Gases have unique properties. Some important properties of gases are listed below.
The properties of gases
Transcript of The properties of gases
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Atkins & de Paula: Elements of Physical Chemistry, Seventh Edition
ANSWERS TO END OF CHAPTER EXERCISES
1
Focus 1
The properties of gases
Answers to exercises
Topic 1A The perfect gas
1A.1 (a) 810 Torr
(b) 0.962 atm
(c) 0.222 atm
(d) 1.03 ร 105 Pa
1A.2 92 kPa
1A.3 2.25 kPa
1A.4 4.33 mmol
1A.5 660 bar
1A.6 10.0 atm
1A.7 418 kPa
1A.8 173 kPa
1A.9 โ243.6 โ
1A.10 394 K
1A.11 (a) 3.6 m3
(b) 178 m3
1A.12 3.4 ร 105 m3
1A.13 benzene 0.355๏ผ toluene 0.645
1A.14 (a) 1.32 ร 10โ3m3
(b) 61.2 ร 103 Pa
Topic 1B The kinetic model of gases
1B.1 (a) 493 m sโ1
(b) 615 m sโ1
1B.2 (a) ๐ฃmean(79 K) = 647 m sโ1
๐ฃmean(315 K) = 1.29 km sโ1
๐ฃmean(1500 K) = 2.82 km sโ1
(b) ๐ฃmean(79 K) = 323 m sโ1
๐ฃmean(315 K) = 645 m sโ1
๐ฃmean(1500 K) = 1.41 km sโ1
1B.3 3.72
1B.4 ๐N2 0.80 g
๐He 0.30 g
1B.5 65 mPa
1B.6 ๐ = 0.97 ฮผm
๐ = 120 ร 103
1B.7 (a) 7.0 ร 1010
(b) 7.0 ร 108
(c) 7.0 ร 104
1B.9 (a) 6.8 nm
(b) 68 nm
(c) 6.8 mm
Topic 1C Real gases
1C.1 ๐c = 0.242
1C.2 CH4 ๐c = 0.288
C2H6 ๐c = 0.274
C3H8 ๐c = 0.276
1C.3 2.15 MPa
1C.4 โ3.37 ร 10โ5 m3molโ1
1C.5 โ3.49 ร 10โ8 Paโ1
1C.6 (a) (i) 101 kPa
(ii) 83.1 MPa
(b) (i) 101 kPa
(ii) 206 MPa
1C.7 โ0.608 MPa
1C.8 ๐ = 4.6 ร 10โ5 m3 molโ1
๐ = 0.66
1C.9 1842 K
Answers to problems
1.1 0.50 m3
1.2 28.82 g molโ1
130 kg
1.3 6.8 kPa
1.4 713 Torr
1.5 ๐ฅN2= 0.7809
๐ฅO2= 0.2094
๐ฅAr = 0.0098
1.6 132 g molโ1
1.7 16.4 g molโ1
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Atkins & de Paula: Elements of Physical Chemistry, Seventh Edition
ANSWERS TO END OF CHAPTER EXERCISES
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1.8 (a) ๐H2= 200 kPa
๐N2= 100 kPa
(b) 300 kPa
1.9 (a) 72 K
(b) 943 m sโ1
1.10 1.0 ร 1013 sโ1
1.11 0.57 dm3 molโ1
1.12 ๐ = 0.656 Pa m6molโ2
๐ = 5.54 ร 10โ5 m3 molโ1
1.13 ๐ = 0.321 Pa m6 molโ2
๐ = 6.50 ร 10โ5 m3molโ1
๐ = 1.86 ร 10โ10 m
1.14 ๐ = ๐. ๐๐๐ ๐๐ ๐ฆ๐ ๐ฆ๐จ๐ฅโ๐
๐ = ๐. ๐ ร ๐๐โ๐๐ฆ๐ ๐ฆ๐จ๐ฅโ๐
Answers to projects
1.1 (d) ๐ โ 10โ2
1.2 (a) 720 Mbar
(d) 0.21 Mbar
(e) 0.029 Mbar
1.3 (c) 1030 K
1.4 (c) ๐c = 101.3 bar
๐c = 0.1327 dm3 molโ1
๐c = 431.3 K
Focus 2
The First Law of thermodynamics
Answers to exercises
Topic 2A Work
2A.1 (a) ๐คexpansion = โ0.10 J
(b) ๐คexpansion = โ100 J
(a) ๐คcompression = +0.10 J
(b) ๐คcompression = +100 J
2A.2 โ5.5 kJ
2A.3 (a) โ99 J
(b) โ167 J
2A.4 +123 J
2A.5 +29.9 J
2A.6 โ1.25 kJ
2A.7 (a) 0
(b) โ783 J
2A.8 โ100 J
Topic 2B Heat
2B.1 23.7 J Kโ1
2B.2 (a) 27 J Kโ1
(b) 0.45 J Kโ1gโ1
(c) 25 J Kโ1molโ1
2B.3 42 kJ
2B.4 87 kJ
2B.5 ๐ถ๐,m = 29.9 J Kโ1molโ1
๐ถ๐,m = 38.2 J Kโ1molโ1
Topic 2C Internal energy
2C.1 โ41 kJ
2C.2 +42.5 J
Topic 2D Enthalpy
2D.1 +20 kJ
2D.2 0
2D.3 (a) exothermic
(b) endothermic
(c) endothermic
(d) endothermic
(e) endothermic
2D.4 ฮ๐ป = ๐๐ = โ1.2 kJ
๐ถ๐ = 80 J Kโ1
2D.5 ฮ๐ป = ๐๐ = +2.2 kJ
ฮ๐ = +1.6 kJ
2D.6 28.25 J Kโ1molโ1
Topic 2E Physical change
2E.1 1740 kJ molโ1
2E.2 19.5 kJ molโ1
2E.3 +492 kJ molโ1
2E.4 +2.83 ร 104 kJ
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2E.5 (a) +2.44 kJ molโ1
(b) +2.26 kJ molโ1
2E.6 +93 kJ molโ1
2E.7 ๐๐ = ฮ๐ป = +80.0 kJ
๐ค = โ5.20 kJ
ฮ๐ = +74.8 kJ
2E.8 2.58 kJ molโ1
2E.9 +239 kJ molโ1
Topic 2F Chemical change
2F.1 โ124 kJ molโ1
2F.2 (a) 388 kJ molโ1
(b) smaller
(c) ฮf๐ปo โ 38 kJ molโ1
2F.3 398 kJ molโ1
2F.4 (a) +16 kJ molโ1
(b) โ772 kJ molโ1
2F.5 (a) โ1560 kJ molโ1
(b) +51.88 kJ gโ1
(c) methane: +55.5 kJ gโ1
ethane is less exothermic
2F.6 โ4564.7 kJ molโ1
2F.7 โ85 kJ molโ1
2F.8 (a) โ3290 kJ
(b) โ2710 kJ
2F.9 โ432 kJ molโ1
2F.10 +225 kJ molโ1
Answers to problems
2.1 +920 kJ
610 s
2.2 (a) 37 K
(b) 4.1 kg
2.3 +774 J
2.4 +1.86 kJ
2.5 (a) 175 kJ molโ1
(b) 274 kJ molโ1
(c) 150 kJ molโ1
(d) 449 kJ molโ1
2.6 +2.468 kJ molโ1
2.7 (a) 20.83 J Kโ1molโ1
(b) (i) +641 J molโ1
(ii) +458 J molโ1
2.8 +39.8 kJ molโ1
2.9 2.38 kJ molโ1
2.10 +40.88 kJ molโ1
2.11 +1152 kJ
2.12 4.22 kJ Kโ1
+0.768 K
2.13 (a) โ2800 kJ molโ1
(b) โ2800 kJ molโ1
(c) โ1.27 ร 103 kJ molโ1
2.14 (a) โ1333 kJ molโ1
(b) โ1331 kJ molโ1
(c) โ815 kJ molโ1
2.15 +112.27 kJ molโ1
2.16 โ382.96 kJ molโ1
2.17 (a) โ57.29 kJ molโ1
(b) โ28.6 kJ molโ1
(c) โ138.2 kJ molโ1
(d) โ32.88 kJ molโ1
(e) โ55.84 kJ molโ1
2.19 (a) +1.9 kJ molโ1
(b) +30.6 kJ molโ1
2.20 (a) โ2205 kJ molโ1
(b) โ2200 kJ molโ1
2.21 +11.3 kJ molโ1
2.22 โ56.98 kJ molโ1
2.23 (a) decrease
(b) increase
(c) decrease
2.24 (a) increase
(b) increase
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Atkins & de Paula: Elements of Physical Chemistry, Seventh Edition
ANSWERS TO END OF CHAPTER EXERCISES
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2.25 +7.04 J molโ1
Answers to projects
2.1 (a) more negative
(b) more positive
2.2 (a) ๐ค = โ๐๐ (๐i + ๐๐i) ln(๐f/๐i) + ๐๐ ๐(๐f โ ๐i)
(b) w more negative
2.3 (a) ฮ๐m = ยผ๐๐4
(b) ๐ถ๐,m = ๐ + 2๐๐
2.4 (a) +818 J molโ1
2.6 (a) 40000 K
2.7 ๐ = 29.74 J Kโ1molโ1
๐ = 2.51 ร 10โ2 J Kโ2molโ1
๐ = โ1.55 ร 105 J K molโ1
2.9 (a) 7.4 per cent
(b) 40 kJ
(c) 15 m
(d) blood temperature, 37 C
(e) 25 kJ
(f) 9.1 m
Focus 3
The Second Law of thermodynamics
Answers to exercises
Topic 3A Entropy
3A.1 (a) +1.7 J Kโ1
(b) +1.2 J Kโ1
3A.2 +0.41 J Kโ1
3A.3 1470 K
Topic 3B Entropy changes
3B.1 +14 J Kโ1molโ1
3B.2 2.89 dm3
3B.3 +23.6 J Kโ1
3B.4 โ93.0 J Kโ1
3B.5 โ45.1 kJ
โ165 J Kโ1
3B.6 (a) +120 J Kโ1
(b) โ120 J Kโ1
3B.7 +0.95 J Kโ1molโ1
3B.8 (a) +122 J Kโ1
(b) +130 J Kโ1
(c) +606 J Kโ1
The total entropy change of the system:
+858 J Kโ1
3B.9 (a) +85 J Kโ1molโ1
(b) +34 kJ molโ1
3B.10 (a) +87.8 J Kโ1molโ1
(b) โ87.8 J Kโ1molโ1
Topic 3C Absolute entropy
3C.1 6.69 mJ Kโ1molโ1
3C.3 +11.5 J Kโ1molโ1
Topic 3D The Gibbs energy
3D.1 (a) positive
(b) negative
(c) positive
3D.2 (a) โ412.9 J Kโ1molโ1
(b) +92.6 J Kโ1molโ1
(c) โ153.1 J Kโ1molโ1
(d) โ21.0 J Kโ1molโ1
(e) +512.0 J Kโ1molโ1
3D.3 (a) โ198.72 J Kโ1 molโ1
(b) +309 J Kโ1 molโ1
Answers to problems
3.1 (a) +33 J Kโ1
3.2 โ7.9 J Kโ1molโ1
3.3 0.63 ๐i
3.5 +5.1 J Kโ1
3.6 +79 J Kโ1molโ1
3.7 (b) 4.1 ร 10โ23 J Kโ1
3.8 (c) 3.37 J Kโ1 molโ1
3.9 4.0 ร 10โ4J Kโ1molโ1
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Atkins & de Paula: Elements of Physical Chemistry, Seventh Edition
ANSWERS TO END OF CHAPTER EXERCISES
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3.10 0.256 J Kโ1molโ1
3.11 +5.03 kJ Kโ1
3.12 (a) โ0.69 J Kโ1molโ1
(b) +0.14 J Kโ1molโ1
3.13 (a) โ93 kJ molโ1
(b) Yes
(c) +300 J Kโ1molโ1
3.14 0.41 g
3.15 +17 J
3.16 8.2 ร 1023molecules
Answers to projects
3.1 (a) 3.3 kW
(b) 180 kW
3.2 ฮ๐ = ๐ ln(๐f/๐i) + ๐(๐f โ ๐i)
โยฝ๐(๐fโ2 โ ๐i
โ2)
3.3 (b) 2.02 ร 10โ22 J Kโ1molโ1
(d) ๐
๐< 0.01
3.4 (a) Yes
(b) 0.46 mol
(c) โ12 W mโ3
(d) battery: โ150 ร 103 W mโ3
computer battery
Focus 4
Physical transformation
Answers to exercises
Topic 4A The thermodynamics of transition
4A.2 graphite
4A.3 No
4A.4 (a) +2.7 kJ molโ1
(b) โ20 kJ molโ1
4A.5 +4.2 kJ molโ1
4A.6 โ3.5 kJ molโ1
Topic 4B Phase diagrams of pure substances
4B.1 (a) 7.9 kg
(b) 15 kg
(c) 1.1 g
4B.2 0.709 atm
which is equivalent to 0.719 bar
4B.3 331 K
4B.4 758 mbar
4B.5 36.7 kJ molโ1
4B.6 A: 15.15 B: unchanged
4B.7 1
4B.8 2
Topic 4C Partial molar quantities
4C.1 886.8 cm3
4C.2 96.9 cm3
4C.3 +1.8 kJ molโ1
4C.4 +32.631 J molโ1
4C.5 (a) โ1.31 kJ molโ1
(b) +4.38 J Kโ1molโ1
(c) spontaneous
4C.6 (a) ฮ๐บm โ 1.40 kJ molโ1
ฮ๐m + 4.71 J Kโ1molโ1
(b) spontaneous
4C.7 4.99 kPa
Topic 4D Solutions
4D.1 17.5 g
4D.2 8.92 ร 10โ2 mol kgโ1
4D.3 ๐sucrose = 0.403 mol dmโ3
๐sucrose = 0.388 mol kgโ1
4D.4 1.80 ร 10โ3
4D.5 โ37 J molโ1
4D.6 ๐ฅCO2= 4.8 ร 10โ3
4D.7 129 kPa
4D.8 7985 Pa
4D.9 (a) 1.3 mmol dmโ3
(b) 17.0 mmol dmโ3
4D.10 ๐N2= 0.51 mmol kgโ1
๐O2= 0.28 mmol kgโ1
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ANSWERS TO END OF CHAPTER EXERCISES
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4D.11 34.3 mmol dmโ3
4D.12 ๐ฅT = 0.93 ๐ฅX ๏ผ0.07
๐ฆT = 0.97 ๐ฆX = 0.03
4D.13 +5.6 kJ molโ1
Topic 4E Colligative properties
4E.1 59.1 g molโ1
4E.2 +0.061 K
4E.3 +0.36 K
4E.4 207 g molโ1
Topic 4F Phase diagrams of mixtures
4F.1 ๐โฒ
๐โฒโฒ = 0.31
4F.2 ๐Eโฒ (aq) = 0.050 mol dmโ3
๐Eโฒ (org) = 0.0075 mol dmโ3
4F.3 0.25
Answers to problems
4.1 (b) 711 K
4.3 (a) โ0.1346 bar Kโ1
(b) +135.6 bar
4.4 (a) 31.69 kJ molโ1
(b) 341.7 K
4.5 353 K
4.6 3.0 Torr
4.11 2.30 kPa
4.12 (a) 171.03 Torr
(b) 6.92 Torr
(c) ๐ฆeth = 0.96111
๐ฆchl = 0.03889
(d) 692 Torr
4.13 (a) 43.95 Torr
(b) 1.13 Torr
(c) 22.6 kPa
4.14 6.41 ร 103 kPa
4.15 A: ๐พHโฒ = 861 Torr
B: ๐พHโฒ = 1103 Torr
4.16 A: KH = 242 Torr
B: KH = 397 Torr
4.17 0.11 C
4.18 ๐ = 88.19 kg molโ1
4.19 13.9 kg molโ1
4.20 (a) yT = 0.36
(b) yT = 0.81
4.21 (a) 0.150
(b) ๐โฒ
๐โฒโฒ = 9.81
4.22 (a) 0.345
(b) ๐โฒ
๐โฒโฒ = 0.135
4.25 (c) 5% tin by mass
(d) No Ag3Sn in the solid
(e) 20% Ag3Sn by mass
Answers to projects
4.1 (a) 6.4 kPa
(c) 5.7 kPa
4.2 (b) greater
(c) 0.69 per cent
4.3 (a) ๐ฅethanol = 0.072
(b) 53.1039 cm3 mol
-1
4.4 (a) ๐water/cm3 molโ1 =
18.068 + 6.557 ร 10โ3๐2 โ 1.018 ร 10โ3๐3
4.5 (a) 4.4 cm3O2
(b) 4.0 atm: 56 ฮผg N2,
1.0 atm: 14 ฮผg N2
(c) 170 ฮผg N2
Focus 5
Chemical change
Answers to exercises
Topic 5A The thermodynamics of reaction
5A.1 (a) ๐ = ๐CO2(g)
6
[CH3COCOOH]2๐O2(g)5 ร (๐o2/๐o)
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ANSWERS TO END OF CHAPTER EXERCISES
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(b) ๐ = [FeSO4]
[PbSO4]
(c) ๐ = [HCl]2
๐H2(g)ร
๐o
๐o2
(d) ๐ = [CuCl2]
[CuCl]2 ร ๐o
5A.2 +12.3 kJ molโ1
5A.3 +6.8 kJ molโ1
5A.4 โ25.1 kJ molโ1
5A.5 +26 kJ molโ1
5A.7 โ14.4 kJ molโ1
formation of NH3
5A.8 2.31
5A.9 (a) 5.2 ร 1011
(b) 850
5A.10 1
5A.11 โ2.42 kJ molโ1
5A.12 3.01
5A.13 glucose-1-phosphate 3.4 ร 103
glucose-6-phosphate 2.5 ร 102
glucose-3-phosphate 36
Topic 5B The equilibrium constant
5B.1 ๐CO2= 10.2 kPa
5B.2 3.3 ร 106
5B.3 6.94
5B.4 3.1 ร 10โ3
5B.5 4.31 ร 1043
Topic 5C Response to conditions
5C.1 (a) 52.9 kJ molโ1
(b) โ52.9 kJ molโ1
5C.2 โ92.2 kJ molโ1
5C.3 ๐พ = 7.23 ร 1011
5C.4 (a) products
(b) products
(c) reactants
(d) products
Topic 5D Proton transfer equilibria
5D.3 (a) pH = 4.8
pOH = 9. 2
(b) pH = 2.8
pOH = 11.2
(c) pH = 13.3
pOH = 0.7
(d) pH = 4.3
pOH = 9.7
5D.4 (a) 9.5 mmol dmโ3
pH = 2.0
(b) 5.01 ร 10โ13mol dmโ3
pH = 12.3
(c) 53 mmol dmโ3
pH = 1.3
Topic 5E Polyprotic acids
5E.1 (a) 9.7 ร 10โ4
(b) 3.8 ร 10โ10
5E.2 (a) ๐(H2S) = 1.0
๐(HSโ) = 1.3 ร 10โ3
๐(S2โ) = 9.2 ร 10โ14
undissociated (H2S) form
(b) ๐(H2S) = 7.7 ร 10โ4
๐(HSโ) = 1.0
๐(S2โ) = 7.1 ร 10โ5
HSโ ions
Topic 5F Acidโbase equilibria of salts in water
5F.1 4.36
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5F.2 (a) acidic
NH4+(aq) + H2O(l) โ H3O+(aq) + NH3(aq)
(b) basic
H2O(l) + CO32โ(aq) โ HCO3
(aq) + OHโ(aq)
(c) basic
H2O(l) + Fโ (aq) โ HF(aq) + OHโ(aq)
(d) neutral
(e) acidic
[Al(H2O)6]3+(aq) + H2O(l) โ
[Al(H2O)5OH]2+(aq) + H3O+(aq)
(f) acidic
[Co(H2O)6]2+(aq) + H2O(l) โ
[Co(H2O)OH]+(aq) + H3O+(aq)
5F.3 (a) pH 2โ4
(b) pH 3โ5
(c) pH 11.5โ13.5
(d) pH 6โ8
(e) pH 5โ7
5F.4 (a) H3PO4 and NaH2PO4
(b) NaH2PO4 and Na2HPO4, or
NaHSO3 and Na2SO3
Topic 5G Solubility equilibria
5G.2 (a) 1.0 ร 10โ5 mol dmโ3
(b) 1.2 ร 10โ4 mol dmโ3
(c) 9.3 ร 10โ11 mol dmโ3
(d) 6.9 ร 10โ7 mol dmโ3
5G.3 (a) 5.5 ร 10โ10mol dmโ3
(b) 3.2 ร 10โ3 mol dmโ3
(c) 1.6 ร 10โ7 mol dmโ3
(d) 2.5 ร 10โ7 mol dmโ3
Topic 5H Ions in solution
5H.1 1.35
5H.3 7.63 mS m2molโ1
5H.4 347 ฮผm sโ1
Topic 5I Electrochemical cells
5I.2 (a) ๐ฃ = 2
(b) ๐ฃ = 2
(c) ๐ฃ = 4
(d) ๐ฃ = 2
(e) ๐ฃ = 2
(f) ๐ฃ = 1
5I.3 โ212 kJ molโ1
5I.4 +7.7 kJ molโ1
Topic 5J Standard potentials
5J.1 Exercise 5I.1
(a) 0
(b) 0
(c) +0.87 V
(d) โ0.27 V
(e) โ0.62 V
(f) +1.67 V
Exercise 5I.2
(a) +0.08 V
(b) +0.27 V
(c) +1.23 V
(d) +0.695 V
(e) +0.54 V
(f) +0.37 V
5J.2 ๐ธโ = +1.14 V
ฮr๐บโ = โ440 kJ molโ1
5J.3 110
5J.4 0.320 V
Answers to problems
5.1 (a) โ91.14 kJ molโ1
(b) +594.6 kJ molโ1
(c) โ66.8 kJ molโ1
(d) +99.8 kJ molโ1
(e) โ415.80 kJ molโ1
5.2 +279 kJ molโ1
5.3 (a) โ32 kJ molโ1
(b) (i) โ49 kJ molโ1
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ANSWERS TO END OF CHAPTER EXERCISES
9
(ii) โ67 kJ molโ1
5.4 โ0.7 kJ molโ1
5.5 (a) exergonic
(b) endergonic
(c) endergonic
(d) exergonic
5.6 (a) 1120 K
(b) 397 K
5.7 1500 K
5.8 (a) K > 1
(b) K < 1
(c) K > 1
(d) K > 1
(e) K > 1
5.10 ๐พr1/๐พr2 = 1.4 ร 1046
5.11 โ245 kJ molโ1
5.12 0.0958, 0.9042
5.13 ๐NH3(g) = 1.93 bar
๐H3(g) = 1.10 bar
๐N3(g) = 0.03 bar
5.14 2.7 ร 10โ4bar
5.15 (a) โPCl5โ = 0.016 mol dmโ3
[PCl3] = [Cl2] = 0.013 mol dmโ3
(b) 45 per cent
5.16 ๐H2(g) โ 0.20 bar
๐N2(g) โ 0.20 bar
๐NH3(g) = 7.6 ร 10โ5 bar
5.17 +41.1 kJ molโ1
5.19 (a) 9.24
(b) โ12.9 kJ molโ1
(c) +161 kJ molโ1
(d) +248 J Kโ1molโ1
5.20 โ187.78 kJ molโ1
5.21 (a) +12.50 kJ molโ1
(b) +9.05 kJ molโ1
(c) โ8.6 J Kโ1molโ1
5.22 (a) [H3O+] = 1.6 ร 10โ7 mol dmโ3
pH = 6.8
(b) [OHโ] = 1.6 ร 10โ7 mol dmโ3
pOH = 6.8
5.23 (a) 2 D2O(l) โ D3O+(aq) + OD
โ(aq)
(b) 14.9
(c) 3.67 ร 10โ8 mol dmโ3
(d) 7.43
(e) pD + pOD = p๐พw = 14.9
5.24 ideal: pH = 0.30
๐พH3O+ = 0.769: pH = 0.42
5.26 +57.2 kJ molโ1
๐.28 p๐พa = 8.02
5.29 (a) 5 per cent
(b) 0.34 per cent
(c) 2.4 per cent
5.30 (a) pH = 1.94
pOH = 12.1
7.4 per cent
(b) pH = 3.7
pOH = 10.3
81 per cent
(c) pH = 0.84
pOH = 13.16
58 per cent
5.31 (a) pH = 6.6
(b) pH = 2.1
(c) pH = 1.5
5.32 [(COOH)2] = 0.08 mol dmโ3
[HOOCCO2โ] = 0.07 mol dmโ3
[(CO2)22โ] = 6.5 ร 10โ5 mol dmโ3
[H3O+] = 0.07 mol dmโ3
[OHโ] = 1.4 ร 10โ13 mol dmโ3
5.33 [H2S] = 0.065 mol dmโ3
[HSโ] = 9.2 ร 10โ5mol dmโ3
[S2โ] = 7.1 ร 10โ15mol dmโ3
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ANSWERS TO END OF CHAPTER EXERCISES
10
[H3O+] = 9.2 ร 10โ5mol dmโ3
[OHโ] = 1.1 ร 10โ10 mol dmโ3
๐.35 pH = 9.2
5.36 pH = 4.8
5.38 (a) [acid]
[base]= 1.6 ร 10โ5
(b) [acid]
[base]= 1
(c) [acid]
[base]= 5.0
5.40 pH = 2.71
5.41 (a) pH = 5.1
(b) pH = 9.1
(c) pH = 2.7
5.42 (a) pH = 2.9
(b) pH = 4.6
(c) 12.5 cm3
(d) pH = 4.75
(e) 25.0 cm3
(f) pH = 8.72
5.43 ๐พa = 6.92 ร 10โ6
pKa = 5.16
pH = 3.38
5.44 8.00
5.46 (a) pKa = 3.08
๐พa = 8.32 ร 10โ4
(b) pH = 2.78
5.47 pH = 8.3
5.48 (a) pH = 4.75
(b) pH = 5.0
(c) pH = 4.1
5.49 ฮs๐บo = +241 kJ molโ1
5.50 ๐ = 1.25 ร 10โ5 mol dmโ3
5.51 (b) increase
5.52 (a) 2.73 g
(b) 2.92 g
5.53 0.015 mol kgโ1 MgF2
๐พยฑ,MgF2= 0.538
๐Mg2+ = 0.0081
๐Fโ = 0.016
0.025 mol kgโ1 NaCl
๐พยฑ,NaCl = 0.733
๐Na+ = 0.018
๐Clโ = 0.018
5.54 ๐ต = 2.022
5.55 13.83 mS m2molโ1
5.56 (a) 12.6 mS m2 molโ1
(b) 210 S mol1/2m1/2
5.57 1.364 ร 10โ5 mol dmโ3
5.58 3.70
5.59 4.85
5.60 +28 mV
5.61 โ1.18 V
5.62 (a) +1.23 V
(b) +1.11 V
5.63 (a) right-hand
(b) +1.06 V
5.64 (a) โ1.20 V
(b) โ 1.19 V
5.65 (a) โ394 kJ molโ1
(b) โ787 kJ molโ1
(c) +75 kJ molโ1
(d) โ284 kJ molโ1
(e) โ291 kJ molโ1
(f) +498 kJ molโ1
5.66 (a) ๐ธcello = โ0.46 V
ฮr๐บo = +88.8 kJ molโ1
ฮr๐ปo = +146.39 kJ molโ1
(b) +86.9 kJ molโ1
5.67 (a) ๐ธcello = +1.57 V
ฮr๐บo = โ606 kJ molโ1
(b) โ604 kJ molโ1
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ANSWERS TO END OF CHAPTER EXERCISES
11
5.70 (a) โ40 kJ molโ1
(b) +29.7 kJ molโ1
(c) โ313 kJ molโ1
5.71 (a) +0.324 V
(b) +0.45 V
5.72 +0.56 V
5.73 (a) 6.4 ร 109
(b) 1.3 ร 107
(c) 9.4 ร 1043
(d) 1.1 ร 1025
(e) 8.2 ร 10โ7
(f) 3.4 ร 1013
5.75 (a) +0.94 V
(b) {1.51 + 0.041 ร ln(10โpH)} V
5.76 +0.22 V
5.77 (a) โ0.6119 V
(b) โ0.22 V
(d) +0.41 V
(e) p๐พa = 10.28
5.79 ฮr๐o = โ324 J Kโ1molโ1
ฮr๐ปo = โ571 kJ molโ1
Answers to projects
5.3 (b) +0.2234 V
5.4 (b) +0.206 V
Focus 6
Chemical kinetics
Answers to exercises
Topic 6A Empirical chemical kinetics
6A.1 1.2 mmol dmโ3
6A.2 A: 1.6 mol dmโ3sโ1
B: 0.80 mol dmโ3sโ1
D: 2.4 mol dmโ3sโ1
6A.3 0.80 mol dmโ3sโ1
Topic 6B Rate laws
6B.1 molโ2dm6 sโ1
6B.2 ๐r1: molโ1dm3sโ1
๐r2: molโ1dm3
6B.3 ๐r1: kPaโ1/2sโ1
๐r2: dimensionless
6B.4 3.7 ร 106 dm3molโ1sโ1
Topic 6C Integrated rate laws
6C.1 1.58 ร 10โ3 sโ1
6C.2 1.12 ร 10โ4sโ1
6C.5 (a) 14 Pa sโ1
(b) 1.5 ร 103s
6C.7 1326 s
6C.8 3100 a
6C.9 (a) 0.63 ฮผg
(b) 0.16 ฮผg
6C.10 (a) 0.138 mol dmโ3
(b) 0.095 mol dmโ3
6C.11 13.6 s
6C.12 ๐ก1/2 = 5.70 h
(a) 78.4 kPa
(b) 77.6 kPa
Topic 6D The temperature dependence of
reaction rates
6D.1 7.5 ร 10โ14molโ1dm3sโ1
6D.2 (a) 1.86 ร 1023a
(b) 75.8 s
6D.3 ๐ด = 1.37 ร 1015dm3molโ1sโ1
6D.4 298.86 K
6D.5 52 kJ mol1
6D.6 35.9 kJ molโ1
6D.7 121 kJ molโ1
6D.8 โ21.6 kJ molโ1
6D.9 (a) 27.2 kJ molโ1
(b) 54.3 kJ molโ1
6D.10 ๐ด = 1.44 ร 1012 molโ1 dm3 sโ1
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ANSWERS TO END OF CHAPTER EXERCISES
12
6D.11 0.8 nm2
Topic 6E The approach to equilibrium
6E.1 7.5 ร 105 sโ1
6E.2 23.8 msโ1
6E.3 21 ms
Topic 6F Reaction mechanisms
6F.1 39.1 d
6F.2 increase
6F.3 1.89 ร 10โ6 Paโ1sโ1
Topic 6G Reactions in solution
6G.1 (a) 6.61 ร 106 m3molโ1sโ1
(b) 3.0 ร 107 m3molโ1sโ1
6G.2 (a) โ3.1 ร 1016 mol mโ2sโ1
(b) 1.6 ร 10โ11mol
6G.3 (a) 27 h
(b) 2.7 ร 103 h
(c) 3.0 ร 103 a
6G.4 ๐ = 1 ร 106
6G.5 17 kJ molโ1
Topic 6H Homogeneous catalysis
6H.1 5.6 ร 1022
6H.2 1.62 mmol dmโ3
6H.3 ๐cat = 1.18 ร 105 sโ1
๐ = 7.9 ร 106 molโ1dm3sโ1
Topic 6I Heterogeneous catalysis
6I.1 172 m2
6I.2 (a) 60 Pa
(b) 4.9 kPa
6I.3 (a) 0.068
(b) 0.42
Answers to problems
6.1 (a) first order
(b) 4.977 s1
6.2 (a) complex: first order
Y: second order
(b) 1.9 mol1
dm3 s1
6.3 (a) ๐ฃ = ๐๐[ICl][H2]
(b) kr = 0.162 mol1
dm3 s1
(c) 20.6 ร 10โ7mol dmโ3sโ1
6.4 0.248 s1
6.5
(a) second order
(b) 7.80 ร 10โ3
dm3 mol
โ1 s
โ1
6.6 (a) second order
(b) 1.32 dm3 mol
โ1 s
โ1
6.9 second order
0.287 molโ1dm3minโ1
6.10 ๐ธa = 272 kJ molโ1
6.11 ๐ธa = 180 kJ molโ1
A = 2.11 molโ1
dm3 s
โ1
6.12
(a) ๐(20 โ) = 1.7 ร 10โ20
(b) ๐(200 โ) = 5.6 ร 10โ13
๐ด = 3 ร 1011 molโ1dm3sโ1
6.13 (a) 126 kJ molโ1
(b) ฮ๐โก = 0
6.15 ๐r,eff = 7.12 ร 105 sโ1
๐rโฒ = 4.00 ร 1010 molโ1 dm3sโ1
6.16 {๐b(๐a/๐aโฒ )1/2}[A2]1/2[B]
6.19 (a) 3 ClO(aq) ClO3(aq) + 2 Cl(aq)
(b) first step
6.26 ๐พM = 1.11 ฮผmol dmโ3
๐ฃmax = 2.31 ฮผmol dmโ3 sโ1
๐cat = 1.2 ร 102 sโ1
6.27 ๐พM = 87 mmol dmโ3
๐ฃmax = 16 ฮผmol dmโ3 sโ1
6.28 ๐ผ = 2.809 Paโ1
๐โ = 0.5659 cm3
6.29 gold: zeroth order
Platinum: first order
6.33 ๐ = 165
๐mon = 13.1 cm3
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ANSWERS TO END OF CHAPTER EXERCISES
13
Answers to projects
6.1 (a) 1
[A]0โ[B]0ln (
[B]/[B]0
[A]/[A]0) = ๐r๐ก
(b) 1
[A]โ
1
[A]0= ๐r๐ก
6.2 (b) ๐ธa = 105.1 kJ molโ1
ฮr๐บo = โ26.6 kJ molโ1
ฮr๐ปo = โ34.3 kJ molโ1
6.6 (a) ๐พM = 24.9 mmol dmโ3
๐ฃmax = 4.80 mol dmโ3sโ1
(b) ๐พM = 25.0 mmol dmโ3
๐ฃmax = 4.81 mol dmโ3sโ1
(c) ๐พM = 25.0 mmol dmโ3
๐ฃmax = 4.80 molโ1 dm3sโ1
Focus 7
Quantum theory
Answers to exercises
Topic 7A The emergence of quantum theory
7A.1 3.05 ร 10โ19 J
7A.2 8.226 ร 104 cmโ1
7A.3 (a) 6.6 ร 10โ19 J
4.0 ร 102 kJ molโ1
(b) 3.3 ร 10โ20 J
20 kJ molโ1
(c) 1.3 ร 10โ33 J
7.8 ร 10โ13 kJ molโ1
7A.4 (a) ๐ธ(750 nm) = 2.65 ร 10โ19 J
(b) ๐(250 nm) = 9.96 ร 105 m sโ1
7A.5 (a) 6.6 ร 10โ31m
(b) 6.6 ร 10โ39 m
(c) 99.7 pm
7A.6 1.3 ร 106 m sโ1
7A.7 4 ร 10โ36m
7A.8 (a) 1.10 ร 10โ27 kg m sโ1
(b) 9.5 ร 10โ24 kg m sโ1
(c) 3.31 ร 10โ36 kg m sโ1
7A.9 2.2 ร 10โ24 m sโ1
Topic 7B The dynamics of microscopic systems
7B.1 ฮ๐ฅ โฅ 0.900 nm
7B.2 ฮ๐ฃ โฅ 2.1 ร 10โ29 m sโ1
7B.3 ฮ๐ฅ โฅ 1.1 ร 10โ26 m
7B.4 ฮ๐ฅ = 100 ร 10โ12 m
ฮ๐ฃ โฅ 5.8 ร 105 m sโ1
Topic 7C Translation
7C.1 (a) ๐ฅ = ๐ฟ/2
(b) ๐ฅ = 3๐ฟ/4
(c) ๐ฅ = 5๐ฟ/6
7C.2 9.84 ร 10โ23 J
7C.3 ๐ฟ = 1.00 ร 10โ9 m
Topic 7D Rotation
7D.1 ๐ = 0: โ
๐ = 1: 628 pm
๐ = 2: 314 pm
7D.2 (a) 4.34 ร 10โ47 kg m2
(b) 1.55 mm
7D.3 6
7D.4 ml = โ4, โ3, โ2, โ1, 0, +1, +2, +3
7D.5 6.65 ร 10โ22 J
Topic 7E Vibration
7E.1 0.04 N mโ1
7E.2 6.90 ร 1013 sโ1
7E.3 7.94 ร 10โ6 N mโ1
Answers to problems
7.1 2.52 eV
7.2 (a) 1.23 nm
(b) 38.8 pm
(c) 3.88 pm
7.3 (a) 6.1 ร 10โ4 N
(b) 6.1 ร 10โ10 Pa
(c) 1600 s
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ANSWERS TO END OF CHAPTER EXERCISES
14
7.5 ๐ฅ = ยฑ0.5887/๐1/2
7.7 (a) 1.8 ร 10โ4
(b) 5.9 ร 10โ5
7.8 5h2 / 8mL
2: (1,4) (2,2)
5h2 / 4mL
2: (1,6) (3,2)
7.9 ๐ฟ/4 , 3๐ฟ/4
7.10 (a) 2.2 ร 10โ20 J
(b) 9.2 ฮผm
7.12 (a) 0.22
(b) 9.5 ร 10โ3
7.13 8.79 ร 1011sโ1
7.14 2.10 ร 10โ22 J
7.15 0.707
Answers to projects
7.1 (a) ๐ฅ = 0.1 to ๐ฅ = 0.2 nm:
๐(๐ฅ) = 1.84 ร 10โ4, 3.8 per cent
x = 4.9 to x = 5.2 nm:
๐(๐ฅ) = 2.36 ร 10โ4, 74.9 per cent
(b) 0.196
(c) 0.609
(d) 0.196
7.2 (a) (i) ๐(๐ฅ) = (๐/ฯ)1/4eโ๐๐ฅ2/2
(ii) x = 0
(b) (i) ๐(๐ฅ) = (4๐3/ฯ)1/4๐ฅeโ๐๐ฅ2/2
(ii) x = ยฑ1/a1/2
7.3 (a) 6.432 ร 1013 sโ1
(b) 2146 cmโ1
(c) ๐ C13 O16 2098 cmโ1
๐ C12 O18 2094 cmโ1
๐ C13 O18 2045 cmโ1
Focus 8
Atomic structure
Answers to exercises
Topic 8A Hydrogenic atoms
8A.1 4.10296 ร 10โ5cm = 410.296 nm
8A.2 ๐2 = 5
8A.3 ๐2 = 6
8A.4 1.00047
8A.5 27 cmโ1
8A.6 n1 = 2 n2 = 4
8A.7 16
8A.8 (a) 0, 0 angular node, 0 radial nodes
(b) 0, 0 angular node, 2 radial nodes
(c) 61/2โ, 2 angular nodes,
0 radial nodes
(d) 21/2โ, 1 angular node, 0 radial nodes
(e) 21/2โ, 1 angular node, 1 radial node
8A.9 (a) 1
(b) 9
(c) 49
8A.10 (a) 2
(b) 14
(c) 22
8A.11 0, 180, 90, 270
8A.12 (a) (๐ ๐ 1)
(b) l
(c) (๐ 1)
Topic 8B Many-electron atoms
8B.2 (a) [He]2s2p3
(b) [Ar]3d2
(c) [Ar]3d5
Topic 8C Periodic trends of atomic properties
8C.2 349 kJ molโ1
Topic 8D Atomic spectroscopy
8D.1 (b), (c), (e)
8D.3 nd, ng
8D.4 (a) ๐ฟ = 2, 1, 0
(b) ๐ฟ = 4,3, 2, 1, 0
8D.5 S = 2, 1, 0
8D.6 (a) 1S0
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ANSWERS TO END OF CHAPTER EXERCISES
15
(b) 3F4,
3F3,
3F2
(c) 5S2
(d) 5P3, 5P2,
5P1
8D.7 3F,
1F,
3D,
1D,
3P,
1P
8D.8 (a) 3F term,
the lowest level:
3F2
(b) 5
8D.9 [Ar]3d1
๐ฝ = 5/2, 3/2
2D3/2, lowest in energy
8D.10 3F2
8D.11 Al: 2P1/2
Cl: 2P3/2
8D.12 (a), (c)
Answers to problems
8.1 n = 3 2: He3 + 15238.6 cmโ1
He4 + 15239.3 cmโ1
n = 2 1: He3 + 82288.5 cmโ1
He4 + 82292.3 cmโ1
8.2 122.31 eV
8.3 (a) n = 7 6 12368 nm
n = โ 6 3282 nm
(b) n = 8 6 7503 nm
n = 9 6 5908 nm
(c) 12368 nm
8.4 (a) 397.13 nm
(b) 3.400 eV
8.5 (a) 109740 cmโ1
(b) n = 3 2 137170 cmโ1
n = 4 2 185180 cmโ1
(c) 122.5 eV
8.6 14.0 eV
8.7 0.602 ๐0
8.8 (a) 0.262 a0, 2.530 a0
(b) 0.090 a0, 3.845 a0
8.9 (a) 1.4 ร 10โ5
(b) 1.1 ร 10โ4
8.10 (a) 1.9 ๐0 , 7.10 ๐0
(b) 1.87 ๐0, 6.61 ๐0, 15.5 ๐0
8.11 Fe2+
8.12 2.142 meV
Answers to projects
8.1 (a) ๐ = ๐0
(b) (i) 2.69 ร 10โ7
(ii) 2.47 ร 10โ8
(iii) 0
(c) 5.24 a0
(d) 5.236 ๐0
8.3 (a) receding, 338 km sโ1
Focus 9
The chemical bond
Answers to exercises
Topic 9A Valence bond theory
9A.1 1870 kJ molโ1
9A.2 ๐CโH = ๐C(1)๐H(2) + ๐C(2)๐H(1)
9A.3 ๐1(ฯ-bond) =
๐2p๐งA(1)๐2p๐งB(2) + ๐2p๐งA(2)๐2p๐งB(1)
๐2(ฯ-bond) =
๐2p๐ฅA(1)๐2p๐ฅB(2) + ๐2p๐ฅA(2)๐2p๐ฅB(1)
๐3(ฯ-bond) =
๐2p๐ฆA(1)๐2p๐ฆB(2) + ๐2pyA(2)๐2p๐ฆB(1)
9A.5 210 times
9B.2 F2โ: ยฝ
F2: 1
F2+: 1ยฝ
9B.3 O2+: 2ยฝ
O2: 2
O2โ: 1ยฝ
O22โ: 1
O2+ < O2 < O2
โ < O2
2โ
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ANSWERS TO END OF CHAPTER EXERCISES
16
9B.4
(a) H2โ: 1ฯg
21ฯu1
(b) Li2: 1ฯg2
(c) Be2: 1ฯg2 1ฯu
2
(d) C2: 1ฯg2 1ฯu
2 1ฯu4
(e) N2: 1ฯg2 1ฯu
2 2ฯg2 1ฯu
4
(f) O2: 1ฯg2 1ฯu
2 2ฯg2 1ฯu
4 1ฯg 2
9B.5 C2 stronger
9B.6 32 molecular orbitals
Topic 9C Molecular orbital theory:
heteronuclear diatomics
9C.1 (a) nonpolar
(b) polarized
9C.2 (a) C2, CN
(b) NO, O2, F2
9C.3 N2 is shorter
Topic 9D Molecular orbital theory:
polyatomic molecules
9D.1 โ6.26 eV
604 kJ molโ1
๐๐.2 6๐ผ + 8๐ฝ
9D.3 0
9D.4 (a) โ2๐ฝ
(b) โ1.24๐ฝ
(c) โ2๐ฝ
Answers to problems
9.2 bond angle for SO2 is 120
9.8 CO: 1ฯ2 2ฯ2 3ฯ2 1ฯ4
NO: 1ฯ2 2ฯ2 3ฯ2 1ฯ4 2ฯ1
CNโ: 1ฯ2 2ฯ2 3ฯ2 1ฯ4
9.9 XeF+ will have a shorter bond length than
XeF
9.11 1u
2g (two)
3u (two)
4g
9.12 (a) 6.00 eV
(b) 2.70 eV
9.13 (a) ethene โ30750 cmโ1
butadiene โ37280 cmโ1
hexatriene โ44660 cmโ1
octatetraene โ47370 cmโ1
(b) โ71910 cmโ1
9.14 (a) benzene: ๐ผ + 2๐ฝ, ๐ผ + ๐ฝ,
๐ผ + ๐ฝ, ๐ผ โ ๐ฝ, ๐ผ โ ๐ฝ, ๐ผ โ 2๐ฝ
Cyclooctatetraene:
๐ผ + 2๐ฝ, ๐ผ + โ2๐ฝ, ๐ผ + โ2๐ฝ,
๐ผ, ๐ผ, ๐ผ โ โ2๐ฝ, ๐ผ โ โ2๐ฝ, ๐ผ โ 2๐ฝ
(b) benzene: 2๐ฝ
hexatriene: 0.988๐ฝ
(c) cyclooctatetraene: 1.657๐ฝ
octatetraene: 1.516๐ฝ
9.15 ๐ผ + โ2๐ฝ: bonding
๐ผ: non โ bonding
๐ผ โ โ2๐ฝ: antibonding
9.16 (a) C6H6โ: 1ฯu
2 2ฯg4 1ฯu
1
7๐ผ + 7๐ฝ
(b) C6H6+: 1ฯu
2 2ฯg3
5๐ผ + 7๐ฝ
Answers to projects
9.2 (c) ฯ/4, โฯ/4
9.3 (b) (๐ /๐0) = 2.11
(c) ๐1 = ยฑ(0.356๐ด + 0.934๐ต)
๐2 = ยฑ(0.934๐ด โ 0.356๐ต)
Focus 10
Molecular interactions
Answers to exercises
Topic 10A Electric properties of molecules
10A.1 โ36 J molโ1
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10A.2 (a) 1.78 D, 5.9 ร 10โ30C m
(b) 0.94 D, 3.1 ร 10โ30C m
(c) 0.76 D, 2.5 ร 10โ30C m
10A.3 ๐/D = โ0.89
10A.4 1.17 D
10A.5 (a) C2 m
2 J
โ1
(b) (C2 m
2 J
โ1) / (C
2 J
โ1 m
โ1) = m
3
Topic 10B Interactions between molecules
10B.1 โ5.22 ร 10โ24 J
10B.2 ๐(๐) = โ1.9 ร 10โ27 J
๐m(๐) = โ1.19 ร 10โ3 J molโ1
10B.3 479 pm
10B.4 ๐ = 700 pm
๐A๐ = 12.6 kJ molโ1
Answers to problems
10.1 non-polar
10.2 (a) 1,2-dimethylbenzene: 0.69 D
1,3-dimethylbenzene: 0.40 D
1,4-dimethylbenzene: non-polar
(b) (i) 0.80 D
(ii) 0.40 D
(iii) non-polar
10.3 (a) 1.41 D
(b) 2.44 D
(c) 1.06 D
(d) 1.69 D
10.4 ๐ = 37 D
๐ = 11.8ยฐ
10.5 1.17 ร 10โ29 C m = 3.50 D
10.7 (a) 476 kJ molโ1
(b) 87.4 kJ molโ1
10.9 (a) 3.72 kJ molโ1
(b) โ0.365 J molโ1
10.10 196 pm
10.11 ๐(๐) = โ1.6 ร 10โ26 J
๐m(๐) = โ9.6 ร 10โ3J molโ1
๐๐.12 ๐(๐) = โ7.0 ร 10โ20 J,
๐m(๐) = โ42 kJ molโ1
10.14 250 to 410 pm
10.16 (a) 11.6 kJ molโ1
(c) 2.12 ร 1012 sโ1
Focus 11
Molecular spectroscopy
Answers to exercises
11A.1 (a) 6.78 ร 1014 Hz
(b) 22600 cmโ1
11A.2 (a) 2.94 ร 10โ3 cmโ1
(b) 3.41 m
11A.3 (a) 1.48 ร 104 dm3 molโ1 cmโ1
(b) 0.9506%
11A.4 (a) 55 dm3 molโ1 cmโ1
(b) 0.048
11A.5 659.999936 nm
7.02 ร 107 m sโ1
11A.6 8.3 ร 105 K
11A.7 (a) 53 ps
(b) 5.3 ps
(c) 160 ps
11A.8 (a) 53 cmโ1
(b) 0.27 cmโ1
Topic 11B Rotational spectroscopy
11B.1 3.6 ร 1033
11B.2 (a) (i) 4.601 ร 10โ48 kg m2
(ii) 9.194 ร 10โ48 kg m2
(iii), (iv) 7.150 ร 10โ46 kg m2
(b) (i) 1.824 ร 1012 Hz
60.84 cmโ1
(ii) 9.126 ร 1011 Hz
30.44 cmโ1
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(iii), (iv) 1.174 ร 1010 Hz
0.3915 cmโ1
11B.3 (b) 2.66 ร 109 sโ1
0.0888 cmโ1
11B.4 ๐ผโฅ = 4๐B๐B2
๐ผโฅ = 2๐B๐B2
11B.5 ๐ด = 5.149 GHz
๐ต = 10.30 GHz
11B.6 (a) 289
(b) 17
11B.7 232.1 pm
11B.8 ยฝ
11B.9 (a) 10
(b) 19
11B.10 474 K
11B.11 (a) (i) (ii) (iii),(iv)
(b) all
11B.13 (a) 636 GHz
(b) 21.2 cmโ1
11B.14 5990749.416 MHz
11B.15 116.2 pm
11B.16 20643 cmโ1
Topic 11C Vibrational spectroscopy
11C.1 (a) 4.49 ร 1013 Hz
(b) 4.39 ร 1013 Hz
11C.2 (a) 3
(b) 4
(c) 48
(d) 54
11C.3 329 N mโ1
11C.4 (a) (i) HF: 967.4 N mโ1
(ii) HCl: 515.8 N mโ1
(iii) HBr: 411.8 N mโ1
(iv) HI: 314.3 N mโ1
(b) DF: 2930 cmโ1
DCl: 2114 cmโ1
DBr: 1874 cmโ1
DI: 1634 cmโ1
11C.6 3724.66 cmโ1
11C.7 ๐ฅe = 0.0062
11C.8 2699.9 cmโ1
Topic 11D Electronic spectroscopy
11D.1 [A] = 0.56 mol dmโ3
[B] = 0.16 mol dm
โ3
11D.2 1.737 ร 10โ15 J
11D.3 50.8 nm
11D.4 1.602 ร 10โ15 J
11D.5 (a) 2.04 ร 10โ19 J
(b) 669 km sโ1
Topic 11E The decay of excited states
11E.2 0.57
11E.3 4.7 nm
Answers to problems
11.1 33 ฮผg dmโ3
11.2 (a) 162 pm
(b) 179 GHz
11.3 (b) 3.2645 GHz
(c) 237.6 pm
11.4 ๏ฟฝฬ๏ฟฝ = 0.2029 cmโ1
๏ฟฝฬ๏ฟฝ = 6.233 ร 10โ8 cmโ1
11.5 ROC = 116.28 pm
RCS = 155.97 pm
11.9 (b) 126.5 pm
11.11 ๐Q = 5.16 ร 106 molโ1 dm3 sโ1
11.12 kF = 1.276 1010
molโ1
dm3 s
โ1
11.13 kQ =9.146 109 mol
โ1 dm
3 s
โ1
๐ก1/2 = 0.172 ฮผs
11.14 407 ps
11.15 3.49 nm
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Answers to projects
11.1 (a) 4200
(b) 588 nm
11.2 ๐ฝmax = (๐๐/โ๐ต)1/2 โ ยฝ
11.5 2.6 nm
Focus 12
Statistical thermodynamics
Answers to exercises
Topic 12A The Boltzmann distribution
12A.1 ๐2
๐1= 0.37
12A.2 524 K
12A.3 ๐5
๐0= 7.4
Topic 12B The partition function
12B.1 (a) ๐ = 1 + 6eโ2๐/๐๐ + 3eโ5๐/๐๐
(b) ๐ = 1
(c) ๐ = 10
12B.2 (a) ๐T = 1.45 ร 1027
(b) ๐T = 6.49 ร 1027
12B.3 (a) ๐T = 3.2 ร 104
(b) ๐T = 6.2 ร 1027
12B.4 (a) ๐R = 19.5
(b) ๐R = 265
12B.5 eqn 12B.6: ๐V = 1.39
eqn 12B.7: ๐V = 0.789
12B.6 ๐E = 4.23
Topic 12C The origin of thermodynamic
properties
12C.1 ๏ฟฝฬ ๏ฟฝ = (5eโ๐/๐๐+9eโ3๐/๐๐
1+5eโ๐/๐๐+9eโ3๐/๐๐) ๐
12C.2 (a) 1.25 kJ molโ1
(b) 2.08 kJ molโ1
12C.3 โ37.4 kJ molโ1
Answers to problems
12.1 (a) ๐4
๐2= 1.753
(b) ๐4
๐2= 2.27
12.2 (a) ๐๐ = โ ๐๐ฝ๐ฝ=0 eโ๐๐ฝ/๐๐: ๐๐ = 24.816,
Using eqn 12B.5: ๐R = 24.474
12.4 11350 K
12.5 (a) 1.401 (at 500 K)
(b) 3.147 (at 1000 K )
12.6 1.28 ร 1034
12.7 (a) qE = 5
(c) 6.730
12.8 (a) ๐E = 1.293 (at 10 K )
๐E = 7.825 (at 298 K )
12.9 ๐V = 2.14
๐m = 14.6 J Kโ1molโ1
๐๐.10 183.1 J Kโ1molโ1
12.11 (a) S๊(Xe) > S
๊(Ne)
(b) S๊(D2O) > S
๊(H2O)
(c) S๊(graphite) > S
๊(diamond)
12.12 โ54.3 kJ molโ1
12.13 ๐พ = 1.336 ร 10โ25
12.14 ๐พ = 1.951 ร 10โ11
Focus 13
Magnetic Resonance
Answers to exercises
Topic 13A Nuclear magnetic resonance
13A.1 (a) Tโ1 Hz
(c) A s kgโ1
13A.2 ๐ธ3/2 = โ1.949 ร 10โ26 J
๐ธ1/2 = โ6.498 ร 10โ27 J
๐ธโ1/2 = 6.498 ร 10โ27 J
๐ธโ3/2 = 1.949 ร 10โ26 J
13A.3 2.263
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13A.4 (a) 2.9 ร 10โ5
(c) 7.3 ร 10โ6
13A.5 300.5 MHz
13A.6 18.79 T
Topic 13B The information in NMR spectra
13B.1 3.17 kHz
13B.2 (a) 9.1 ฮผT
(b) 38 ฮผT
13B.3 (a) 11
(b) 5
13B.4 (a) 2.4 kHz
(b) 6.0 kHz
13B.5 octet
13B.6 3.78 ms
Topic 13C Electron paramagnetic resonance
13C.1 4.64 ร 10โ24 J
13C.2 (a) 9.02 ร 10โ4
(b) 2.7 ร 10โ3
13C.3 9.25 GHz, 32.4 mm
13C.4 2.0022
13C.5 ๐ = 64.5 MHz
13C.6 (a) 1:3:3:1
(b) 1:3:6:7:6:3:1
13C.7 (a) 331.9 mT
(b) 1.201 T
13C.8 terminal: 0.64
central: 0.180
Answers to problems
13.8 (a) ๐ดโฒ = 1.9 Hz
๐ตโฒ = โ1.4 Hz
๐ถโฒ = 6.4 Hz
(b) 109 ยฐ
13.9 2600 sโ1
13.10 64 sโ1
13.12 1
13.13 ๐ 0.011 mT: 0.0049
๐ 0.172 mT: 0.0764
๐ 0.272 mT: 0.1209
๐ 0.450 mT: 0.2000
๐ 0.108 mT: 0.0480
๐ 0.112 mT: 0.0498
Focus 14
Macromolecules and aggregates
Answers to exercises
Topic 14A Biological and synthetic
macromolecules
14A.1 ๏ฟฝฬ ๏ฟฝn = 95 kg molโ1
๏ฟฝฬ ๏ฟฝw = 93 kg molโ1
14A.2 3.4
14A.3 (a) 0.880 ฮผm
(b) 31.1 nm
(c) 12.7 nm
14A.4 ๐ c = 2.74 ฮผm
๐ rms = 29.1 nm
14A.5 13000
14A.6 โ0.042 J Kโ1molโ1
14A.7 8 aJ
Topic 14B Mesophases and disperse systems
14B.1 5.8 cm
14B.2 23 mN mโ1
14B.3 (a) 1.4 kPa
(b) 0.14 kPa
14B.4 97 mmol mโ2
Answers to problems
14.1 ๏ฟฝฬ ๏ฟฝn = 20 kg molโ1
๏ฟฝฬ ๏ฟฝw = 22 kg molโ1
14.2 ๏ฟฝฬ ๏ฟฝw/๏ฟฝฬ ๏ฟฝn = 1.27
14.4 โฑ = 1.37 pN
14.6 pH = 6.9
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14.7 68 ฮผJ
Answers to projects
14.1 (a) โจ๐ 2โฉ1/2 = 10.9 nm
(b) โจ๐ โฉ = 10.0 nm
(c) ๐ โ = 8.89 nm
14.3 (a) 2.70 pN
Focus 15
Solids
Answers to exercises
Topic 15A Crystal structure
15A.1 ๐ = 0.396 nm3
๐ = 2.41 ร 103kg mโ3
15A.2 ๐ = 3.9
๐ = 4.01 ร 103 kg mโ3
๐๐๐.3 (a) 221 pm
(b) 110 pm
15A.4 {1 1 1} 330 pm, {2 1 1} 234 pm,
{1 0 0} 572 pm
15A.5 {1 2 3} 135 pm
{2 3 6} 70 pm
15A.6 564 pm
15A.7 ๐ = 363 pm
๐ = 564 pm
15A.8 112 pm
15A.9 1.28 mV
15A.10 66.1 pm
15A.11 ๐ = 798 pm
Topic 15B Bonding in solids
15B.1 (a) zinc-blende
(b) zinc blende
(c) rock-salt
15B.2 ฮL๐ป๊(SrO)
ฮL๐ป๊(CaO)= 0.947
15B.3 3000 kJ molโ1
Topic 15C The properties of solids
15C.3 549 nm
Answers to problems
15.2 (321). (111). (122). (32ฬ 2ฬ ).
15.6 bcc
15.7 (b) 8.97 ร 103 kg mโ3
15.8 0.740
15.9 0.740 g cmโ3
15.10 520 nm
15.11 (a) 424 nm
(b) 600 nm
15.12 (a) less dense
(b) 92 per cent
15.15 ๐ = โ๐๐ง2๐2ฯ
48๐0๐
15.16 โ8.16 ร 10โ18 J
15.18 +3500 kJ molโ1
15.19 +2421 kJ molโ1