Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition

ANSWERS TO END OF CHAPTER EXERCISES

INTRODUCTION E0.18 459.67F

E0.1 8.0 102 N

E0.19 (a) / C 100 / C
(b) F / F 212 9 5 / C
E0.2 0.43%
E0.20 P / P 7.092 / C 209.9
E0.3 2.6 kJ (a) P / P 7.092 T / K 63.25
(b) P / P 3.940 F / F 345.8F
E0.4 36 J

E0.21 671.67R
E0.5 1.4 102 kJ

E0.22 3.3 1022 glucose molecules

E0.6 2.3 kJ

E0.23 3.711024 octane molecules

E0.7 2.483 1024 J

E0.8 12 J E0.24 3.7 1019 myoglobin molecules

E0.9 (a) 1.602 1019 J E0.25 0.97

1
(b) 96.47 kJ mol
E0.26 M / Vm

E0.10 (a) 2.4 1019 J

E0.27 73.0 mmol dm3
(b) 1.4 102 kJ mol1
E0.28 17.5 g NaCl
E0.11 11.6 GJ
E0.29 (a)
(i) Water: 17.5 g NaCl
E0.12 (a) 810. Torr
(ii) Benzene: 9.02 102 mol dm3
(b) 0.962 atm (b)
(c) 0.222 atm (i) Water: 9.12 102 mol kg 1
(d) 1.03 10 Pa
5
(ii) Benzene: 0.105 mol kg 1

E0.13 1.24 103 bar E0.32 9.574 mol kg 1

E0.33 2.17 kg
E0.14 0.98 atm

E0.34 5.3 102 kg

E0.15 (a) 1.5 103 Pa
(b) 5.6 102 Pa
CHAPTER 1
E0.16 Differ by as much as 1 part in 10 6 The Properties of Gasses

E0.17 (a) 9.80665 Pa E1.1 92.1 kPa

(b) 0.0735561 Torr
E1.2 2.25 kPa

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E1.3 4.33 mmol (b)

cCH4 79 K 323 m s 1
E1.4 665 bar cCH4 315 K 645 m s 1
cCH4 1500 K 1.41 km s 1
E1.5 10.0 atm

E1.21 (a) 72 K
E1.6 4.18 bar
(b) 944 m s1
E1.7 173 kPa
E1.22 0.065 Pa
E1.8 29.5 K
E1.23 2.4 106 Pa
E1.9 394 K
E1.24 0.97 m
E1.10 (a) 3.6 m3 E1.25 (a) 5.3 1010 s1
(b) 178 m3 (b) 5.3 109 s1
(c) 5.3 104 s1
E1.11 0.50 m3
E1.26 (a) 6.5 1033 s1
E1.13 3.4 108 dm3 (b) 6.5 1031 s1
(c) 6.5 1021 s1
2
E1.14 6.7 10 atm .
E1.27 4.5 108 s1
3
E1.15 (a) 1.32 dm
(b) 61.2 kPa . E1.28 (a) 6.8 nm
(b) 68 nm
E1.16 713 Torr (c) 7 mm

E1.17 132 g mol1 E1.29 Independent of temperature

E1.18 16.4 g mol1 . E1.30 (a)

(i) 10 1 kPa
E1.19 (a) pH2 2.0 bar, pN2 1.0 bar (ii) 83 1 bar
(b)
(b) 3.0 bar
(i) 0.99 atm
(ii) 1.8 103 atm
E1.20 (a)
cHe 79 K 647 m s 1
E1.31 For a perfect gas: 55.6 atm
cHe 315 K 1.29 km s 1 For a van der Waals gas: 43.0 atm
cHe 1500 K 2.82 km s 1

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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a E2.13 (a) 30 J K 1 mol1

E1.32 B = b and C b 2
RT (b) 38 J K 1 mol1

E1.33 (a) 4.60 102 dm3 mol1

E2.14 (a) 9.2 102 kJ
(b) 0.66
(b) 6.1102 s .

E1.34 (a) 1.26 dm6 atm mol2

E2.15 773 J
(b) 3.46 102 dm3 mol1
E2.16 25 kJ
E1.35 1.03 10 K 3

E2.17 1.86 kJ
CHAPTER 2
E2.18 14.54 J
Thermodynamics: the First Law

E2.1 (a) 0.10 J E2.19 42.5 J

(b) 100. J
E2.20 20 kJ .
E2.2 5.5 kJ
E2.22 2.468kJ mol1
E2.3 (a) 99 J
(b) 167 J
E2.23 (a) 1.2 kJ
E2.4 +123 J (b) 1.2 kJ
(c) 80 J K 1
E2.5 +2.99 kJ
E2.24 (a) +2.2 kJ
E2.6 1.25 kJ (b) +2.2 kJ
(c) 1.6 kJ
E2.7 (a) 0
(b) 782 J E2.25 20.83 J K1 mol1

E2.8 1.0 102 J E2.26 (a) 641 J mol1

(b) 458 J mol1
1
E2.9 23.7 J K
CHAPTER 3
1 1 Thermodynamics:
E2.10 (a) 0.45 J K g
Applications of the First Law
(b) 25 J K 1 mol1
E3.1 6.91 mJ mol1
E2.11 42 kJ
E3.2 +2.83 104 kJ
E2.12 8.7 10 J4

E3.3 (a) 2.44 103 kJ

(b) 2.26 103 kJ

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E3.4 39.8 kJ mol1 E3.21 (a) 2.80 MJ mol1

(b) 2.80 MJ mol1
E3.5 (a) 80.0 kJ (c) 1.27 MJ mol1
(b) 5.20 kJ
(c) 74.8 kJ E3.22 (a) 1333 kJ mol1 .
(b) 1331 kJ mol1
E3.7 +239 kJ
(c) 815 kJ mol1

E3.8 4.96 kJ mol1

E3.24 112.27 kJ mol1
E3.9 2.48 kJ mol1
E3.25 383 kJ mol1
E3.10 163 kJ

E3.11 (a) +354.8 kJ mol1 E3.26 1.9 kJ mol1 .

(b) +352.3 kJ mol1
E3.27 +30.6 kJ mol1
E3.12 (a) 388 kJ mol1
(b) smaller. E3.28 (a) 37C
(b) 4.1 kg
1
E3.13 (a) 16 kJ mol
(b) 3028 kJ mol1 E3.29 (a) 2205 kJ mol1
(b) 2200 kJ mol1
E3.14 (a) 3.29 GJ
(b) 2.71 GJ E3.30 (a) exothermic, r H O negative
(b) endothermic, H O positive
E3.15 (a) 1560 kJ mol1 (c) endothermic, vap H O positive
1
(b) 51.88 kJ g
(d) endothermic, fus H O positive
(c) Ethane is a less efficient fuel
(e) endothermic, sub H O positive

E3.16 4564.7 kJ mol1

E3.31 (a) 57.20 kJ mol1

E3.17 85 kJ mol1 (b) 28.6 kJ mol1

(c) 138.2 kJ mol1
E3.18 432 kJ mol1 (d) 32.88 kJ mol1
(e) 55.84 kJ mol1
E3.19 225 kJ mol1
E3.32 11.3 kJ mol1 .
E3.20 (a) 4.22 kJ K1
(b) 0.769 K E3.33 56.98 kJ mol1

E3.34 40.88 kJ mol1

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E3.35 (a) Decrease E4.17 (a) 87.8 J K1 mol1

(b) Decrease (b) 87.8 J K1 mol1 .
(c) Increase
E4.18 79 J K 1 mol1
E3.36 (a) Increase
(b) Increase E4.19 (a) +85 J K 1 mol1 .
(b) +34 kJ K1 mol1
CHAPTER 4
Thermodynamics: the Second Law
V
E4.20 kN ln f
E4.1 0.410 J K1 Vi
E4.21 11.5 J K 1 mol1
E4.2 (a) 0.12 kJ K1 .
(b) 0.12 kJ K1 E4.22 (a) positive
(b) negative
(c) positive
E4.3 (a) 45.1 kJ
(b) 165 J K1
E4.23 (a) 386.1 JK1mol1
(b) 92.6JK1mol1
E4.5 14 J K1 mol1 (c) 153.1 J K 1 mol1
(d) 21.0 J K1 mol1
3
E4.6 2.91 dm
(e) 512.0 J K1 mol1

E4.7 33 J K 1
E4.24 5.03 kJ K1

E4.8 23.6 J K 1
E4.25 (a) 198.72 J K 1
(b) 309 J K 1
E4.9 93.0 J K1

E4.26 (a) 0.75 J K1

E4.10 8.64% high
(b) 0.15 J K1

E4.11 7.9 J K 1 mol1

E4.27 32.99 kJ

E4.12 0.6300 Ti
E4.28 (a) 93 kJ mol1
(b) Yes, G is negative.
E4.14 4.0 104 J K1 mol1
(c) 0.30 kJ K1 mol1

E4.15 5.11 J K 1 E4.29 0.41 g

E4.16 0.95 J K 1 mol1 E4.30 17 J

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E4.31 (a) Yes E5.14 0.758 Pa

(b) 0.46 mol ATP
E5.15 36.7 kJ mol1
E4.32 8.1 1023 molecules of ATP
E5.16 353 K
3
E4.33 (a) Density of cell 13 W m
E5.17 (a) 3
(b) Density of battery 150 kW m3
(b) 1
(c) The battery.

E5.18 (a) 2
CHAPTER 5 (b) 2
Physical Equilibria: Pure Substances
E5.19 (a) Yes
E5.1 Rhombic sulfur (b) 3.0 Torr or more

E5.2 No
CHAPTER 6
The Properties of Mixtures
E5.3 (a) +2.03 kJ mol1
(b) 1.50 J mol1 E6.1 886.8 cm3

E5.4 +14 kJ mol1 E6.2 96.9 cm3

E5.5 (a) 2.7 kJ mol1 E6.3 1.8 kJ mol1

(b) 2.0 kJ mol1
E6.4 32.631 J mol1

E5.6 4.2 kJ mol1

E6.5 (a) 1.31 kJ mol1
(b) 4.38 J K1 mol1
E5.7 710 K
(c) Yes.

E5.8 3.5 kJ mol1

E6.7 4.99 kPa

E5.10 (a) 1.1 kg

E6.8 2.30 kPa
(b) 15 kg
(c) 1.1 g E6.9 6.4 103 kPa

E5.11 (a) 134.6 bar K1 E6.10 4.8 103

(b) 135.6 bar .
E6.11 128 kPa
1
E5.12 (a) 31.69 kJ mol
(b) 373 K E6.12 (a) 1.3 mmol dm3
(b) 17.0 mmol dm3
E5.13 8.330

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E6.14 34.5 mmol dm3 pCOCl pCl

E7.2 (a) K
pCO pCl2
E6.18 5.6 kJ mol1 2
pSO
(b) K 2
3

pSO 2
pO2
E6.19 59.1 g mol1 2
pHBr
(c) K
pH2 pBr2
E6.20 0.068 C pO3 2
(d) K
pO2 3
E6.21 0.40 C

E7.3 14.4 kJ mol1

1
E6.22 207 g mol
r (p* p ) E7.4 2.31
1
cp
E6.23 K= 2
.
2r ( p* p E7.5 (a) 5.2 1011
c 1
cp (b) 8.5 102

E6.24 0.11C E7.6 2.42 kJ mol1

E6.25 86.4 kg mol1 E7.7 3.01

E6.26 13.93 kg mol1 E7.8 1.38 1046 .

E7.9 245 kJ mol1

E6.32 (a) 5% tin by mass
(b) No Ag3Sn in the sold
E7.10 K 1
(c) 20% Ag3Sn by mass
E7.11 K G1P 3.5 103
E6.38 0.25
K G6P 2.3 102
CHAPTER 7 K G3P 36
Chemical Equilibrium: The Principles

6
pCO E7.12 (a) 48.3 kJ mol1
E7.1 (a) Q 2

CH3COCOOH (b) 66.1 kJ mol1

2
pO5 2

(b) Q
FeSO4
PbSO4 E7.13 30 kJ mol1

HCl
2

(c) K E7.14 0.7 kJ mol1

pH2

(d) Q
CuCl2
E7.15 6.8 kJ mol1
CuCl
2

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

E7.16 (a) 1110 K (837o C) E7.33 +12.3 kJ mol1

(b) 397 K (124 C)
E7.36 2.7 104 bar

E7.17 1.50 103 K

E7.37 (a) 0.016 mol dm3
E7.18 0.0031 (b) 45%

E7.20 (a) , exergonic E7.39 p1/ 2

(b) +, endergonic
(c) +, endergonic
E7.40 41.0 kJ mol1
(d) , exergonic

1
E7.41 (a) 52.9 kJ mol1
E7.21 (a) 91.14 kJ mol
(b) 52.9 kJ mol1
(b) 594.6 kJ mol1
(c) 66.8 kJ mol1 E7.42 (a)
(d) 99.8 kJ mol1 (1) 9.24
1
(e) 415.80 kJ mol (2) 31.08
(b)
E7.22 (a) 522.1 kJ mol1 , K > 1 (1) 12.9 kJ mol1
(b) +25.78 kJ mol1 , K < 1 (2) 20.9 kJ mol1
(c) 178.6 kJ mol1 , K >1
(c) 161 kJ mol1
(d) 212.55 kJ mol1 , K >1
(d) +248 J K1 mol1
(e) 5798 kJ mol1 , K >1

CHAPTER 8
E7.23 (a) 1.1105 kJ
Chemical Equilibrium: Equilibria In Solution
(b) 1.0 105 kJ
E8.1 (a)
conjugate
E7.24 (a) 2.8 10 kJ
4

(b) 3.1104 kJ H 2SO 4 H 2 O H 3O HSO 4
acid1 base 2 acid 2 base1
E7.26 49.8 kJ mol 1
conjugate

E7.27 817.90 kJ mol 1 (b)

conjugate

E7.28 25.1 kJ mol1 HF H 2 O H 3O F
acid1 base 2 acid 2 base1

E7.29 26 kJ mol1 conjugate

E7.32 16.8 J K1 mol1

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E8.18 (a) 1.6%

(c)
conjugate
(b) 0.33%

C6 H 5 NH 3+ H 2 O H 3O C6 H 5 NH 2
acid1 base 2 acid 2 base1 (c) 2.4%

conjugate
E8.22 2.71

(d)
conjugate E8.23 (a) 6.54

H 2 PO 4 H 2 O H 3 O HPO 24
(b) 2.12
acid1 base 2 acid 2 base1
(c) 1.49
conjugate

(e) E8.25 (a) 1.59 105

conjugate
(b) 0

HCOOH H 2 O H 3 O HCO 2
acid1 base 2 acid 2 base1 (c) 5.01

conjugate
E8.27 (a) 2.9

(f ) (b) 4.6
conjugate
(c) 12.5 cm3 of 0.10 M NaOH aq
NH 2 NH 3 H 2 O H 3 O NH 2 NH 2
acid1 base 2 acid 2 base1 (d) 4.74

conjugate
(e) 25.0 cm3

(f) 8.72
r H O
E8.6
ln10 R E8.28 (a) 4.75

E8.7 57.1 kJ mol1 (b) 5.04

E8.9 8.02 (c) 4.15

E8.13 9.2 E8.29 (a) 24

E8.14 4.77 (b) 35

(c) 11.513. 5
E8.15 none of the Br is protonated
(d) 68
E8.16 (a) 8.32 104
(b) 2.78 (e) 57

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E8.31 (a) 5.1 CHAPTER 9

Chemical Equilibrium: Electrochemistry
(b) pOH 5.0
pH 9.0 E9.1 1.35

(c) 2.7
E9.2 (a) 2.73 g

(b) 2.92 g
E8.32 8.00

E8.34 (a) H3PO4 and NaH2PO4 2

1/3
E9.3
(b) NaH2PO4 and Na2HPO4, or NaHSO3
and Na2SO3 E9.5 B 2.01

E8.35 (a) Ks = [Ag+] [I] E9.6 13.83 mS m2 mol1

(b) Ks = [Hg 2+2 ] [S2 ]

E9.7 7.63 mS m2 mol1
(c) Ks = [Fe3+] [OH]3
E9.10 1.36 105 M
+ 2 2
(d) Ks = [Ag ] [CrO ] 4

E9.11 3.70
E8.36 (a) 1.0 105 mol dm3
E9.12 4.9
(b) 1.2 104 mol dm3
E9.14 440 kJ mol1
(c) 9.3 10 11
mol dm 3

E9.15 28 mV
(d) 6.9 107 mol dm3

E9.16 1.18V
E8.37 (a) 5.5 1010 mol dm3
E9.17
(b) 3.2 103 mol dm3
(a) R: Ag+(aq, bR) + e Ag(s)
(c) 1.6 107 mol dm3 L: Ag+(aq, bL) + e Ag(s)
RL: Ag+(aq, bR) Ag+(aq, bL)
(d) 2.5 107 mol dm3
(b) R: 2 H+(aq) + 2 e H2(g, pR)
L: 2 H+(aq) + 2 e H2(g, pL)
E8.38 161 kJ mol1 RL: H2(g, pL) H2(g, pR)

E8.39 1.25 105 mol dm3 (c) R: MnO2(s) + 4 H+(aq) + 2 e Mn2+(aq)

+ 2 H2O(l)
S
s H O 1 1

L: [Fe(CN)6]3(aq) + e [Fe(CN)6]4(aq)
2R T T
E8.40 (a) e RL: MnO2(s) + 4 H+(aq) + 2 [Fe(CN)6]4
S (aq) Mn2+ (aq) + 2 [Fe(CN)6]3(aq) +
2 H2O(l)
(b) Increases.

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

(d) R: Br2(l) + 2 e 2 Br(aq) (f) 1.67 V

L: Cl2(g) + 2 e 2 Cl (aq)
RL: Br2(l) + 2 Cl(aq) Cl2(g) + 2 Br(aq)
E9.21 (a) 0.08 V
4+
(e) R: Sn (aq) + 2 e Sn (aq) 2+
(b) 0.27
L: 2 Fe3+(aq) + 2 e 2 Fe2+(aq) (c) 1.23 V
RL: Sn4+(aq) + 2 Fe2+(aq) Sn2+(aq) + 2
Fe3+(aq) (d) +0.695 V
(e) +0.54 V
(f) R: MnO2(s) + 4 H+(aq) + 2e Mn2+(aq)
(f) 0.36 V
+ 2 H2O(l)
L: Fe2+(aq) + 2 e Fe(s)
RL: Fe(s) + MnO2(s) + 4 H+(aq) E9.22 (a) 1.23 V
Fe2+(aq) + Mn2+(aq) + 2 H2O(l) (b) 1.11 V

RT bL
E9.18 (a) E E O ln E9.23 (a) partial oxidation of methane occurs
F bR at the cathode.
RT pR (b) 0.09 V
(b) E EO ln
2 F pL
(c) E9.24 (a) 0.94 V

RT [Mn 2+ ][Fe(CN)63 ]2 (b) E 1.51 0.0947 pH

E EO ln
2 F [H ]4 [Fe(CN)64 ]2
E9.25 (a) E decreases,
RT pCl2 [Br ]
2

(d) E E O ln RT [Ag ]L
2 F [Cl ]2
\ E EO ln
F [Ag ]R
(e)
(b) E increases,
RT [Sn ][Fe ]
2 3 2
RT pR
E EO ln E EO ln
2 F [Sn 4 ][Fe2 ]2 2 F pL
(f) (c) E increases,
RT [Mn 2+ ][Fe(CN)36 ]2
RT [Fe2 ][Mn 2 ] E EO ln 4- 2
E EO ln 2F + 4
[H ] [Fe(CN)6 ]
2F [H ]4
(d) E increases,
E9.19 (a) v 2
RT [Br ] pCl2
2
(b) v 2 E EO ln
2 F [Cl ]2

(c) v 4
(d) v 2 (e) E decreases,
(e) v 2 RT [Sn 2 ][Fe3 ]2
E EO ln 4 2 2
(f) v 1 2F [Sn ][Fe ]
(f) E increases,
E9.20 (a) 0
RT [Fe2 ][Mn 2 ]
(b) 0 E EO ln
2F [H ]4
(c) 0.87 V
(d) 0.27 V
(e) 0.62 V

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

E9.26 (a) decreases E E9.36 (a) 0.6111 V

(b) decreases E (b) 0.22 V .
(c) increases E RT aHCO3 aOH
(c) Ecell Ecell
O
ln
(d) increases E F aCO 2
3
(e)
(d) 0.41
(i) decreases E
(e) 10.33
(ii) decreases E
(f) no effect
E9.37 (a) 6.5 109

E9.27 (a) 1.20 V (b) 1.2 107

(b) 1.19 V (c) K e101 7.3 1043
(d) 1.0 1025
E9.28 (a) 1.55 V (e) 8.3 107
(b) chlorinespontaneously oxidizes (f) 1.6 103
water to oxygen under both acidic and
basic conditions
RT a 2 3+
394 kJ mol 1 E9.38 E EO ln Cr
.
E9.29 (a) 6F aCr O2 a14
2 7 H+
(b) 788 kJ mol1 .

(c) +75 kJ mol1 E9.39 (1) 1.80 1010

(d) 291 kJ mol1 (2) 9.04 107

(e) 291 kJ mol1 . E9.40 0.78

(f) +498 kJ mol1
E9.41 0.73 V
1
E9.30 (a) 440 kJ mol
(b) +29.7 kJ mol1 E9.42 (a) 9.19 109 mol dm3
(c) 313 kJ mol1 (b) 8.45 1017

E9.31 (a) 0.324 V CHAPTER 10

(b) +0.45 V Chemical Kinetics: The Rates of Reactions

E9.32 0.37 V E10.1 2.1 mmol dm3

E9.34 (a) 667 kJ mol1 E10.3 0.80 mol dm3 s1 .

(b) 604 kJ mol1
E10.4 mol2 dm6 s1
E9.35 0.22 V
E10.5 mol1 dm3 s1

E10.6 kPa 1/2 s1

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

E10.7 3.7 107 dm3 mol1 s1 E10.34 298.86 K

E10.35 Ea 52 kJ mol1
E10.12 1.12 104 s1 E10.36 35.9 kJ mol1

E10.13 7.7 105 s1 E10.38 121 kJ mol1

E10.14 1.09 103 dm3 mol1 s1 E10.39 21.6 kJ mol1

E10.15 1.12 104 s1 E10.40 47.8 kJ mol1

E10.16 3.19 106 Pa 1 s1 E10.41 (a) 1.62 1020 .

(b) 5.52 1013 .
1
E10.17 (a) 0.014 kPa s
(b) 1.5 103 s E10.42 4 1011 dm3 mol1 s1

E10.18 (a) v kr ICl H2

E10.43 2.1 nm2
(b) 0.16 dm3 mol1 s1
(c) 2.0 106 moldm3 s1
E10.44 126 kJ mol1

E10.23 B0 13 A0 kr t A0 / 1 kr t A0
E10.45 S 0
3
E10.26 1.33 10 s

CHAPTER 11
E10.27 3067 a 100 a.
Accounting for the Rate Laws

E10.28 (a) 0.63 g

E11.1 7.5 105 s1
(b) 0.16 g

E11.2 (a) 1.28 104 mol1 dm3 s1

E10.29 633 s
(b) 4.00 1010 mol1 dm3 s1

E10.30 (a) 0.138 mol dm3

E11.3 39.1 d
(b) 0.095 mol dm3
E11.4 The reaction is first order in H202 and
E10.31 6.8 s in Br , and second order overall

E10.32 (a) 1.86 1023 a . kr,eff A2 B where kr,eff kb ( K

1/ 2
E11.5
(b) 27.1 s .

k1k2 O3
2

E10.33 (a) Ea = 104 kJ mol 1 E11.7 v

k1 O2 k2 O3
(b) A 1.12 1015 mol dm3 s1

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ANSWERS TO END OF CHAPTER EXERCISES

ka kb M
E11.8 kr,eff A where kr,eff
ka M kb E11.23 1.62 mmol dm3 s1

E11.24 7.9 106 dm3 mol1 s1

E11.9
E11.27 AH A H
k
a
initiation
kr,eff A where kr,eff
kA A kM M kb
kA A kM M kb A
bk
B C propagation
AH B A D
kc
propagation
E11.11 1.89 106 Pa1 s1
A B P
kd
termination

E11.12 (a) 6.61106 m3 mol1 s1 CHAPTER 12

1 1
(b) 30 10 m mol s7 3
Quantum Theory
E11.13 (a) 5.2 108 mol m2 s1
E12.1 3.05 1019 J
(b) 1.6 1011 mol
E12.2 8.226 104 cm1
E11.14 (a) 27 h
(b) 2.7 103 h E12.3 8.4 1011 s1
(c) 3.0 10 a 3

E12.5 (a) 1.911018 s1

(b) 1.911018 s1
E11.15 (a) 6.3 109 m2 s1
(b) 1.6 109 m2 s1 E12.6 2.03 103 s

E11.16 8.55 104 a

E12.7 6.90 1029 s1
E11.17 1106 steps
E12.10 1.32 106 m s1
1
E11.18 16.8 kJ mol

22
E12.11 (a) 6.6 1031 m
E11.19 5.6 10
(b) 6.6 1039 m
(c) 99.7 pm
E11.20

kr1 HA B
E12.12 (a) 1.23 nm
(a) Concentration: [A ]
kr 2 BH + kr3 HA
(b) 39 pm
(c) 3.88 pm

kr1kr3 HA B
2

(b)Rate equation: E12.13 3.5 1036 m

kr 2 BH kr3 HA
+

E12.14 (a) 1.10 1027 kg m s1

ka k b (b) 9.5 1024 kg m s1
E11.21 HA H B
ka
(c) 3.311036 kg m s1

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

E12.16 2.2 1024 m s1 E12.37 2.911022 J

E12.17 (a) 6.14 104 N E12.38 1.05 1022 J
(b) 614 pPa
(c) 0.452 h E12.39 0.04 N m1

E12.18 50.6 nm E12.40 (a) 6.89 10 13 s1

(b) 4.35 m
15
E12.19 1.74 10 J
CHAPTER 13
2
d
2
Atomic Structure
E12.20 2
ax4 E
2m dx
E13.1 410.296 nm
4
E12.22 (a) 1.77 10
E13.2 6
(b) 5.92 105
E13.3 (a)
27414 cm1 20572 cm1 6842 cm1
E12.23 0.90 nm
(b) 1.36 1019 J

E12.24 2.11029 m s1
E13.4 27 cm1
E12.25 1.0 1026 m
E13.5 n1 2 and n2 4

E12.26 5.8 105 m s1

E13.8 122.31 eV
23
E12.28 9.84 10 J
E13.9 16 orbitals
E12.29 L / 4 and 3L / 4
E13.10 All lines fit
(a) n2 6
E12.30 (a) 2.17 1020 J
(b) 9.2 m (b) 12372 nm, 7503 nm, 5908 nm,
1/ 2
5129 nm, 3908 nm at n2 15 ,
1 converging to 3282 nm as n2
E12.31 .
L

E13.11 3093.00 nm
E12.32 1.24 m

E13.12 (a) 397.13 nm

E12.35 (a) 4.34 1047 kg m2
(b) 274 19 cm1or 3.40 eV
(b) 1.55 mm

E13.13 (a) RLi 2+ 109 740 cm1

11 1
E12.36 8.79 10 s

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(b) 137 175 cm1 , 185 186 cm1 ,

(c) 987660 cm1 or 122.45 eV
E13.14 r 0.602 a 0 E13.30
(a) Forbidden
E13.16 (b) Allowed
(c) Allowed
E13.17 (a) 1.3 105 (d) Forbidden
(e) Allowed
(b) 5.1105
(f) Forbidden

E13.19 Sin goes to zero at = 0 and 180

E13.32
cos goes to zero at 90 and 270
(a) Allowed
(b) Forbidden
E13.20 (a) ang. mom. 0
(c) Allowed
(b) ang. mom. 0
(c) ang. mom. 6 CHAPTER 14
The Chemical Bond
(d) ang. mom. 2
(e) ang. mom. 2 E14.3

E13.21 (a) g 1
1 (-bond) 2p A (1) 2p B (2) 2p A (2) 2p B (1)
z z z z

(b) g 9
2 (-bond) 2p A (1) 2p B (2) 2p A (2) 2p B (1)
(c) g 49 x x x x

3 (-bond) 2p A (1) 2p B (2) 2p A (2) 2p B (1)

y y y y
E13.22 2(2l + 1)

E14.4 1.87 106 J mol1

E13.23 I1 Eea

E14.5 1 h1 (1) 1sH1 (2) h1 (2) 1sH1 (1)

E13.24 14.0 eV
2 h2 (1) 1sH2 (2) h2 (2) 1sH2 (1)
E13.26 3
F2 3 h3 (1) 1sH3 (2) h3 (2) 1sH3 (1)
4 h4 (1) 1sH4 (2) h4 (2) 1sH4 (1)
E13.27 2, 1, and 0
E14.8 210 times.
E13.28 (a) 1 level
(b) 3 levels E14.10 45
(c) 1 level
(d) 3 levels E14.12

E13.29 Ti2+: [Ar]3d2 (a) Li 2 1g 2 b 1

(a) 3F (b) Be2 1 g 21u 2 b0
(b) 5 (c) C2 1 g 1u 1u
2 2 4
b2

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ANSWERS TO END OF CHAPTER EXERCISES

E14.26 O+2 O2 O2 O22

E14.13 E14.27 O2+ > O2 > O2 > O22

(a) H2 1g 21u1 b 12
E14.30 (a) nonpolar
(b) N2 1g 21u 21u 4 2g 2 b3 (b) polarized
(c) O2 1g 21u 2 2g 21u 41g 2 b2
E14.34 32 molecular oribtals

E14.14 E14.35
(a) / hc ~ 40000 cm1 5.0 eV
(a) CO 1 2* 1 3
2 2 4 2
b3
(b) NO 1 2* 1 3 2*
2 2 4 2 1
b 52 (b) Edeloc / hc 60720 cm1 7.35 eV
(c) CN 12 2*214 32 b3
CHAPTER 15
E14.15 C 2 Molecular Interactions

E14.16 C2 and CN are stabilized by anion E15.1 1.9 D

formation. NO, O2, and F2 are stabilized by
6.3 1030 C m
cation formation.

E15.2 nonpolar
E14.17 C 2
E15.3 (a) 0.7 D
E14.14 XeF+ will have a shorter bond length
than XeF (b) 0.4 D
(c) 0
E14.19 (a) g
(b) inapplicable E15.4 1.26 D
(c) g
(d) u E15.5 (a) 0.8 D
(b) 0.4 D
E14.21 (a) g (c) 0
u
g E15.6 (a) 1.414 D
u (b) 2.45 D
(c) 1.06 D
(b) If v is even, v is g.
(d) 1.70 D
If v is odd, v is u.

E15.8 3.50 D
E14.23 N 2

E15.10 (a) 476 kJ mol1

E14.24 F F2 F
2 2
(b) 87.4 kJ mol1

E14.25 F2 F2 F2 E15.12 (a) 3.7 kJ mol1

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
ANSWERS TO END OF CHAPTER EXERCISES

(b) 0.365 J mol1 (b) 0.14 kPa

(c) Yes.
E16.16 5.8 cm
E15.14 196 pm
E16.17 45 mN m1
E15.15 2.32 1024 J
E16.18 97 mmol m2

E15.16 1.8 1027 J 11103 J mol1 CHAPTER 17

Metallic, Ionic, and Covalent Solids
3 1
E15.17 4.2 10 J mol
E17.1 (a) n-type
(b) p-type
E15.18 42 kJ mol1

E17.2 metallic condusctor

E15.20 R 461.2 pm

CHAPTER 16 E17.6 3500. kJ mol1

Materials: Macromolecules and Aggregates
E17.7 2149.8 kJ mol1

E16.1 (1) 95 kg mol1

Q Nze
(2) 97 kg mol1 E17.8
48 0 d
E16.2 (a) 18 kg mol1
(b) 20 kg mol1 E17.9 1.06

E16.3 1.27
E17.10 6.0 K
E16.4 244
E17.16 d111 330 pm
E16.5 3.1103 kg mol1 d211 234 pm
d100 572 pm
E16.6 (a) 880 nm
(b) 31.1 nm
E17.17 d123 135 pm
d236 70.1 pm
E16.8 1.3 104

E16.11 5.0 103 E17.18 66.1 pm

1 1 8 K Stotal
S and
E17.19 bbc unit cell
4K
E16.13
1 1 8 K Stotal E17.20 (b) 8.97 g cm3
S2 Stotal
1

2 4K

E17.22 0.9069

E16.15 (a) 1.4 kPa

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ANSWERS TO END OF CHAPTER EXERCISES

E17.24 0.740 g cm3

s0 e Ed / RT
E18.8
2 mkT
1/ 2
E17.25 (a) 8 A
(b) 6
(c) 520 nm E18.10 25 kJ mol1
(d) 600 nm
1
2

E18.12 p
K 1
E17.26 (a) 12
(b) 6 ( Kp)1/3
E18.13
(c) 424 nm 1 ( Kp)1/3
(d) 600 nm
E18.16 45 s
E17.27 (a) less dense
(b) 92% E18.17 (a) 611 kJ mol1
(b) 9.3 1012 s1
E17.28 V 3.96 1028 m3
d 2.41106 g m3 E18.18 (a) 2.7 1091 a

(b) 0.17 ms
E17.29 (a) N 4
(b) 4.01 g cm3
E18.19 0.45

E17.30 (a) 220 pm E18.22 155 mV

(b) 110 pm
E18.23 1.68 mA cm2
CHAPTER 18
2
Solid Surfaces E18.24 (a) 0.31mA cm
2
E18.2 0.088 bar (b) 5.41mA cm
2
(c) 1.43 1039 A cm
1
E18.3 2.110 s 5

E18.25 (a) 4.9 1015 s1

E18.4 1.15
(b) 1.6 1016 s1

1
(c) 3.1107 s1
E18.5 (a) 1. 1 10 s 10

(b) 0.24 CHAPTER 19

Spectroscopy: Molecular rotations and
vibrations
E18.6 49 m2
E19.1 (a) 6.78 1014 s-1 = 6.78 1014 Hz
E18.7 (a) 0.060 kPa
(b) 4.9 kPa (b) 2.26 104 cm-1

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E19.16 20603 cm- 1

E19.2 (a) 2.94 10 cm
-3 -1

(b) 3.40 m E19.17 116.2 pm

E19.3 4 1033
E19.18 (a) 162.2 pm
(b) 194 GHz
E19.4 (a) 4.6011048 kg m2
(b) 9.196 1048 kg m2 E19.19 (a) B 0.202852 cm1
(c) 7.15 1046 kg m2 (b) D 6.2 108 cm1
(d) 7.156.67 1046 kg m2
E19.20 (a) 116.28 pm
(b) 155.97 pm
E19.5 (a) 1.824 1012 Hz
(b) 9.126 1011 Hz
E19.21 (a) 0.999 999 9029 660 nm
(c) 1.17 1010 Hz
(b) 6.36 107 m s1
(d) 1.17 10 Hz
10

E19.22 (a) 2.397 107 m s1

E19.6 (a) I 4mB R 2
(b) 8.4 105 K
(b) 2.663 10 Hz 9

E19.23 (a) 53 ps
E19.8 (a) 5.152 109 Hz (b) 5.3 ps
(b) Could not be used.
(c) 1.6 102 ps

E19.9 (a) Yes

(b) Yes E19.24 (a) 53 cm1 .
(c) Yes (b) 0.27 cm1 .
(d) Yes
(e) No E19.25 (a) 4.49 1013 Hz
(b) 4.39 1013 Hz
E19.10 All will show

E19.26 329 N m1
E19.11 289

E19.29 2700.6 cm1

E19.12 17

E19.13 (a) 636 GHz, 1272 GHz, 1908 GHz (b) HCl, (c) CO2 , (d) H 2 O,
E19.30
(e) CH3 CH3 , (f) CH4 , and (g) CH3 C1
(b) 21.21 cm1
21.21 cm1 , 42.42 cm1 , 63.63 cm1,
E19.31 (a) 3
(b) 4
E19.14 232.1 pm
(c) 48
(d) 54
E19.15 Lower

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CHAPTER 20 E20.25 4 1010 s or 0.4ns

Electronic Transitions and Photochemistry
CHAPTER 21
E20.1 (a) 1.48104 dm3 mol1 cm1 Spectroscopy: Magnetic Resonance
(b) 0.938%
E21.1 4.64 1024 J
E20.2 Absorbance: 0.658
Longer Cell: 1.3 E21.2 1.300 1026 J mI
Transmittance: 0.048

E21.3 (a) T 1Hz

E20.3 33 g dm3
(b) As kg 1

E20.4 cA 0.56 mol dm3

E21.4 2.263
cB 0.16 mol dm3
E21.5 (a) 8.96 104
E20.5 Only two solutes in equilibrium with (b) 2.69 103
each other are present.

v 9.248 GHz
E20.6 Lengthen. E21.6
0.0324 m
Blue.

E21.7 (a) 2.9 105

E20.11 16.01019 kJ
(b) 7.3 106

E20.12 (a) 2.11019 J

E21.8 300.5 MHz
(b) 6.8 105 m s-1

E21.9 43.69 MHz

E20.13 10.20eV, 12.98 eV, and 15.99 eV

E21.10 18.79 T
E20.14 2.0

E21.11 3.17 kHz

E20.15 2.80

E21.12 (a) 9.1 T

E20.16 Molecules destroyed: 1.47 1019 s-1
Chemical destroyed: 2.4 10-5 mol s-1 (b) 38 T
E20.17 Triplet state

E21.13 (a) 2.4 kHz

E20.19 33 1018
(b) 6.0 kHz
1 1
E20.21 1.27 10 mol dm s
10 3

E21.14 1: 7 : 21: 35 : 35 : 21: 7 :1

E20.23 0.43
E21.15 (a) quintet1: 2 : 3: 2 :1
E20.24 R0 352 nm (b) septet1: 3: 6 : 7 : 6 : 3:1

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(f
(e))
conjugate
conjugate
Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
NH 2 NH3 H
HCOOH HO2 O HHO3 O NH
HCO 22 NH 2
2 3
acid11 base
acid base acid base ANSWERS TO END OF CHAPTER EXERCISES
2 2 acid 2 2 base1 1

conjugate
conjugate
E21.22 2.6 103 s1 E22.12 (a) 3.2 104
(b) 6.2 1027
[E]0 v
E21.23 [I]0 KI
v E22.13 (a) 24.816
(b) 24.480
E21.24 20022
E22.14 T 38.96 K
E21.25 20025
E22.15 (a) 19.5
E21.27 (a) 331.9 mT (b) 265
(b) 1.201T
E22.17 1 5e / kT 3e3 / kT

CHAPTER 22 E22.20 11.5 J K 1 mol1

Statistical Thermodynamics

E22.21 9.57 1015 J K 1

ES22.1 0.37

E22.22 191.4 J K1 mol1

E22.2 (a) 0.9999895
(b) 0.9998955 O O
E22.23 (a) S (Xe) > S (Ne)
O O
(b) S (D2 O) > S (H 2 O) .
E22.3 0.99849
O O
(c) S (Graphite) > S (Diamond)
E22.4 1.753
1 1
E22.24 40 kJ K mol
E22.5 2.27

2 / kT
E22.25 56.9 kJ mol1
E22.6 (a) 1 6e 3e5 / kT
(b) q 1 O
(qNH / NA )2
E22.26 K e E / RT
3,m
(c) 10
(qNO ,m / N A )( qHO ,m / N A )3
2 2

E22.7 (a) 1.29

(b) 7.82 E22.27 1.37 1025

E22.8 (a) 5 E22.28 1.93 1011

(b) 6.731

E22.9 T 17762 K

E22.10 (a) 1.401

(b) 3.147

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