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

ANSWERS TO END OF CHAPTER EXERCISES

INTRODUCTION E0.18 459.67°F

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  345.8F
E0.4 36 J

E0.21 671.67R
E0.5 1.4 102 kJ

E0.22 3.3 1022 glucose molecules

E0.6 2.3 kJ

E0.23 3.711024 octane molecules

E0.7 2.483 1024 J

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

E0.9 (a) 1.602 1019 J E0.25 0.97

1
(b) 96.47 kJ mol
E0.26   M / Vm

E0.10 (a) 2.4 1019 J

E0.27 73.0 mmol dm3
(b) 1.4 102 kJ mol1
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 102 mol dm3
(b) 0.962 atm (b)
(c) 0.222 atm (i) Water: 9.12 102 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 s1
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 μm
E1.10 (a) 3.6 m3 E1.25 (a) 5.3  1010 s1
(b) 178 m3 (b) 5.3  109 s1
(c) 5.3  104 s1
E1.11 0.50 m3
E1.26 (a) 6.5  1033 s1
E1.13 3.4 108 dm3 (b) 6.5  1031 s1
(c) 6.5  1021 s1
2
E1.14 6.7 10 atm .
E1.27 4.5 108 s1
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 mol1 E1.29 Independent of temperature

E1.18 16.4 g mol1 . 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 mol1

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

E1.33 (a) 4.60 102 dm3 mol1

E2.14 (a) 9.2 102 kJ
(b) 0.66
(b) 6.1102 s .

E1.34 (a) 1.26 dm6 atm mol2

E2.15 773 J
(b) 3.46  102 dm3 mol1
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 mol1
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 K1 mol1

E2.8 1.0 102 J E2.26 (a) 641 J mol1

(b) 458 J mol1
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 mol1
E3.1 6.91 mJ mol1
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 mol1 E3.21 (a) 2.80 MJ mol1

(b) 2.80 MJ mol1
E3.5 (a) 80.0 kJ (c) 1.27 MJ mol1
(b) 5.20 kJ
(c) 74.8 kJ E3.22 (a) 1333 kJ mol1 .
(b) 1331 kJ mol1
E3.7 +239 kJ
(c) 815 kJ mol1

E3.8 4.96 kJ mol1

E3.24 112.27 kJ mol1
E3.9 2.48 kJ mol1
E3.25 383 kJ mol1
E3.10 163 kJ

E3.11 (a) +354.8 kJ mol1 E3.26 1.9 kJ mol1 .

(b) +352.3 kJ mol1
E3.27 +30.6 kJ mol1
E3.12 (a) 388 kJ mol1
(b) smaller. E3.28 (a) 37C
(b) 4.1 kg
1
E3.13 (a) 16 kJ mol
(b) 3028 kJ mol1 E3.29 (a) 2205 kJ mol1
(b) 2200 kJ mol1
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 mol1 (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 mol1

E3.31 (a) 57.20 kJ mol1

E3.17 85 kJ mol1 (b) 28.6 kJ mol1

(c) 138.2 kJ mol1
E3.18 432 kJ mol1 (d) 32.88 kJ mol1
(e) 55.84 kJ mol1
E3.19 225 kJ mol1
E3.32 11.3 kJ mol1 .
E3.20 (a) 4.22 kJ K1
(b) 0.769 K E3.33 56.98 kJ mol1

E3.34 40.88 kJ mol1

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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 K1 mol1

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

E4.7 33 J K 1
E4.24 5.03 kJ K1

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 K1

E4.26 (a) 0.75 J K1

E4.10 8.64% high
(b) 0.15 J K1

E4.11 –7.9 J K –1 mol1

E4.27 32.99 kJ

E4.12 0.6300 Ti
E4.28 (a) 93 kJ mol1
(b) Yes, ΔG is negative.
E4.14 4.0 104 J K1 mol1
(c) 0.30 kJ K1 mol1

E4.15 5.11 J K 1 E4.29 0.41 g

E4.16 0.95 J K 1 mol1 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 mol1
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 m3
(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 mol1
(b) 1.50 J mol1 E6.1 886.8 cm3

E5.4 +14 kJ mol1 E6.2 96.9 cm3

E5.5 (a) 2.7 kJ mol1 E6.3 1.8 kJ mol1

(b) 2.0 kJ mol1
E6.4 32.631 J mol1

E5.6 4.2 kJ mol1

E6.5 (a) 1.31 kJ mol1
(b) 4.38 J K1 mol1
E5.7 710 K
(c) Yes.

E5.8 3.5 kJ mol1

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 K1 E6.10 4.8 103

(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 dm3
(b) 17.0 mmol dm3
E5.13 8.330

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E6.14 34.5 mmol dm3 pCOCl pCl

E7.2 (a) K 
pCO pCl2
E6.18 5.6 kJ mol1 2
pSO
(b) K  2
3

pSO 2
pO2
E6.19 59.1 g mol1 2
pHBr
(c) K 
pH2 pBr2
E6.20 –0.068º C pO3 2
(d) K 
pO2 3
E6.21 –0.40º C

E7.3 14.4 kJ mol1

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 –0.11C E7.6 2.42 kJ mol1

E6.25 86.4 kg mol1 E7.7 3.01

E6.26 13.93 kg mol1 E7.8 1.38 1046 .

E7.9 245 kJ mol1

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 mol1
E7.1 (a) Q  2

CH3COCOOH (b) 66.1 kJ mol1

2
pO5 2

(b) Q 
 FeSO4 
 PbSO4  E7.13 30 kJ mol1

 HCl
2

(c) K  E7.14 0.7 kJ mol1

pH2

(d) Q 
CuCl2 
E7.15 6.8 kJ mol1
CuCl
2

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 Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
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E7.16 (a) 1110 K (837o C) E7.33 +12.3 kJ mol1

(b) 397 K (124 C)
E7.36 2.7 104 bar

E7.17 1.50 103 K

E7.37 (a) 0.016 mol dm–3
E7.18 0.0031 (b) 45%

E7.20 (a) –, exergonic E7.39   p1/ 2

(b) +, endergonic
(c) +, endergonic
E7.40 41.0 kJ mol1
(d) –, exergonic

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

CHAPTER 8
E7.23 (a) 1.1105 kJ
Chemical Equilibrium: Equilibria In Solution
(b) 1.0 105 kJ
E8.1 (a)
conjugate
E7.24 (a) 2.8 10 kJ
4

 
(b) 3.1104 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 mol1 HF  H 2 O H 3O   F
acid1 base 2 acid 2 base1
 
E7.29 26 kJ mol1 conjugate

E7.32 16.8 J K1 mol1

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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 × 105

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 mol1 (b) 5.04

E8.9 8.02 (c) 4.15

E8.13 9.2 E8.29 (a) 2–4

E8.14 4.77 (b) 3–5

(c) 11.5–13. 5
E8.15 none of the Br – is protonated
(d) 6–8
E8.16 (a) 8.32 104
(b) 2.78 (e) 5–7

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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 mol1

(b) Ks = [Hg 2+2 ] [S2 ]

E9.7 7.63 mS m2 mol1
(c) Ks = [Fe3+] [OH–]3
E9.10 1.36 105 M
+ 2 2
(d) Ks = [Ag ] [CrO ] 4

E9.11 3.70
E8.36 (a) 1.0  10–5 mol dm–3
E9.12 4.9
(b) 1.2  10–4 mol dm–3
E9.14 440 kJ mol1
(c) 9.3  10 –11
mol dm –3

E9.15 28 mV
(d) 6.9  10–7 mol dm–3

E9.16 1.18V
E8.37 (a) 5.5  10–10 mol dm–3
E9.17
(b) 3.2 103 mol dm3
(a) R: Ag+(aq, bR) + e– → Ag(s)
(c) 1.6  10–7 mol dm–3 L: Ag+(aq, bL) + e– → Ag(s)
R–L: Ag+(aq, bR) → Ag+(aq, bL)
(d) 2.5 107 mol dm3
(b) R: 2 H+(aq) + 2 e– → H2(g, pR)
L: 2 H+(aq) + 2 e– → H2(g, pL)
E8.38 161 kJ mol1 R–L: H2(g, pL) → H2(g, pR)

E8.39 1.25 105 mol dm3 (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 R–L: 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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(d) R: Br2(l) + 2 e– → 2 Br–(aq) (f) 1.67 V

L: Cl2(g) + 2 e– → 2 Cl– (aq)
R–L: 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
R–L: 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)
R–L: 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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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 107
(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 mol1 .

(c) +75 kJ mol1 E9.39 (1) 1.80 1010

(d) 291 kJ mol1 (2) 9.04 107

(e) 291 kJ mol1 . E9.40 0.78

(f) +498 kJ mol1
E9.41 0.73 V
1
E9.30 (a) 440 kJ mol
(b) +29.7 kJ mol1 E9.42 (a) 9.19 109 mol dm3
(c) 313 kJ mol1 (b) 8.45 1017

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 dm3

E9.34 (a) 667 kJ mol1 E10.3 0.80 mol dm3 s1 .

(b) 604 kJ mol1
E10.4 mol2 dm6 s1
E9.35 0.22 V
E10.5 mol1 dm3 s1

E10.6 kPa 1/2 s1

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E10.7 3.7 107 dm3 mol1 s1 E10.34 298.86 K

E10.35 Ea  52 kJ mol–1
E10.12 1.12 104 s1 E10.36 35.9 kJ mol1

E10.13 7.7 105 s1 E10.38 121 kJ mol1

E10.14 1.09 103 dm3 mol1 s1 E10.39 21.6 kJ mol1

E10.15 1.12 104 s1 E10.40 47.8 kJ mol1

E10.16 3.19 106 Pa 1 s1 E10.41 (a) 1.62 1020 .

(b) 5.52 1013 .
1
E10.17 (a) 0.014 kPa s
(b) 1.5 103 s E10.42 4 1011 dm3 mol1 s1

E10.18 (a) v  kr  ICl  H2 

E10.43 2.1 nm2
(b) 0.16 dm3 mol1 s1
(c) 2.0 106 moldm3 s1
E10.44 126 kJ mol1

E10.23  B0  13 A0 kr t A0 / 1  kr t A0 

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 μg

E11.1 7.5 105 s1
(b) 0.16 μg

E11.2 (a) 1.28 104 mol1 dm3 s1

E10.29 633 s
(b) 4.00 1010 mol1 dm3 s1

E10.30 (a) 0.138 mol dm3

E11.3 39.1 d
(b) 0.095 mol dm3
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 dm3 s1

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ka kb  M 
E11.8 kr,eff  A  where kr,eff 
ka   M   kb E11.23 1.62 mmol dm3 s1

E11.24 7.9 106 dm3 mol1 s1

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 106 Pa1 s1
A   B   P
kd
termination

E11.12 (a) 6.61106 m3 mol1 s1 CHAPTER 12

1 1
(b) 30 10 m mol s7 3
Quantum Theory
E11.13 (a) 5.2 108 mol m2 s1
E12.1 3.05 1019 J
(b) 1.6 1011 mol
E12.2 8.226 104 cm1
E11.14 (a) 27 h
(b) 2.7 103 h E12.3 8.4 1011 s1
(c) 3.0 10 a 3

E12.5 (a) 1.911018 s1

(b) 1.911018 s1
E11.15 (a) 6.3 109 m2 s1
(b) 1.6 109 m2 s1 E12.6 2.03 103 s

E11.16 8.55 104 a

E12.7 6.90 1029 s1
E11.17 1106 steps
E12.10 1.32 106 m s1
1
E11.18 16.8 kJ mol

22
E12.11 (a) 6.6 1031 m
E11.19 5.6 ×10
(b) 6.6 1039 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 1036 m

kr 2  BH   kr3  HA 
+

E12.14 (a) 1.10 1027 kg m s1

ka k b (b) 9.5 1024 kg m s1
E11.21  HA H   B
ka
(c) 3.311036 kg m s1

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E12.16 2.2 1024 m s1 E12.37 2.911022 J

E12.17 (a) 6.14 104 N E12.38 1.05 1022 J
(b) 614 pPa
(c) 0.452 h E12.39 0.04 N m1

E12.18 50.6 nm E12.40 (a) 6.89 10 13 s1

(b) 4.35 μm
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 105
E13.3 (a)
27414 cm1  20572 cm1  6842 cm1
E12.23 0.90 nm
(b) 1.36 1019 J

E12.24 2.11029 m s1

E13.4 27 cm1
E12.25 1.0 1026 m
E13.5 n1  2 and n2  4

E12.26 5.8 105 m s1

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  1020 J
(b) 9.2 μm (b) 12372 nm, 7503 nm, 5908 nm,
1/ 2
5129 nm, ¼ 3908 nm  at n2  15 ,
1 converging to 3282 nm as n2  
E12.31     .
L

E13.11 3093.00 nm
E12.32 1.24 μm

E13.12 (a) 397.13 nm

E12.35 (a) 4.34 1047 kg m2
(b) 274 19 cm1or 3.40 eV
(b) 1.55 mm

E13.13 (a) RLi 2+  109 740 cm1

11 1
E12.36 8.79 10 s

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(b) 137 175 cm1 , 185 186 cm1 ,

(c) 987660 cm1 or 122.45 eV
E13.14 r  0.602 a 0 E13.30
(a) Forbidden
E13.16 ½ (b) Allowed
(c) Allowed
E13.17 (a) 1.3 105 (d) Forbidden
(e) Allowed
(b) 5.1105
(f) Forbidden

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

E13.32
cos θ 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 (σ-bond)   2p A (1)  2p B (2)  2p A (2)  2p B (1)
z z z z

(b) g  9
 2 (π-bond)   2p A (1)  2p B (2)  2p A (2)  2p B (1)
(c) g  49 x x x x

 3 (π-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 mol–1

E13.23 I1  Eea

E14.5  σ1  h1 (1) 1sH1 (2)  h1 (2) 1sH1 (1)

E13.24 14.0 eV
 σ2  h2 (1) 1sH2 (2)  h2 (2) 1sH2 (1)
E13.26 3
F2  σ3  h3 (1) 1sH3 (2)  h3 (2) 1sH3 (1)
 σ4  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 1σg 2 b 1

(a) 3F (b) Be2 1 σg 21σu 2 b0
(b) 5 (c) C2 1 σg 1σu 1πu
2 2 4
b2

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E14.26 O+2  O2  O2  O22

E14.13 E14.27 O2+ > O2 > O2 > O22

(a) H2 1σg 21σu1 b  12

E14.30 (a) nonpolar
(b) N2 1σg 21σu 21πu 4 2σg 2 b3 (b) polarized
(c) O2 1σg 21σu 2 2σg 21πu 41πg 2 b2
E14.34 32 molecular oribtals

E14.14 E14.35
(a)  / hc ~  40000 cm1  5.0 eV 
(a) CO 1σ 2σ* 1π 3σ
2 2 4 2
b3
(b) NO 1σ 2σ* 1π 3σ 2π*
2 2 4 2 1
b  52 (b) Edeloc / hc  60720 cm1  7.35 eV 
(c) CN 1σ2 2σ*21π4 3σ2 b3
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 1030 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, ψv is g.
(d) 1.70 D
If v is odd, ψv is u.

E15.8 3.50 D
E14.23 N 2

E15.10 (a) 476 kJ mol1

 
E14.24 F  F2  F
2 2
(b) 87.4 kJ mol1

E14.25 F2  F2  F2 E15.12 (a) 3.7 kJ mol1

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(b) 0.365 J mol1 (b) 0.14 kPa

(c) Yes.
E16.16 5.8 cm
E15.14 196 pm
E16.17 45 mN m1
E15.15 2.32 1024 J
E16.18 97 mmol m2

E15.16 1.8 1027 J  11103 J mol1 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 mol1

E17.2 metallic condusctor

E15.20 R  461.2 pm

CHAPTER 16 E17.6 3500. kJ mol1

Materials: Macromolecules and Aggregates
E17.7 2149.8 kJ mol1

E16.1 (1) 95 kg mol1

Q Nze 
(2) 97 kg mol1 E17.8
48  0 d
E16.2 (a) 18 kg mol1
(b) 20 kg mol1 E17.9 1.06

E16.3 1.27
E17.10 6.0 K
E16.4 244
E17.16 d111  330 pm
E16.5 3.1103 kg mol1 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 103 E17.18 66.1 pm

1  1  8 K Stotal
S  and
E17.19 bbc unit cell
4K
E16.13
 1  1  8 K Stotal  E17.20 (b) 8.97 g cm3
S2   Stotal  
1

2 4K
 
E17.22 0.9069

E16.15 (a) 1.4 kPa

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E17.24 0.740 g cm3

s0 e Ed / RT
E18.8
 2 mkT 
1/ 2
E17.25 (a) 8 A
(b) 6
(c) 520 nm E18.10 25 kJ mol1
(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 mol1
(b) 9.3 1012 s1
E17.28 V  3.96 1028 m3
d  2.41106 g m3 E18.18 (a) 2.7 1091 a

(b) 0.17 ms
E17.29 (a) N  4
(b) 4.01 g cm3
E18.19 0.45

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

(b) 110 pm
E18.23 1.68 mA cm2
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 2.110 s 5

E18.25 (a) 4.9 1015 s1

E18.4 1.15
(b) 1.6 1016 s1

1
(c) 3.1107 s1
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) 4.6011048 kg m2
(b) 9.196 1048 kg m2 E19.19 (a) B  0.202852 cm1
(c) 7.15 1046 kg m2 (b) D  6.2 108 cm1
(d) 7.156.67  10–46 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 s1
(d) 1.17 10 Hz
10

E19.22 (a) 2.397 107 m s1

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 cm1 .
(c) Yes (b)   0.27 cm1 .
(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 m1

E19.11 289

E19.29 2700.6 cm1

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 cm1
21.21 cm1 , 42.42 cm1 , 63.63 cm1,
E19.31 (a) 3
(b) 4
E19.14 232.1 pm
(c) 48
(d) 54
E19.15 Lower

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

CHAPTER 20 E20.25 4 1010 s or 0.4ns

Electronic Transitions and Photochemistry
CHAPTER 21
E20.1 (a) 1.48×104 dm3 mol1 cm1 Spectroscopy: Magnetic Resonance
(b) 0.938%
E21.1 4.64 1024 J
E20.2 Absorbance: 0.658
Longer Cell: 1.3 E21.2 1.300 1026 J  mI
Transmittance: 0.048

E21.3 (a) T 1Hz

E20.3 33 μg dm3
(b) As kg –1

E20.4 cA  0.56 mol dm3

E21.4 2.263
cB  0.16 mol dm3
E21.5 (a) 8.96 104
E20.5 Only two solutes in equilibrium with (b) 2.69 103
each other are present.

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

E21.7 (a) 2.9 105

E20.11 16.0´10–19 kJ
(b) 7.3 106

E20.12 (a) 2.1´10–19 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 µT

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

E21.13 (a) 2.4 kHz

E20.19 33 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  352 nm (b) septet1: 3: 6 : 7 : 6 : 3:1

Higher Education
© Oxford University Press, 2009. All rights reserved.
(f
(e))
conjugate
conjugate
    Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition
NH 2 NH3 H
HCOOH  HO2 O HHO3 O    NH
 HCO 22 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 s1 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 20022
E22.14 T  38.96 K
E21.25 20025
E22.15 (a) 19.5
E21.27 (a) 331.9 mT (b) 265
(b) 1.201T
E22.17 1  5e / kT  3e3 / kT

CHAPTER 22 E22.20 11.5 J K 1 mol1

Statistical Thermodynamics

E22.21 9.57 1015 J K 1

ES22.1 0.37

E22.22 191.4 J K1 mol1

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 mol1
E22.6 (a) 1  6e  3e5 / 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 1025

E22.8 (a) 5 E22.28 1.93 1011

(b) 6.731

E22.9 T  17762 K

E22.10 (a) 1.401

(b) 3.147

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