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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1 ANSWRS T ND F CHAPTR XRCISS INTRDUCTIN N % 0..6 kj J 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 kj R 0.6. kj 0.. glucose molecules J octane molecules J myoglobin molecules 0.9 (a) J kj mol M / Vm 0. (a) GJ 19.4 J kj mol 0.1 (a) 8. Torr 0.96 atm 0. atm Pa mmol dm 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 bar mol kg atm 0.15 (a) 1.5 Pa 5.6 Pa 0.16 Differ by as much as 1 part in (a) Pa Torr kg kg CHAPTR 1 The Properties of Gasses kpa 1..5 kpa xford University Press, 009. All rights reserved.
2 ANSWRS T ND F CHAPTR XRCISS mmol bar atm c c c CH4 CH4 CH4 79 K m s 1 15 K 645 m s K 1.41 km s bar kpa K K 1. (a) m 178 m 0.50 m dm (a) 6.7 atm. 1. dm 61. kpa Torr 1.1 (a) 7 K Pa m s Pa μm 1.5 (a) 1 5. s 5. s s (a) 6.5 s s s s 1.8 (a) 6.8 nm 68 nm 7 mm g mol Independent of temperature (a) 1.0 (a) 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 K.8 km s (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.
3 ANSWRS T ND F CHAPTR XRCISS 1. a B = b and C b RT.1 (a) 0 J K mol J K mol (a) 4.60 dm mol 1.4 (a) 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 kj kj.7 (a) (a) 78 J 1.0 J.7 J K kj J K g J K mol J (a) J 9. kj 6.1 s kj kj J 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 J mol J mol 1 CHAPTR Thermodynamics: Applications of the First Law mj mol kj. (a).44 kj.6 kj xford University Press, 009. All rights reserved.
4 ANSWRS T ND F CHAPTR XRCISS 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 MJ mol 1 1 kj mol kj mol kj mol kj mol 1.48 kj mol kj kj mol 1 8 kj mol 1.11 (a) kj mol 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) GJ 1560 kj mol kj g 1 thane is a less efficient fuel kj mol 1 85 kj mol 1 4 kj mol 1 5 kj mol 1.0 (a) 4. kj K K kj mol 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 kj mol kj mol 1.88 kj mol kj mol kj mol kj mol 1 fus subh positive kj mol 1 xford University Press, 009. All rights reserved.
5 ANSWRS T ND F CHAPTR XRCISS.5 (a) Decrease Decrease Increase.6 (a) Increase Increase CHAPTR 4 Thermodynamics: the Second Law (a) 0.4 J K kj K kj K 1 4. (a) 45.1 kj J K 1 14 J K mol.91 dm (a) (a) 87.8 J K mol J K mol. 79 J K mol J K mol. +4 kj K mol f 4.0 kn ln V Vi J K mol 4. (a) positive negative positive (a) 86.1 JK mol JK mol 15.1 J K mol J K mol 1 1 (e) 51.0 J K mol J K kj K J K J K (a) J K 1 09 J K % high 4.6 (a) 0.75 J K J K J K mol kj T i J K mol (a) 9 kj mol 1 Yes, ΔG is negative. 0.0 kj K mol J K J K mol g J xford University Press, 009. All rights reserved.
6 ANSWRS T ND F CHAPTR XRCISS 4.1 (a) Yes (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 J mol Pa K 5.17 (a) 6.7 kj mol (a) 5.19 (a) Yes CHAPTR 6.0 Torr or more The Properties of Mixtures cm kj mol cm 5.5 (a).7 kj mol 1.0 kj mol kj mol 1.61 J mol K 4. kj mol (a) 1.1 kj mol J K mol Yes kj mol kpa 5. (a) 1.1 kg 15 kg 1.1 g kpa kpa 5.11 (a) 14.6 bar K bar. 5.1 (a) 1.69 kj mol 1 7 K xford University Press, 009. All rights reserved kpa 6.1 (a) 1. mmol dm 17.0 mmol dm
7 ANSWRS T ND F CHAPTR XRCISS mmol dm 5.6 kj mol g mol ºC ºC 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 g mol 1 * r( p p) 1 cp K = * ( r p p c 1 cp (a) 14.4 kj mol C kj mol kg mol kg mol 1 6. (a) 5% tin by mass 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 K 1 45 kj mol K G1P (a) K G6P. K GP kj mol kj mol 1 0 kj mol kj mol kj mol 1 xford University Press, 009. All rights reserved.
8 ANSWRS T ND F CHAPTR XRCISS 7.16 (a) o 11 K (87 C) 97 K (14 C) kj mol bar K (a) mol dm 45% 7.0 (a), exergonic +, endergonic +, endergonic, exergonic p 1/ 41.0 kj mol (a) (e) kj mol kj mol kj mol kj mol kj mol (a) 5.1 kj mol, K > kj mol, K < kj mol, K > 1 7. (a) kj mol, K>1 1 (e) 5798 kj mol, K >1 7.4 (a) kj kj 4.8 kj 4.1 kj 49.8 kj mol (a) 7.4 (a) CHAPTR 8 (a) 5.9 kj mol kj mol 1 (1) 9.4 () 1.08 (1) () 161 kj mol kj mol kj mol J K mol 1 1 Chemical quilibrium: quilibria In Solution 8.1 H S H H HS 4 4 acid base acid base kj mol 5.1 kj mol 1 6 kj mol 1 HF H H F acid b ase a c id ba s e J K mol 1 1 xford University Press, 009. All rights reserved.
9 ANSWRS T ND F CHAPTR XRCISS C H NH H H C H NH acid 1 base acid base (a) 1.6% 0.%.4% H P H H HP 4 4 acid base acid base (a) (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) (a) cm of 0. M NaH aq 4.74 (e) 5.0 cm rh ln R 57.1 kj mol 1 (f) (a) none of the Br is protonated 8.16 (a) (a) (e) 5 7 xford University Press, 009. All rights reserved.
10 ANSWRS T ND F CHAPTR XRCISS 8.1 (a) 5.1 ph 5.0 ph (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 (a).7 g.9 g 9. 1/ 9.5 B (a) K s = [Ag + ] [I ] ms m mol 8.6 (a) K = [Hg ] [S ] + s K s = [Fe + ] [H ] + K = [Ag ] [Cr ] 8.7 (a) (a) s mol dm 4 1. mol dm mol dm mol dm 5.5 mol dm. mol dm mol dm.5 mol dm 161 kj mol mol dm S S 5 e Increases. sh 1 1 R T T ms m mol M 440 kj mol mv V 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.
11 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 (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 V V (e) V (f) 0.6 V 9. (a) 1. V 1.11 V 9. (a) partial oxidation of methane occurs at the cathode V 9.4 (a) 0.94 V 9.5 (a) decreases, \ ph RT [Ag ] L ln F [Ag ] R increases, RT R ln F pl increases, RT p + 6 ln 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.
12 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 kj mol kj mol 1 91 kj mol 1 91 kj mol kj mol kj mol kj mol 1 1 kj mol (a) 0.4 V V 9.6 (a) V 0. V. 9.7 (a) 9.8 cell 0.41 (e). (e) (f) RT ln a a HC H cell F a C 1 4 K e (1) 1.80 () V RT a ln 6F a a 9.4 (a) 9.19 mol dm CHAPTR + Cr 14 + Cr 7 H 9. Chemical Kinetics: The Rates of Reactions V.1.1 mmol dm 9.4 (a) 667 kj mol kj mol V 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
13 ANSWRS T ND F CHAPTR XRCISS dm mol s 1.1 s K.5.6 a 5 kj mol 5.9 kj mol s kj mol dm mol s kj mol s kj mol (a).19 Pa s kpa s s.18 (a) v k ICl H r dm mol s.0 moldm s 6 1. B A k ta / 1 k ta r 0 r 0 1. s a 0 a..41 (a) dm mol s.1 nm kj mol 1 S 0 CHAPTR 11 Accounting for the Rate Laws.8 (a) 0.6 μg 0.16 μg s.9 6 s.0 (a) s. (a) 0.18 mol dm mol dm 1.86 a. 7.1 s. 1. (a) a = 4 kj mol 15 1 A 1.1 mol dm s (a) 1.8 mol dm s mol dm s d 11.4 The reaction is first order in H 0 and in Br, and second order overall 1/ 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.
14 ANSWRS T ND F CHAPTR XRCISS 11.8 k A r,eff where k r,eff a kk a bm k M k b mmol dm s 11.9 k r,eff A where k r,eff Pa s 11.1 (a) 6.61 m mol s 11.1 (a) (a) 7 h (a) A M A M ka km kb k k k m mol s mol m s mol.7 h.0 a A M b m s m s 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 (a) J cm s s s.0 s a 6 1 steps 16.8 kj mol s m s (a) 6.6 m 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 m 1.14 (a) 1. kg m s kg m s kg m s 6 1 xford University Press, 009. All rights reserved.
15 ANSWRS T ND F CHAPTR XRCISS (a). m s N 614 ppa 0.45 h J 1.05 J 0.04 N m nm (a) J d 4 ax m dx nm (a) s 4.5 μm CHAPTR 1 Atomic Structure nm (a) cm 057 cm 684 cm J m s m m s 9.84 J cm n1 and n ev orbitals 1.9 L/ 4 and L / (a).17 J μm 1 L μm 1.5 (a) 1/. 4.4 kg m 1.55 mm 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 nm 1.1 (a) 97.1 nm cm or.40 ev s 1.1 (a) R Li cm 1 xford University Press, 009. All rights reserved.
16 ANSWRS T ND F CHAPTR XRCISS 1.14 r 0.60 a ½ 1.17 (a) cm, cm, cm or 1.45 ev (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 (a) ang. mom. 0 ang. mom. 0 ang. mom. 6 ang. mom. (e) ang. mom. 1.1 (a) g 1 g 9 g (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 J mol ev 1.6 F 1.7, 1, and (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 (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
17 ANSWRS T ND F CHAPTR XRCISS > > > + (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 (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 C C and CN are stabilized by anion formation. N,, and F are stabilized by cation formation C XeF + will have a shorter bond length than XeF (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 F F F 14.5 F F F 14.0 (a) nonpolar polarized 14.4 molecular oribtals (a) / hc ~ cm 5.0 ev / hc 6070 cm ev deloc CHAPTR 15 Molecular Interactions D 0 6. C m 15. nonpolar 15. (a) 0.7 D 0.4 D D 15.5 (a) 0.8 D 0.4 D (a) D.45 D 1.06 D 1.70 D D 15. (a) 476 kj mol kj mol (a).7 kj mol 1 xford University Press, 009. All rights reserved.
18 ANSWRS T ND F CHAPTR XRCISS Yes pm J mol 4. J kpa cm mn m mmol m J 11 J mol 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 kj mol kj mol (1) 95 kg mol 1 () 97 kg mol 16. (a) 18 kg mol kg mol kg mol 16.6 (a) 880 nm 1.1 nm Q Nze 48 d K d111 0 pm 0 d11 4 pm d0 57 pm d1 15 pm d pm S S 1 1 8K S total S and 4K K S 4K total total pm bbc unit cell g cm (a) 1.4 kpa xford University Press, 009. All rights reserved.
19 ANSWRS T ND F CHAPTR XRCISS (a) g cm 6 50 nm 600 nm s e d / RT 0 1/ mkt A 5 kj mol (a) nm 600 nm 17.7 (a) less dense % V.96 m 8 d.41 g m 17.9 (a) N g cm 17.0 (a) 0 pm 1 pm CHAPTR 18 Solid Surfaces bar s s 1 p K 1 1/ ( Kp) 1 ( Kp) 1/ (a) 611 kj mol 1 9. s (a) a 0.17 ms mv ma cm 18.4 (a) 0.1mAcm 5.41mAcm Acm (a) s 18.5 (a) s s s m 18.7 (a) kpa 4.9 kpa CHAPTR 19 Spectroscopy: Molecular rotations and vibrations 19.1 (a) s -1 = Hz.6 4 cm -1 xford University Press, 009. All rights reserved.
20 ANSWRS T ND F CHAPTR XRCISS 19. (a).94 - cm m (a) kg m kg m 19.5 (a) 19.6 (a) 19.8 (a) 19.9 (a) Yes kg m kg m Hz Hz 1.17 Hz 1.17 Hz I 4m R B 9.66 Hz Hz Could not be used. Yes Yes Yes (e) No 19. All will show cm pm (a) 16. pm (a) 194 GHz B cm D 6. cm 19.0 (a) pm pm (a) nm 19. (a) 19. (a) 5 ps m s m s K 5. ps 1.6 ps (a) 5 cm (a) cm Hz Hz N m cm (a) 66 GHz, 17 GHz, 1908 GHz 1.1 cm cm, 4.4 cm, 6.6 cm, pm Lower xford University Press, 009. All rights reserved (a) 4 HCl, C, H, (e) CH CH, (f) CH, and (g) CH C
21 ANSWRS T ND F CHAPTR XRCISS CHAPTR 0 lectronic Transitions and Photochemistry 0.1 (a) 1.48 dm mol cm % 0. Absorbance: Longer Cell: 1. Transmittance: s or 0.4ns CHAPTR 1 Spectroscopy: Magnetic Resonance J 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 (a) Lengthen. Blue. 1.6 v 9.48 GHz 0.04 m kj 1.7 (a) (a) 19.1 J m s eV, 1.98 ev, and ev Molecules destroyed: s -1 Chemical destroyed:.4-5 mol s Triplet state mol dm s 0.4 R0 5 nm 1 1 xford University Press, 009. All rights reserved MHz MHz T khz 1.1 (a) 9.1 µt 8 µt 1.1 (a).4 khz 6.0 khz : 7 : 1:5:5: 1: 7 : (a) quintet1: : : :1 septet1:: 6: 7 : 6::1
22 (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 base s 4.1 (a). [] 0 v 1. [I] K v I (a) T 8.96 K (a) 1.9 mt 1.01T CHAPTR Statistical Thermodynamics.15 (a) e e / kt / kt 11.5 J K mol 1 1 S J K (a) kt.6 (a) 16e e q 1 / 5 / kt J K mol 1 1. (a) S (Xe) > S (Ne) S (D ) > S (H ). S (Graphite) > S 40 kj K mol kj mol 1 (Diamond) ( q / N ) K ( q / N )( q / N ) NH,m A / RT N,m A H,m A e.7 (a) (a) T 1776 K. (a) xford University Press, 009. All rights reserved.
Atkins & de Paula: Elements of Physical Chemistry, Fifth Edition ANSWERS TO END OF CHAPTER EXERCISES E F. E0.19 (a) θ / C= 100 θ / C.
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) θ / C= 0 θ / C θ 9 F / F= 1 5 θ / C 0.0 θ P / P = 7.09 ( θ / C + 09.9) (a) θ P / P = 7.09 ( T / K 6.5) θ
2. Chemical Thermodynamics and Energetics - I
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