 57, in an adiabatic process, this is B = = γP.

κ2

ms nM (nRT)M PM

Also, ρ = = = = where ms is the sample mass. Then, the speed of

V V V(RT) RT

γR T

γP

B RT

sound in the ideal gas is v = = =

ρ

PM M

(b) v= = 344 m/s

0.0289 kg/mol

This nearly agrees with the 343 m/s listed in Table 17.1.

26 Chapter 21 Solutions

R γR T γkBN AT γkBT

(c) We use kB = and M = mNA: v = = =

NA M mN A m

2kBT

The most probable molecular speed is ,

m

8kBT 3kBT

the average speed is , and the rms speed is .

πm m

2πkBT

m 3/2

2

v 2e (–v2/v mp )

2 π k B T

=

N v (v) v 2 (1 – v2/v2 )

and e

N v (v mp ) vmp mp

N v (v) 1 2

For v = vmp/50,

N v (v mp ) 50

The other values are computed similarly, with the following results:

v N v (v)

vmp N v (v mp )

1/50 1.09 × 10–3

1/10 2.69 × 10–2

1/2 0.529

1 1.00

2 0.199

10 1.01 × 10–41

50 1.25 × 10–1082

= 10log2500e(ln10)(–2499/ln10) = 10log250010–2499/ln10

Chapter 21 Solutions 27

1 2 1 2 1

mv i – mv f = (0.142 kg) [(47.2)2 – (42.5)2]m2/s2 = 29.9 J

2 2 2

and its quantity is n = = = 3.47 mol

RT (8.315 J/mol ⋅ K)(293 K)

Q 29.9 J

∆T = = = 0.296 C°

nCP (3.47 mol)(7/2)(8.315 J/mol ⋅ K)

21.61 (a) The effect of high angular speed is like the effect of a very high gravitational field on

an atmosphere. The result is:

The larger-mass molecules settle to the outside while the region at smaller r has a

higher concentration of low-mass molecules.

(b) Consider a single kind of molecules, all of mass m. To supply the centripetal force on the

molecules between r and r + dr, the pressure must increase outward according to

∑Fr = mar. Thus,

where n is the number of molecules per unit volume and A is the area of any cylindrical

surface. This reduces to dP = nmω2rdr.

dn mω2 n dn mω2 r

= r dr giving ⌠

⌡n n = k T ⌠

⌡0r dr or

n kBT 0 B

r

n mω2 r2

ln(n)n0 =

kBT 2 0

n mω2 2

ln

2 2

= r and solving for n: n = n0emr ω /2kBT

n0 2kBT

28 Chapter 21 Solutions

1 ∞ m

21.62

2

First find vav as vav =

2

⌠

⌡0 v2N vdv . Let a = 2kBT .

N

Then, vav =

N ⌡0 v e dv = [4a3/2π –1/2] 8a 2 a

=

m

2 3kBT

The root-mean square speed is then vrms = v av =

m

1 ∞

vav = ⌠

⌡0 vN vdv =

N

(4Na 3/2 π –1/2 ) ∞ 4a π 3/2 –1/2

⌠

⌡0 v 3e–av2dv = =

N 2a 2 P(atm)

8kBT 3.00 B

πm

*21.63 (a) n= =

RT (8.315 J/mol ⋅ K)(300 K) 2.00

n = 0.203 mol

1.00 A C

TB = TA = (300 K)

PB 3.00

(b) = 900 K

A

P 1.00

VC = VA

T C

= (5.00 L)

900

= 15.0 L

TA 300

3 3

(c) Eint,A = nRTA = (0.203 mol)(8.315 J/mol ⋅ K)(300 K) = 760 J

2 2

3 3

Eint,C = Eint,B = nRTB = (0.203 mol)(8.315 J/mol ⋅ K)(900 K) = 2.28 kJ

2 2

(d)

P(atm) V(L) T(K) Eint (kJ)

A 1.00 5.00 300 0.760

B 3.00 5.00 900 2.28

C 1.00 15.00 900 2.28

(e) For the process AB, lock the piston in place and put the cylinder into an oven at 900 K.

For BC, keep the sample in the oven while gradually letting the gas expand to lift a

Chapter 21 Solutions 29

load on the piston as far as it can. For CA, carry the cylinder back into the room at 300 K

and let the gas cool without touching the piston.

30 Chapter 21 Solutions

Q = ∆Eint + W = 1.52 kJ

Q = ∆Eint + W = 1.67 kJ

W = P ∆V = nR ∆T

(g) We add the amounts of energy for each process to find them for the whole cycle.

Chapter 21 Solutions 31

21.64 With number-per-volume n0e(–mgy/kBT), the number of molecules above unit ground area is

∞ h

⌠ ⌠ n(y)dy . So,

⌡0 n(y)dy , and the number below altitude h is ⌡ 0

h h h

⌠ n(y)d y

⌡ n0⌠

⌡ e(–mgy/kBT)dy ⌠ e(–mgy/kBT)(–mg dy/kBT)

–kBT/mg ⌡

0 o 0

(a) f= ∞ = ∞ = ∞

⌠ ⌠ e(–mgy/kBT)dy –kBT/mg ⌡

⌡0 n(y)d y n0⌡ ⌠ e(–mgy/kBT)(–mg dy/kBT)

0 0

h

e(–mgy/kBT)0 e(–mgh/kBT) – 1

= ∞ = = 1 – e(–mgh/kBT)

e(–mgy/kBT)0 0–1

1

(b) = 1 – e(–mgh'/kBT)

2

1

e(–mgh'/kBT) = or e(+mgh'/kBT) = 2

2

mgh'/kBT = ln 2 so

h' = = = 5.47 km

mg (28.9 u)(1.66 × 10–27 kg/u)(9.80 m/s2)

*21.65 (a) (10 000 g) = 3.34 × 1026 molecules

18.0 g 1.00 mol

(b) After one day, 10–1 of the original molecules would remain. After two days, the fraction

would be 10–2, and so on. After 26 days, only 3 of the original molecules would likely

remain, and after 27 days , likely none.

1.32 × 1021 kg

Therefore, today’s soup likely contains this fraction of the original molecules. The

number of original molecules likely in the pot again today is:

1.32 × 1021 kg

1 GmM GM

21.66 (a) For escape, mv2 = . Since the free-fall acceleration at the surface is g = 2 ,

2 R R

1 GmM

this can also be written as: mv2 = = mgR

2 R

0.0320 kg/mol

m= = 5.32 × 10–26 kg/molecule

6.02 × 1023 molecules/mol

32 Chapter 21 Solutions

T= = = 1.60 × 10 4 K

15k B 15(1.38 × 10–23 J/mol ⋅ K)

21.67 (a) For sodium atoms (with a molar mass M = 32.0 g/mol)

1 3

mv2 = kBT

2 2

1M 2 3

v = kBT

2 N A 2

(a) vrms = = = 0.510 m/s

M 23.0 × 10–3 kg

d 0.010 m

(b) t= = ≈ 20 ms

v rms 0.510 m/s

Chapter 21 Solutions 33

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