You are on page 1of 33

# Chapter 21 Solutions

*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

## NAm = 4.00 g/mol

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.

## NkT 3NA kB T 3RT 3(8.315 N · m/mol · K)(293 K)

P= = = = = 9.13 × 105 Pa
V V V 8.00 × 10–3 m 3

## – ∆v [8.00 sin 45.0° – (–8.00 sin 45.0°)]m/s

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

## – ∆v [vxf – vxi] [v sin θ – (–v sin θ)] 2v sin θ

F = Nm = Nm = Nm = Nm
∆t t t t

F 2v sin θ
P = = Nm
A At

## – (5.00 × 1023)(2 × 4.68 × 10–26 kg × 300 m/s)

*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

## 3PV 3(8.00 atm)(1.013 × 105 Pa/atm)(5.00 × 10–3 m3)

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

## Kav = 5.05 × 10–21 J/molecule

2N —
21.7 P= (KE) Equation 21.2
3V

## 3 PV 3 (1.20 × 10 5)(4.00 × 10 –3)

N= = = 2.00 × 1024 molecules
2 — 2 (3.60 × 10 –22 )
(K E)

## N 2.00 × 1024 molecules

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

## PV (1.20 × 105 N/m2)(4.00 × 10–3 m3)

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

## PV (1.013 × 105 Pa) 43 π (0.150 m)3

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

## mv 2 3kBT 3RT 3 (8.315)(300)

(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

## m = 6.64 × 10–27 kg/molecule

4 Chapter 21 Solutions

## Similarly for argon,

39.9 g/mol
m= = 6.63 × 10–23 g/molecule
6.02 × 1023 molecules/mol

## Substituting in (1) above, we find

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)

## Thus, Vf = Vi + ∆V = 5.00 L + 2.52 L = 7.52 L

Chapter 21 Solutions 5

## (a) ∆Eint = Q – W = 209 J – 0 = 209 J

∆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)

## T = Ti + ∆T = 300 K + 16.8 K = 317 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 

## 7 (1.013 × 105 N/m2)(100 m3)

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

## R =  8.315   1.00 mol  = 719 J = 0.719 kJ

5 5 J
*21.18 (a) CV =
2 2 mol ⋅ K 0.0289 kg kg ⋅ K kg ⋅ K

m = nM = M 
PV
(b)
RT 

## kg  (200 × 103 Pa)(0.350 m3)

m =  0.0289 = 0.811 kg
 mol (8.315 J/mol ⋅ K)(300 K)

6 Chapter 21 Solutions

## Q = mCv ∆T = (0.811 kg)  0.719

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= mCP ∆T = m(CV + R)∆T = m(7R/2)∆T = m(7CV/5)∆T

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:

## m airC P,air(Tf – Ti,air) [ρV]air CP,air(90.0°C – 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.

## R =  8.315   1.00 mol = 1.01 J/g ⋅ C°

7 7 J
CP,air =
2 2 mol ⋅ C°  28.9 g 

## [(1.20 × 10–3 g/cm3)(200 cm3)](1.01 J/g ⋅ C°)(70.0 C°)

(∆T)w = –
[(1.00 g/cm3)(800 cm3)](4.186 J/g ⋅ C°)

## or (∆T)w ≈ 5.05 × 10–3 C°

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

## In the isobaric process, V doubles so T must double, to 2Ti .

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

## Q = n  R  (2Ti – Ti) + n  R  (6Ti – 2Ti)

7 5
2  2 

Q = 13.5nRTi = 13.5PV

Chapter 21 Solutions 7

## 21.21 In the isovolumetric process A → B, W = 0 and Q = nCV ∆T = 500 J

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)

## In the isobaric process B → C,

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

## Won gas = –Wby gas = –(WAB + WBC) = –(0 – 200 J)

or W on gas = +200 J

## 21.22 (a) The heat required to produce a temperature change is

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.

## Since the pressure is proportional to volume in this process,

P =
P Pi Pi 
= = constant or V
V Vi V i

## Then, PV = nRT becomes

 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

## and the energy transferred to the gas as heat is

15 3
Q = ∆Eint + W = P V + P V = 9PiVi
2 i i 2 i i

## γ γ Vf  Pi 1/γ  1.00 5/7

*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

## (c) Since the process is adiabatic, Q = 0

CP R + CV 5
Since γ = 1.40 = = , CV = R, and ∆T = 2.35Ti – Ti = 1.35Ti
CV CV 2

## ∆Eint = nCV ∆T = (0.0160 mol) 

5  J  [1.35(300 K)] = 135 J
8.315
 
2 mol ⋅ K

## and W = Q – ∆Eint = 0 – 135 J = –135 J

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

## PiVi (5.00)(1.013 × 105 Pa)(12.0 × 10–3 m 3)

(b) Ti = = = 366 K
nR (2.00 mol)(8.315 J/mol ⋅ K)

## PfVf (1.39)(1.013 × 105 Pa)(30.0 × 10–3 m 3)

Tf = = = 253 K
nR (2.00 mol)(8.315 J/mol ⋅ K)

## (c) The process is adiabatic: Q=0

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 

## PiVi (1.013 × 105 Pa)(2.45 × 10–4 m 3)

n= =
RTi (8.315 J/mol ⋅ K)(300 K)

γ γ
(a) PiV f = PfVf

## Vf = Vi(Pi/Pf)1/γ = 2.45 × 10–4 m3(101.3/901.3)5/7

Vf = 5.15 × 10–5 m 3

## (b) PfVf = nRTf

Pf Pi 1/γ
= Ti  
PfVf
Tf = Ti = Ti(Pi/Pf)(1/γ – 1)
P iV i Pi Pf

## Tf = 300 K(101.3/901.3)(5/7 – 1) = 560 K

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

## The overall warming process is described by

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

## Tff – 300 K = 2.24 K

Tf  V i γ – 1  1 0.400
21.27 = =
Ti V f 2

## If Ti = 300 K, then Tf = 227 K

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

## For the isothermal process, Isothermal,

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

## Thus, –Wab' = (5.00 mol)  8.315  (293 K) ln (10.0)

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

## Then, from Equation 21.20,

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

## (c) For the isothermal process, we have Pb'Vb' = PaVa

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 = 31/γVi = 35/7Vi = 2.19Vi

VC = 2.19(4.00 L) = 8.79 L

## (c) PBVB = nRTB = 3PiVi = 3nRTi

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 

## WABCA = 0.830(1.013 × 105 Pa)(4.00 × 10–3 m3) = 336 J

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

## (c) PBVB = nRTB = 3PiVi = 3nRTi

TB = 3Ti Pi
A C
V (L)
(d) After one whole cycle, TA = Ti
Vi VC

5
(e)
2 

7
2 

## WABCA = QABCA = 0.830nRTi = 0.830PiVi

14 Chapter 21 Solutions

## 21.31 We suppose the air plus burnt gasoline behaves likes a

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

## Now Q = 0, and W = –∆Eint = –nCV(Tf – Ti)

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

## I = 1.17 × 10–45 kg ⋅ m2 ω = 2.00 × 1012 s–1

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,

## kBT = (1.38 × 10–23 J/K)(273 K) = 3.77 × 10–21 J

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

## (2.70 × 1025)exp(–1.63 × 10–18 J/3.77 × 10–21 J) = (2.70 × 1025)e–433

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

At 10000°C,

## = (2.70 × 1025)e–11.5 = 2.70 × 1020

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.

## nN = nNO exp (–mNgy/kBT)

n0 n00
and = exp (–m0gy/kBT + mNgy/kBT)
nN nN0

16 Chapter 21 Solutions

(n0/nN)
So = exp [–(m0 – mN)gy/kBT]
(n00/nN0)

## (32.0 – 28.0) u (1.66 × 10–27 kg/u)(9.80 m/s2)104 m

= 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.

## V rms,35 3RT/M35  37.0 g/mol 1/2

21.38 (a) = = = 1.03
V rms,37 3RT/M37 35.0 g/mol

## (b) The lighter atom, 35 C l , moves faster.

∑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

## 2kBT 2(1.38 × 10–23 J/K)(4.20 K)

vmp = = = 132 m/s
m 6.64 × 10–27 kg

## 21.41 Use Equation 21.26.

= 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

## (6.64 × 10–27 kg)(1.12 × 104 m/s)2

T= = 2.01 × 10 4 K
3(1.38 × 10–23 J/mol ⋅ K)

## (6.64 × 10–27 kg)(2.37 × 103 m/s)2

(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

## T = 4T0 = 4(273 K) = 1092 K = 819°C

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.

## 2430 J  18.0 g  1 mol 

(a) 2430 J/g =
g 1 mol  6.02 × 1023 molecules

## = 7.27 × 10–20 J/molecule

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

## (1.00 × 10 –10)(133)(1.00)(6.02 × 10 23)

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

## (1.00 × 10–10 torr)(133 Pa/torr)(6.02 × 1023 molecules/mol)

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

## l = 7.78 × 105 m = 778 km

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= 8(8.315 J/mol ⋅ K)3.00 K/π(2.016 × 10–3 kg/mol)

v = 178 m/s

Chapter 21 Solutions 19

## (a) The mean free path is

1 1
l= =
2 π d 2n V 2π(0.200 × 10–9 m)2 1/m3

l = 5.63 × 1018 m

## (b) Now nV is 106 times larger, to make l smaller by 106 times:

l = 5.63 × 1012 m

## Thus, l/v = 3.17 × 1010 s = 1.00 × 103 yr

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)

## ∴l = 6.93 × 10–8 m, or about 193 molecular diameters

kBT
21.49 Using P = nVkBT, Equation 21.30 becomes l = (1)
2 π Pd 2

## (1.38 × 10–23 J/K)(293 K)

(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

## (1.00 atm)(9.36 × 10–8m)

P2 = = 9.36 × 10–8 atm
1.00 m

20 Chapter 21 Solutions

P3 = = 302 atm
3.10 × 10–10 m

## PV (1.013 × 105 Pa)(4.20 m × 3.00 m × 2.50 m)

*21.50 (a) n= = = 1.31 × 103 mol
RT (8.315 J/mol ⋅ K)(293 K)

## (b) m = nM = (1.31 × 103 mol)(0.0289 kg/mol) = 37.9 kg

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

## (d) For one molecule,

M 0.0289 kg/mol
m0 = = = 4.80 × 10–26 kg/molecule
N A 6.02 × 1023 molecules/mol

## 2(6.07 × 10–21 J/molecule)

vrms = = 503 m/s
4.80 × 10–26 kg/molecule

## (e) and (f)

Eint = nCVT = n  R  T = PV
5 5
2  2

5
Eint = (1.013 × 105 Pa)(31.5 m3) = 7.98 MJ
2

## nRTf (2.00 mol)(8.315 J/mol ⋅ K)(400 K)

Vf = = = 0.0665 m3 = 66.5 L
Pf 100 × 103 Pa

## Q = ∆Eint + W = 5.82 kJ + 1.66 kJ = 7.48 kJ

Chapter 21 Solutions 21

(b) Tf = 400 K

## nRTi (2.00 mol)(8.315 J/mol ⋅ K)(300 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

## ∆Eint = 3.50nR ∆T = 0 since T = constant

= nRTi ln   = nRTi ln  
Vf dV Vf Pi

W = ∫ P dV = nRTi ⌡
Vi V  i
V Pf

100 kPa
= –910 J
120 kPa

## CP CV + R 3.50R + R 4.50 4.50 9

(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

## ∆Eint = 3.50nR ∆T = 3.50(2.00 mol)(8.315 J/mol ⋅ K)(12.4 K) = 722 J

Q = 0 (abiabatic process)

## W = Q – ∆Eint = 0 – 722 J = –722 J

22 Chapter 21 Solutions

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

## [2(v) + 3(2v) + 5(3v) + 4(4v) + 3(5v) + 2(6v) + 1(7v)]

v av = = 3.65v
(2 + 3 + 5 + 4 + 3 + 2 + 1)

## 2 [2(v)2 + 3(2v) 2 + 5(3v) 2 + 4(4v) 2 + 3(5v) 2 + 2(6v) 2 + 1(7v) 2 ]

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 

## (e) The average kinetic energy for each particle is

– 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

## (b) dEint = dQ – dW and dQ = 0 for an adiabatic process.

3
Therefore, W = –∆Eint = – nR ∆T = nCV(Ti – Tf)
2

## To show consistency between these 2 equations, consider that γ = CP/CV and CP – CV = R.

Therefore, 1/(γ – 1) = CV/R.

## Using this, the result found in part (a) becomes

CV
W = (PiVi – PfVf)
R

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

Chapter 21 Solutions 23

## 21.54 (a) Maxwell’s speed distribution function is

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

## N v = (1.71 × 10–4)v 2e–(3.85 × 10–6)v2

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.

## 8kBT 8(1.38 × 10 –23)(500)

(c) vav = = = 575 m/s
πm π (5.32 × 10 –26 )

## 3kBT 3(1.38 × 10 –23)(500)

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:

## P = 1.00 atm + (4.90 × 105 Pa) 

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,

## (5.00 mol He)g (20.0 g)g

= = 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

## nRTi (41.5 mol)(8.315 J/mol ⋅ K)(298 K)

(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

## PfVf (400 × 103 Pa)(2.06 m 3)

(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

## 2  200 × 103 Pa

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 

## Q = ∆Eint + W = 1.80 × 106 J + 4.80 × 105 J = 2.28 × 106 J = 2.28 MJ

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

## 1 d  C  1/γ 1  1  C1/γ P1/γ 1

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

## 1.40(8.315 J/mol ⋅ K)(293 K)

(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 

## Thus, N v(v) = 4πN 

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

## =   e[1 – (1/50)2] = 1.09 × 10–3

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

## (50) 2 e 1 – 2500 = 2500e –2499

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

## = 10log2500 – 2499/ln10 = 10–1081.904

Chapter 21 Solutions 27

## *21.60 The ball loses energy

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

## PV (1.013 × 105 Pa)(0.0834 m3)

and its quantity is n = = = 3.47 mol
RT (8.315 J/mol ⋅ K)(293 K)

## The air absorbs energy according to Q = nCP ∆T, so

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,

## PA – (P + dP)A = –(nmA dr)(rω2)

where n is the number of molecules per unit volume and A is the area of any cylindrical
surface. This reduces to dP = nmω2rdr.

## But also P = nkBT, so dP = kBT dn. Therefore, the equation becomes

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

## 2 [4N π –1/2a3/2] ⌠∞ 4 –av2 3 π 3kBT

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

## To find the average speed, we have

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

## PV (1.013 × 105 Pa)(5.00 × 10–3 m 3)

*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

## TC = TB = 900 K 0 5.0 10.0 15.0 V(L)

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

## (f) For AB: W = 0 , ∆Eint = Eint,B – Eint,A = (2.28 – 0.769) kJ = 1.52 kJ

Q = ∆Eint + W = 1.52 kJ

## W = (0.203 mol)(8.315 J/mol ⋅ K)(900 K) ln(3.00) = 1.67 kJ

Q = ∆Eint + W = 1.67 kJ

W = P ∆V = nR ∆T

## Q = ∆Eint + W = –1.52 kJ – 1.01 kJ = –2.53 kJ

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

## (∆Eint)ABCA = +1.52 kJ + 0 – 1.52 kJ = 0

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

## k B T ln 2 (1.38 × 10 –23 J/K)(270 K)(ln 2)

h' = = = 5.47 km
mg (28.9 u)(1.66 × 10–27 kg/u)(9.80 m/s2)

## 1.00 mol  6.02 × 1023 molecules

*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.

## (c) The soup is this fraction of the hydrosphere:  10.0 kg 

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:

##  10.0 kg  (3.34 × 1026 molecules) = 2.53 × 106 molecules

 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

## (b) For O2, the mass of one molecule is

0.0320 kg/mol
m= = 5.32 × 10–26 kg/molecule
6.02 × 1023 molecules/mol

32 Chapter 21 Solutions

## mgR (5.32 × 10–26 kg)(9.80 m/s2)(6.37 × 106 m)

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

1M 2 3
v = kBT
2 N A  2

## 3RT 3(8.315 J/mol ⋅ K)(2.40 × 10–4 K)

(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