Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition ANSWERS TO END OF CHAPTER EXERCISES E F. E0.19 (a) / C 100 / C E0.

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ANSWRS T ND F CHAPTR XRCISS INTRDUCTIN 0.1 8.0 N 0. 0.4% 0..6 kj 0.4 6 J 0.18 459.67 F 0.19 (a) / C 0 / C 9 F / F 1 5 / C 0.0 P / P 7.09 / C 09.9 (a) P / P 7.09 T / K 6.5 / P.940 / F 45.8 F P F 0.5 1.4 kj 0.1 671.67 R 0.6. kj 0.. glucose molecules 0.7 4.48 J 0. 4.71 octane molecules 0.8 1 J 0.4 19.7 myoglobin molecules 0.9 (a) 19 1.60 J 96.47 kj mol 1 0.5 0.97 0.6 M / Vm 0. (a) 0.11 11.6 GJ 19.4 J 1 1.4 kj mol 0.1 (a) 8. Torr 0.96 atm 0. atm 5 1.0 Pa 0.7 7.0 mmol dm 0.8 17.5 g NaCl 0.9 (a) (i) Water: 17.5 g NaCl (ii) Benzene: 9.0 mol dm 1 (i) Water: 9.1 mol kg (ii) Benzene: 0.5 mol kg 1 0.1 1.4 bar 0. 9.574 mol kg 1 0.14 0.98 atm 0.15 (a) 1.5 Pa 5.6 Pa 0.16 Differ by as much as 1 part in 6 0.17 (a) 9.80665 Pa 0.075561 Torr 0..17 kg 0.4 5. kg CHAPTR 1 The Properties of Gasses 1.1 9.1 kpa 1..5 kpa xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 1. 4. mmol 1.4 665 bar 1.5.0 atm c c c CH4 CH4 CH4 79 K m s 1 15 K 645 m s 1 1500 K 1.41 km s 1 1.6 4.18 bar 1.7 17 kpa 1.8 9.5 K 1.9 94 K 1. (a) 1.11.6 m 178 m 0.50 m 8 1.1.4 dm 1.14 1.15 (a) 6.7 atm. 1. dm 61. kpa. 1.16 71 Torr 1.1 (a) 7 K 1. 0.065 Pa 1. 944 m s 1 6.4 Pa 1.4 0.97 μm 1.5 (a) 1 5. s 5. s 9 1 5. s 4 1 1.6 (a) 6.5 s 1.7 1 6.5 s 1 1 6.5 s 8 1 4.5 s 1.8 (a) 6.8 nm 68 nm 7 mm 1 1 1.17 1 g mol 1 1.9 Independent of temperature 1.18 1.19 (a) 1.0 (a) 1 16.4 g mol. p.0 bar, p 1.0 bar H N.0 bar c c c He He He 79 K 647 m s 1 15 K 1.9 km s 1 1500 K.8 km s 1 1.0 (a) (i) 1 kpa (ii) 81 bar (i) (ii) 0.99 atm 1.8 atm 1.1 For a perfect gas: 55.6 atm For a van der Waals gas: 4.0 atm xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 1. a B = b and C b RT.1 (a) 0 J K mol 1 1 8 J K mol 1 1 1 1. (a) 4.60 dm mol 1.4 (a) 1.5 0.66 6 1.6 dm atm mol.46 dm mol 1.0 K CHAPTR 1 Thermodynamics: the First Law.1 (a) 0. J 0. J. 5.5 kj. (a) 99 J 167 J.4 +1 J.5 +.99 kj.6 1.5 kj.7 (a) 0.8.9. (a) 78 J 1.0 J.7 J K 1.11 4 kj.1 0.45 J K g 1 1 5 J K mol 4 8.7 J 1 1.14 (a).15 77 J 9. kj 6.1 s..16 5 kj.17 1.86 kj.18 14.54 J.19 4.5 J.0 0 kj...468kj mol 1. (a) 1. kj 1. kj 80 J K 1.4 (a) +. kj.5.6 (a) +. kj 1.6 kj 0.8 J K mol 1 1 641 J mol 1 458 J mol 1 CHAPTR Thermodynamics: Applications of the First Law.1. 6.91 mj mol 1 4 +.8 kj. (a).44 kj.6 kj xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS.4 9.8 kj mol 1.5 (a) 80.0 kj 5.0 kj 74.8 kj.7 +9 kj.1 (a). (a).80 MJ mol 1.80 MJ mol 1 1.7 MJ mol 1 1 kj mol 1. 11 kj mol 1 815 kj mol 1.8.9 4.96 kj mol 1.48 kj mol 1. 16 kj.4.5 11.7 kj mol 1 8 kj mol 1.11 (a) +54.8 kj mol 1 +5. kj mol 1.1 (a) 88 kj mol 1 smaller..1 (a) 16 kj mol 1 08 kj mol 1.14 (a).9 GJ.15 (a).16.17.18.19.71 GJ 1560 kj mol 1 51.88 kj g 1 thane is a less efficient fuel 4564.7 kj mol 1 85 kj mol 1 4 kj mol 1 5 kj mol 1.0 (a) 4. kj K 1 0.769 K.6.7 1.9 kj mol 1. +0.6 kj mol 1.8 (a) 7 C.9 (a) 4.1 kg 05 kj mol 1 00 kj mol 1.0 (a) exothermic,.1 (a).. rh negative endothermic, H positive endothermic, vap H positive endothermic, H positive (e) endothermic, (e) 57.0 kj mol 1 8.6 kj mol 1 18. kj mol 1.88 kj mol 1 55.84 kj mol 1 11. kj mol 1. 56.98 kj mol 1 fus subh positive.4 40.88 kj mol 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS.5 (a) Decrease Decrease Increase.6 (a) Increase Increase CHAPTR 4 Thermodynamics: the Second Law 4.1 4. (a) 0.4 J K 1 0.1 kj K 1. 0.1 kj K 1 4. (a) 45.1 kj 4.5 4.6 165 J K 1 14 J K mol.91 dm 1 1 4.17 (a) 4.18 4.19 (a) 87.8 J K mol 1 1 1 1 87.8 J K mol. 79 J K mol 1 1 1 1 +85 J K mol. +4 kj K mol f 4.0 kn ln V Vi 4.1 11.5 J K mol 4. (a) positive negative positive 1 1 1 1 1 1 4. (a) 86.1 JK mol 1 1 9.6JK mol 15.1 J K mol 1 1 1.0 J K mol 1 1 (e) 51.0 J K mol 1 1 4.7 J K 1 4.4 5.0 kj K 1 4.8 4.9.6 J K 1 9.0 J K 1 4.5 (a) 198.7 J K 1 09 J K 1 4. 8.64% high 4.6 (a) 0.75 J K 1 0.15 J K 1 4.11 1 1 7.9 J K mol 4.7.99 kj 4.1 0.600 T i 4.14 4.0 J K mol 4 1 1 4.8 (a) 9 kj mol 1 Yes, ΔG is negative. 0.0 kj K mol 1 1 4.15 4.16 5.11 J K 1 0.95 J K mol 1 1 4.9 0.41 g 4.0 17 J xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 4.1 (a) Yes 4. 4. (a) 0.46 mol ATP 8.1 molecules of ATP CHAPTR 5 Density of cell 1 W m Density of battery 150 kw m The battery. Physical quilibria: Pure Substances 5.1 Rhombic sulfur 5. No 5. (a) +.0 kj mol 1 1.50 J mol 1 5.14 0.758 Pa 5.15 5.16 5 K 5.17 (a) 6.7 kj mol 1 1 5.18 (a) 5.19 (a) Yes CHAPTR 6.0 Torr or more The Properties of Mixtures 6.1 886.8 cm 5.4 +14 kj mol 1 6. 96.9 cm 5.5 (a).7 kj mol 1.0 kj mol 1 6. 6.4 1.8 kj mol 1.61 J mol 1 5.6 5.7 7 K 4. kj mol 1 6.5 (a) 1.1 kj mol 1 4.8 J K mol Yes. 1 1 5.8.5 kj mol 1 6.7 4.99 kpa 5. (a) 1.1 kg 15 kg 1.1 g 6.8.0 kpa 6.9 6.4 kpa 5.11 (a) 14.6 bar K 1 15.6 bar. 5.1 (a) 1.69 kj mol 1 7 K 5.1 8.0 xford University Press, 009. All rights reserved. 6. 4.8 6.11 18 kpa 6.1 (a) 1. mmol dm 17.0 mmol dm

ANSWRS T ND F CHAPTR XRCISS 6.14 6.18 6.19 4.5 mmol dm 5.6 kj mol 1 59.1 g mol 1 6.0 0.068ºC 6.1 0.40ºC p 7. (a) K p CCl C p p ps K p p Cl Cl S p K p p p K p H Br HBr 6. 6. 07 g mol 1 * r( p p) 1 cp K = * ( r p p c 1 cp. 7. 7.4.1 7.5 (a) 14.4 kj mol 1 11 5. 8.5 6.4 0.11 C 7.6.4 kj mol 1 6.5 86.4 kg mol 1 7.7.01 6.6 1.9 kg mol 1 6. (a) 5% tin by mass 6.8 0.5 No Ag Sn in the sold 0% Ag Sn by mass CHAPTR 7 Chemical quilibrium: The Principles p 7.1 (a) Q CH CCH FeS Q PbS K HCl p 6 C 5 p H CuCl Q CuCl 4 4 7.8 7.9 46 1.8. 7. K 1 45 kj mol 1 7.11 K G1P.5 7.1 (a) 7.1 7.14 7.15 K G6P. K GP 6 48. kj mol 1 66.1 kj mol 1 0 kj mol 1 0.7 kj mol 1 6.8 kj mol 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 7.16 (a) o 11 K (87 C) 97 K (14 C) 7. 7.6 +1. kj mol 1 4.7 bar 7.17 1.50 K 7.18 0.001 7.7 (a) 0.016 mol dm 45% 7.0 (a), exergonic +, endergonic +, endergonic, exergonic 7.9 7.40 p 1/ 41.0 kj mol 1 7.1 (a) (e) 91.14 kj mol 1 594.6 kj mol 1 66.8 kj mol 1 99.8 kj mol 1 415.80 kj mol 1 1 7. (a) 5.1 kj mol, K > 1 1 +5.78 kj mol, K < 1 1 178.6 kj mol, K > 1 7. (a) 1 1.55 kj mol, K>1 1 (e) 5798 kj mol, K >1 7.4 (a) 7.6 5 1.1 kj 5 1.0 kj 4.8 kj 4.1 kj 49.8 kj mol 1 7.41 (a) 7.4 (a) CHAPTR 8 (a) 5.9 kj mol 1 5.9 kj mol 1 (1) 9.4 () 1.08 (1) () 161 kj mol 1 1.9 kj mol 1 0.9 kj mol 1 +48 J K mol 1 1 Chemical quilibrium: quilibria In Solution 8.1 H S H H HS 4 4 acid base acid base 1 1 7.7 7.8 7.9 1 817.90 kj mol 5.1 kj mol 1 6 kj mol 1 HF H H F acid b ase a c id ba s e 1 1 7. 16.8 J K mol 1 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS C H NH H H C H NH acid 1 base acid base1 + 6 5 6 5 8.18 (a) 1.6% 0.%.4% 8..71 H P H H HP 4 4 acid base acid base 1 1 8. (a) 6.54.1 1.49 (e) HCH H H HC acid 1 base acid base1 (f ) NH NH H H NH NH acid 1 base acid base1 8.5 (a) 0 5.01 8.7 (a).9 4.6 1.59 5 1.5 cm of 0. M NaH aq 4.74 (e) 5.0 cm 8.6 8.7 rh ln R 57.1 kj mol 1 (f) 8.7 8.8 (a) 4.75 5.04 8.9 8.0 8.1 9. 8.14 4.77 8.15 none of the Br is protonated 8.16 (a) 8. 4.78 4.15 8.9 (a) 4 5 11.5 1. 5 6 8 (e) 5 7 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 8.1 (a) 5.1 ph 5.0 ph 9.0.7 8. 8.00 8.4 (a) H P 4 and NaH P 4 NaH P 4 and Na HP 4, or NaHS and Na S CHAPTR 9 Chemical quilibrium: lectrochemistry 9.1 1.5 9. (a).7 g.9 g 9. 1/ 9.5 B.01 8.5 (a) K s = [Ag + ] [I ] 9.6 1 1.8 ms m mol 8.6 (a) K = [Hg ] [S ] + s K s = [Fe + ] [H ] + K = [Ag ] [Cr ] 8.7 (a) 8.8 8.9 8.40 (a) s 4 5 1.0 mol dm 4 1. mol dm 11 9. mol dm 7 6.9 mol dm 5.5 mol dm. mol dm 7 1.6 mol dm.5 mol dm 161 kj mol 1 7 1.5 mol dm S S 5 e Increases. sh 1 1 R T T 9.7 9. 9.11.70 9.1 4.9 9.14 1 7.6 ms m mol 5 1.6 M 440 kj mol 1 9.15 8 mv 9.16 1.18V 9.17 (a) R: Ag + (aq, b R ) + e Ag(s) L: Ag + (aq, b L ) + e Ag(s) R L: Ag + (aq, b R ) Ag + (aq, b L ) R: H + (aq) + e H (g, p R ) L: H + (aq) + e H (g, p L ) R L: H (g, p L ) H (g, p R ) R: Mn (s) + 4 H + (aq) + e Mn + (aq) + H (l) L: [Fe(CN) 6 ] (aq) + e [Fe(CN) 6 ] 4 (aq) R L: Mn (s) + 4 H + (aq) + [Fe(CN) 6 ] 4 (aq) Mn + (aq) + [Fe(CN) 6 ] (aq) + H (l) xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS R: Br (l) + e Br (aq) L: Cl (g) + e Cl (aq) R L: Br (l) + Cl (aq) Cl (g) + Br (aq) (e) R: Sn 4+ (aq) + e Sn + (aq) L: Fe + (aq) + e Fe + (aq) R L: Sn 4+ (aq) + Fe + (aq) Sn + (aq) + Fe + (aq) (f) R: Mn (s) + 4 H + (aq) + e Mn + (aq) + H (l) L: Fe + (aq) + e Fe(s) R L: Fe(s) + Mn (s) + 4 H + (aq) Fe + (aq) + Mn + (aq) + H (l) 9.18 (a) (e) (f) RT ln b F b RT L R RT p ln F p [Mn ][Fe(CN) ] + 6 ln 4 4 F [H ] [Fe(CN) 6 ] 9.19 (a) v p [Br ] F [Cl ] RT Cl ln RT [Sn ][Fe ] F [Sn ][Fe ] ln 4 RT [Fe ][Mn ] F [H ] ln 4 v v 4 v (e) v (f) v 1 9.0 (a) 0 0 (e) 0.87 V 0.7 V 0.6 V R L (f) 1.67 V 9.1 (a) 0.08 V 0.7 1. V +0.695 V (e) +0.54 V (f) 0.6 V 9. (a) 1. V 1.11 V 9. (a) partial oxidation of methane occurs at the cathode. 0.09 V 9.4 (a) 0.94 V 9.5 (a) decreases, \ 1.51 0.0947 ph RT [Ag ] L ln F [Ag ] R increases, RT R ln F pl increases, RT p + 6 ln + 4 4- F [H ] [Fe(CN) 6 ] [Mn ][Fe(CN) ] increases, [Br ] p F [Cl ] RT Cl ln (e) decreases, RT [Sn ][Fe ] F [Sn ][Fe ] ln 4 (f) increases, RT [Fe ][Mn ] F [H ] ln 4 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 9.6 (a) decreases decreases increases increases (e) (f) no effect 9.7 (a) 1.0 V 1.19 V 9.8 (a) 1.55 V 9.9 (a) (i) decreases (ii) decreases chlorinespontaneously oxidizes water to oxygen under both acidic and basic conditions (e) (f) 9.0 (a) 94 kj mol 1 788 kj mol 1. +75 kj mol 1 91 kj mol 1 91 kj mol 1. +498 kj mol 1 440 kj mol 1 +9.7 kj mol 1 1 kj mol 1 9.1 (a) 0.4 V +0.45 V 9.6 (a) 0.6111 V 0. V. 9.7 (a) 9.8 cell 0.41 (e). (e) (f) 9 6.5 7 1. RT ln a a HC H cell F a C 1 4 K e 7. 5 1.0 8. 7 1.6 9.9 (1) 1.80 () 9.04 7 9.40 0.78 9.41 0.7 V RT a ln 6F a a 9.4 (a) 9.19 mol dm 8.45 17 CHAPTR + Cr 14 + Cr 7 H 9. Chemical Kinetics: The Rates of Reactions 9. 0.7 V.1.1 mmol dm 9.4 (a) 667 kj mol 1 604 kj mol 1 9.5 0. V..4.5 1 0.80 mol dm s. 6 1 mol dm s 1 1 mol dm s xford University Press, 009. All rights reserved..6 1/ 1 kpa s

ANSWRS T ND F CHAPTR XRCISS.7.1.7 dm mol s 1.1 s 7 1 1 4 1.4 98.86 K.5.6 a 5 kj mol 5.9 kj mol 1 1.1 7.7 s 5 1.8 11 kj mol 1.14 1.09 dm mol s 1 1.9 1.6 kj mol 1.15 1.1 s 4 1.40 47.8 kj mol 1.16.17 (a).19 Pa s 6 1 1 0.014 kpa s 1 1.5 s.18 (a) v k ICl H r 1 1 0.16 dm mol s.0 moldm s 6 1. B A k ta / 1 k ta.6 1 0 0 r 0 r 0 1. s.7 067 a 0 a..41 (a).4.4.44.45 1.6 0. 5.5 1. 4 dm mol s.1 nm 11 1 1 16 kj mol 1 S 0 CHAPTR 11 Accounting for the Rate Laws.8 (a) 0.6 μg 0.16 μg 11.1 5 1 7.5 s.9 6 s.0 (a).1 6.8 s. (a) 0.18 mol dm 0.095 mol dm 1.86 a. 7.1 s. 1. (a) a = 4 kj mol 15 1 A 1.1 mol dm s 4 1 1 11. (a) 1.8 mol dm s 1 1 4.00 mol dm s 11. 9.1 d 11.4 The reaction is first order in H 0 and in Br, and second order overall 1/ 11.5 11.7 v k k A B where k k ( K r,eff r,eff b kk 1 k 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 11.8 k A r,eff where k r,eff a kk a bm k M k b 11. 1 1.6 mmol dm s 11.9 k r,eff A 11.11 where k r,eff 6 1 1 1.89 Pa s 11.1 (a) 6.61 m mol s 11.1 (a) 11.14 (a) 7 h 11.15 (a) A M A M ka km kb k k k 6 1 1 0 m mol s 7 1 1 5. mol m s 11 1.6 mol.7 h.0 a A M b 8 1 9 1 6. m s 9 1 1.6 m s 11.4 6 1 1 7.9 dm mol s k a 11.7 AH A H initiation kb A B C propagation kc AH B A D propagation kd A B P termination CHAPTR 1 Quantum Theory 1.1 1. 1. 1.5 (a) 1.6 19.05 J 4 1 8.6 cm 11 1 8.4 s 18 1 1.91 s 18 1 1.91 s.0 s 11.16 11.17 11.18 11.19 11.0 4 8.55 a 6 1 steps 16.8 kj mol 1 5.6 1.7 1. 9 1 6.90 s 6 1 1. m s 1 1.11 (a) 6.6 m 9 6.6 m 99.7 pm (a) Concentration: [A ] k Rate equation: kk k k r k k r1 r r k r1 HA + BH HA + BH a b 11.1 HAH B a B k r HA B k r HA 1.1 (a) 1. nm 9 pm.88 pm 1.1 6.5 m 1.14 (a) 1. kg m s 7 1 9.5 kg m s 4 1.1 kg m s 6 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 1.16 1.17 (a). m s 4 1 4 6.14 N 614 ppa 0.45 h 1.7 1.8 1.9.91 J 1.05 J 0.04 N m 1 1.18 50.6 nm 1.19 1.0 1. (a) 15 1.74 J d 4 ax m dx 1.77 4 1. 0.90 nm 5.9 5 1.40 (a) 1 1 6.89 s 4.5 μm CHAPTR 1 Atomic Structure 1.1 4.96 nm 1. 6 1. (a) 1 1 1 7414 cm 057 cm 684 cm 19 1.6 J 1.4 1.5 1.6 1.8.1 m s 9 1 6 1.0 m 5 1 5.8 m s 9.84 J 1.4 7 cm 1 1.5 n1 and n 4 1.8 1.1 ev 1.9 16 orbitals 1.9 L/ 4 and L / 4 0 1.0 (a).17 J 1.1 9. μm 1 L 1. 1.4 μm 1.5 (a) 1/. 4.4 kg m 1.55 mm 47 1. All lines fit (a) n 6 17 nm, 750 nm, 5908 nm, 519 nm, ¼ 908 nm at n 15, converging to 8 nm as n 1.11 09.00 nm 1.1 (a) 97.1 nm 1 74 19 cm or.40 ev 1.6 11 1 8.79 s 1.1 (a) R Li + 9 740 cm 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 1.14 r 0.60 a0 1.16 ½ 1.17 (a) 1 1 17 175 cm, 185 186 cm, 1 987660 cm or 1.45 ev 1. 5 5.1 5 1.0 (a) Forbidden Allowed Allowed Forbidden (e) Allowed (f) Forbidden 1.19 Sin θ goes to zero at θ = 0 and 180 cos θ goes to zero at 90 and 70 1.0 (a) ang. mom. 0 ang. mom. 0 ang. mom. 6 ang. mom. (e) ang. mom. 1.1 (a) g 1 g 9 g 49 1. (l + 1) 1. (a) Allowed Forbidden Allowed CHAPTR 14 The Chemical Bond 14. (σ-bond) (1) () () (1) 1 pza pzb pza pzb (π-bond) (1) () () (1) pxa pxb pxa pxb (π-bond) (1) () () (1) pya pyb pya pyb 1. I 1 ea 14.4 6 1 1.87 J mol 1.4 14.0 ev 1.6 F 1.7, 1, and 0 1.8 (a) 1 level levels 1 level levels 1.9 Ti + : [Ar]d (a) F 5 xford University Press, 009. All rights reserved. h(1) () h() (1) 14.5 σ1 1 1sH1 1 1sH1 h (1) () h () (1) σ 1sH 1sH h (1) () h () (1) σ 1sH 1sH h (1) () h () (1) 14.8 times. 14. 45 14.1 (a) σ4 4 1sH4 4 1sH4 Li 1σg b 1 Be 1 σg 1σ u b 0 4 C 1 σg 1σ u 1π u b

ANSWRS T ND F CHAPTR XRCISS 14.1 14.6 14.7 + > > > + (a) H 1σ 1σ b 1 1 g u 4 N 1σ g 1σ u 1π u σ g b 4 1σ g 1σ u σg 1π u 1π g b 14.14 (a) 4 C 1σ σ* 1π σ b 4 1 N 1σ σ* 1π σ π* b 5 4 CN 1σ σ* 1π σ b 14.15 C 14.16 C and CN are stabilized by anion formation. N,, and F are stabilized by cation formation. 14.17 C 14.14 XeF + will have a shorter bond length than XeF 14.19 (a) g inapplicable g u 14.1 (a) g 14. N u g u If v is even, ψ v is g. If v is odd, ψ v is u. 14.4 F F F 14.5 F F F 14.0 (a) nonpolar polarized 14.4 molecular oribtals 14.5 1 (a) / hc ~ 40000 cm 5.0 ev / hc 6070 cm 1 7.5 ev deloc CHAPTR 15 Molecular Interactions 15.1 1.9 D 0 6. C m 15. nonpolar 15. (a) 0.7 D 0.4 D 0 15.4 1.6 D 15.5 (a) 0.8 D 0.4 D 0 15.6 (a) 1.414 D.45 D 1.06 D 1.70 D 15.8.50 D 15. (a) 476 kj mol 1 87.4 kj mol 1 15.1 (a).7 kj mol 1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS Yes. 15.14 196 pm 15.15 0.65 J mol 4. J 1 0.14 kpa 16.16 5.8 cm 16.17 45 mn m 1 16.18 97 mmol m 15.16 15.17 15.18 1.8 J 11 J mol 7 1 4. J mol 4 kj mol 1 1 CHAPTR 17 Metallic, Ionic, and Covalent Solids 17.1 (a) n-type p-type 15.0 R 461. pm 17. metallic condusctor CHAPTR 16 Materials: Macromolecules and Aggregates 17.6 17.7 500. kj mol 1 149.8 kj mol 1 16.1 (1) 95 kg mol 1 () 97 kg mol 16. (a) 18 kg mol 16. 1.7 16.4 44 16.5 1 1 0 kg mol 1 1.1 kg mol 16.6 (a) 880 nm 1.1 nm 16.8 4 1. 17.8 17.9 1.06 Q Nze 48 d 17. 6.0 K 17.16 d111 0 pm 0 d11 4 pm d0 57 pm 17.17 d1 15 pm d6 70.1 pm 16.11 16.1 5.0 S S 1 1 8K S total S and 4K 1 1 1 8K S 4K total total 17.18 66.1 pm 17.19 bbc unit cell 17.0 8.97 g cm 17. 0.9069 16.15 (a) 1.4 kpa xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 17.4 17.5 (a) 8 0.740 g cm 6 50 nm 600 nm 18.8 18. s e d / RT 0 1/ mkt A 5 kj mol 1 17.6 (a) 1 6 44 nm 600 nm 17.7 (a) less dense 17.8 9% V.96 m 8 d.41 g m 17.9 (a) N 4 4.01 g cm 17.0 (a) 0 pm 1 pm CHAPTR 18 Solid Surfaces 18. 0.088 bar 18. 5 1.1 s 6 18.1 18.1 18.16 45 s 1 p K 1 1/ ( Kp) 1 ( Kp) 1/ 18.17 (a) 611 kj mol 1 9. s 18.18 (a) 18.19 0.45 1 1 91.7 a 0.17 ms 18. 155 mv 18. 1.68 ma cm 18.4 (a) 0.1mAcm 5.41mAcm 9 1.4 Acm 18.4 1.15 18.5 (a) 1 1.1 s 18.5 (a) 15 1 4.9 s 16 1 1.6 s 7 1.1 s 18.6 0.4 49 m 18.7 (a) 0.060 kpa 4.9 kpa CHAPTR 19 Spectroscopy: Molecular rotations and vibrations 19.1 (a) 6.78 14 s -1 = 6.78 14 Hz.6 4 cm -1 xford University Press, 009. All rights reserved.

ANSWRS T ND F CHAPTR XRCISS 19. (a).94 - cm -1.40 m 19. 4 19.4 (a) 4.601 kg m 48 9.196 kg m 19.5 (a) 19.6 (a) 19.8 (a) 19.9 (a) Yes 48 7.15 kg m 46 46 7.156.67 kg m 1 1.84 Hz 11 9.16 Hz 1.17 Hz 1.17 Hz I 4m R B 9.66 Hz 9 5.15 Hz Could not be used. Yes Yes Yes (e) No 19. All will show 19.16 1 060 cm - 19.17 116. pm 19.18 (a) 16. pm 19.19 (a) 194 GHz B 0.085 cm D 6. cm 19.0 (a) 116.8 pm 155.97 pm 1 8 1 19.1 (a) 0.999 999 909 660 nm 19. (a) 19. (a) 5 ps 7 1 6.6 m s 7 1.97 m s 5 8.4 K 5. ps 1.6 ps 1 19.4 (a) 5 cm. 19.5 (a) 1 0.7 cm. 1 4.49 Hz 1 4.9 Hz 19.11 89 19.1 17 19.6 19.9 9 N m 1 700.6 cm 1 19.1 (a) 66 GHz, 17 GHz, 1908 GHz 1.1 cm 1 1 1 1 1.1 cm, 4.4 cm, 6.6 cm, 19.14.1 pm 19.15 Lower xford University Press, 009. All rights reserved. 19.0 19.1 (a) 4 HCl, C, H, (e) CH CH, (f) CH, and (g) CH C1 48 54 4

ANSWRS T ND F CHAPTR XRCISS CHAPTR 0 lectronic Transitions and Photochemistry 0.1 (a) 1.48 dm mol cm 4 1 1 0.98% 0. Absorbance: 0.658 Longer Cell: 1. Transmittance: 0.048 0.5 4 s or 0.4ns CHAPTR 1 Spectroscopy: Magnetic Resonance 1.1 1. 4 4.64 J 6 1.00 J mi 0. μg dm 1. (a) 1 T Hz 1 As kg 0.4 c c A B 0.56 mol dm 0.16 mol dm 0.5 nly two solutes in equilibrium with each other are present. 1.4.6 1.5 (a) 8.96 4.69 0.6 Lengthen. Blue. 1.6 v 9.48 GHz 0.04 m 0.11 19 16.0 kj 1.7 (a).9 5 7. 6 0.1 (a) 19.1 J 6.8 5 m s -1 0.1.0eV, 1.98 ev, and 15.99 ev 0.14.0 0.15.80 0.16 Molecules destroyed: 1.47 19 s -1 Chemical destroyed:.4-5 mol s -1 0.17 Triplet state 0.19 0.1 0. 0.4 18 1.7 mol dm s 0.4 R0 5 nm 1 1 xford University Press, 009. All rights reserved. 1.8 00.5 MHz 1.9 4.69 MHz 1. 18.79 T 1.11.17 khz 1.1 (a) 9.1 µt 8 µt 1.1 (a).4 khz 6.0 khz 1.14 1: 7 : 1:5:5: 1: 7 :1 1.15 (a) quintet1: : : :1 septet1:: 6: 7 : 6::1

(f (e)) NH Atkins & de Paula: lements of Physical Chemistry, Fifth dition NH H H NH HCH H NH H HC acid ANSWRS T ND F CHAPTR XRCISS 1 base acid base 1 base acid base1 1 1 1..6 s 4.1 (a). [] 0 v 1. [I] K v 1.4 00 0 I 7 6..1 (a) 4.816 4.480.14 T 8.96 K 1.5 005 1.7 (a) 1.9 mt 1.01T CHAPTR Statistical Thermodynamics.15 (a) 19.5 65.17.0 15e e / kt / kt 11.5 J K mol 1 1 S.1 0.7.1 9.57 J K 15 1. (a) 0.9999895 0.9998955. 0.99849.4 1.75.5.7 kt.6 (a) 16e e q 1 / 5 / kt. 191.4 J K mol 1 1. (a) S (Xe) > S.4.5.6 (Ne) S (D ) > S (H ). S (Graphite) > S 40 kj K mol 1 1 56.9 kj mol 1 (Diamond) ( q / N ) K ( q / N )( q / N ) NH,m A / RT N,m A H,m A e.7 (a) 1.9 7.8.7 1.7 5.8 (a) 5 6.71.8 1.9 11.9 T 1776 K. (a) 1.401.147 xford University Press, 009. All rights reserved.