Solutions to a) exercises

A horizontal bar over the last digit in some answers denotes an E2.17(a) ΔL H 7 (SrI2,s) = 1953 kJ mol −1
insignificant digit. E2.18(a) −4564.7 kJ mol −1
E2.19(a) Δ f H[(CH2)3,g] = +53 kJ mol −1, Δ r H = −33 kJ mol −1
E2.20(a) ΔcU 7 = −5152 kJ mol −1, C = 1.58 kJ K −1, ΔT = 205 K
Chapter 1 E2.21(a) +65.49 kJ mol −1
E1.1(a) (a) 24 atm (b) 22 atm E2.22(a) −383 kJ mol −1
E1.2(a) (a) 3.42 bar (b) 3.38 atm E2.23(a) (a) Δ r H 7 (3) = −114.40 kJ mol −1, Δ rU = −111.92 kJ mol −1
E1.3(a) 30 lb in−2 (b) Δ f H 7 (HCl,g) = −92.31 kJ mol−1,
E1.4(a) 4.20 × 10 −2 atm Δ f H 7 (H2O,g) = −241.82 kJ mol −1
E1.5(a) 0.50 m3 E2.24(a) −1368 kJ mol −1
E1.6(a) 102 kPa E2.25(a) (a) −392.1 kJ mol −1 (b) −946.6 kJ mol −1
E1.7(a) 8.3147 J K −1 mol −1 E2.26(a) −56.98 kJ mol−1
E1.8(a) S8 E2.27(a) (a) Δ r H 7 (298 K) = +131.29 kJ mol −1,
Δ rU 7 (298 K) = +128.81 kJ mol−1
E1.9(a) 6.2 kg
(b) Δ r H 7 (378 K) = +132.56 kJ mol −1,
E1.10(a) (a) (i) 0.762 (ii) 0.238 (iii) 0.752 bar (iv) 0.235 bar
Δ rU 7 (378 K) = +129.42 kJ mol−1
(b) (i) 0.782 (ii) 0.208 (iii) 0.0099 bar (iv) 0.772 bar (v) 0.205
E2.28(a) −218.66 kJ mol−1
E1.11(a) 169 g mol −1
E2.29(a) −1892 kJ mol−1
E1.12(a) −273°C
E2.30(a) 0.71 K atm−1
E1.13(a) (a) (i) 1.0 atm (ii) 8.2 × 10 2 atm
E2.31(a) ΔU = 131 J mol −1, q = +8.05 × 10 3 J mol −1, w = −7.92 × 10 3 J mol −1
(b) (i) 1.0 atm (ii) 1.8 × 10 3 atm
E2.32(a) 1.31 × 10 −3 K −1
E1.14(a) a = 7.61 × 10 −2 kg m5 s−2 mol −2, b = 2.26 × 10 −5 m3 mol −1
E2.33(a) 1.⁄ × 10 3 atm
E1.15(a) (a) 0.88 (b) 1.2 dm3 mol −1
A ∂Hm D
E1.16(a) 140 atm E2.34(a) B E = −7.2 J atm−1 mol −1, q(supplied) = +8.1 kJ
E1.17(a) (a) 50.7 atm (b) 35.2 atm, 0.695 C ∂p F T
E1.18(a) (a) 0.67, 0.33 (b) 2.0 atm, 1.0 atm (c) 3.0 atm
E1.19(a) 32.9 cm3 mol −1, 1.33 dm6 atm mol −2, 0.118 nm
E1.20(a) (a) 1.41 × 10 3 K (b) 0.139 nm Chapter 3
E1.21(a) (a) T = 3.64 × 10 3 K, p = 8.7 atm (b) T = 2.60 × 10 3 K, p = 4.5 atm
E3.1(a) (a) 92 J K −1 (b) 67 J K −1
(c) T = 46.7 K, p = 0.18 atm
E3.2(a) 152.67 J K −1 mol −1
E1.22(a) 0.66
E3.3(a) −22.1 J K −1
E3.4(a) q = 0, ΔS = 0, ΔU = +4.1 kJ, ΔH = +5.4 kJ
E3.5(a) ΔH = 0, ΔH tot = 0, ΔStot = +93.4 J K −1
Chapter 2
E3.6(a) (a) q = 0 (b) −20 J (c) −20 J (d) −0.34‡ K (e) +0.60 J K −1
E2.1(a) On Earth: 2.6 × 10 3 J needed, on the moon: 4.2 × 10 2 J needed E3.7(a) (a) +87.8 J K −1 mol −1 (b) −87.8 J K −1 mol −1
E2.2(a) −1.0 × 10 2 J E3.8(a) (a) −386.1 J K −1 mol −1 (b) +92.6 J K −1 mol −1
E2.3(a) (a) w = −1.57 kJ, q = +1.57 kJ (b) w = −1.13 kJ, q = +1.13 kJ (c) 0 (c) −153.1 J K −1 mol −1
E2.4(a) p2 = 1.33 atm, w = 0, q = ΔU = +1.25 kJ E3.9(a) (a) −521.5 kJ mol −1 (b) +25.8 kJ mol −1 (c) −178.7 kJ mol −1
E2.5(a) (a) −88 J (b) −167 J E3.10(a) (a) −522.1 kJ mol −1 (b) +25.78 kJ mol −1 (c) −178.6 kJ mol −1
E2.6(a) ΔH = q = −40.656 kJ, w = 3.10 kJ, ΔU = −37.55 kJ E3.11(a) −93.05 kJ mol −1
E2.7(a) w = −1.5 kJ E3.12(a) −50 kJ mol −1
E2.8(a) (a) q = ΔH = +2.83 × 10 4 J = +28.3 kJ, w = −1.45 kJ, E3.13(a) (a) ΔS(gas) = +2.9 J K −1, ΔS(surroundings) = −2.9 J K −1,
ΔU = +26.8 kJ ΔS(total) = 0
(b) ΔH = +28.3 kJ, ΔU = +26.8 kJ, w = 0, q = +26.8 kJ (b) ΔS(gas) = +2.9 J K −1, ΔS(surroundings) = 0,
E2.9(a) 13⁄ K ΔS(total) = +2.9 J K −1
E2.10(a) w = −194 J (c) ΔS(gas) = 0, ΔS(surroundings) = 0, ΔS(total) = 0
E2.11(a) 22 kPa E3.14(a) 817.90 kJ mol −1
E2.12(a) Cp,m = 30 J K −1 mol −1, CV,m = 22 J K −1 mol −1 E3.15(a) η=1−
333 K
= 0.11, η = 1 −
353 K
= 0.38
E2.13(a) q p = +2.2 kJ, ΔH = +2.2 kJ, ΔU = +1.6 kJ 373 K 573 K
E2.14(a) w = −3.2 kJ, ΔU = −3.2 kJ, ΔT = −38 K, ΔH = −4.5 kJ E3.16(a) −3.8 J
E2.15(a) Vf = 0.00944 m3, Tf = 288 K, w = −4.6 × 10 2 J E3.17(a) −36.5 J K −1
E2.16(a) q = +13.0 kJ, w = −1.0 kJ, ΔU = 12.0 kJ E3.18(a) 12 kJ
 SOLUTIONS TO A) EXERCISES 949

E3.19(a) +7.3 kJ mol −1 E5.32(a) (b) 620 Torr (c) 490 Torr (d) xHex = 0.50 yHex = 0.72
E3.20(a) −0.55 kJ mol −1 (e) yHex = 0.50, xHex = 0.30
E3.21(a) +10 kJ
E3.22(a) +11 kJ mol −1
Chapter 6
Chapter 4 E6.1(a) nA = 0.9 mol, nB = 1.2 mol
E6.2(a) ΔG t −0.64 kJ
E4.1(a) (a) single phase (b) three phases (c) two phases (d) two phases E6.3(a) K ≈ 6 × 10 5
E4.2(a) 0.71 J E6.4(a) 2.85 × 10 −6
E4.3(a) −1.0 × 10 −4 K E6.5(a) (a) 0.141 (b) 13.5
E4.4(a) 4 E6.6(a) (a) Δ rG 7 = −68.26 kJ mol −1, K = 9.13 × 10 11 (b) K400 K = 1.32 × 10 9,
5.2 kJ mol −1 7
Δ rG 400 −1
K = −69.8 kJ mol
E4.5(a)
E4.6(a) 70 J mol −1 E6.7(a) −1
K = (0.0831451 K ) × K c T
E4.7(a) 2.71 kPa E6.8(a) (b) 0.33 (c) 0.33 (d) +2.8 kJ mol −1
E4.8(a) Δ fus S = +45.2‹ J K −1 mol −1, Δ fus H = +16 kJ mol −1 E6.9(a) K1 = 0.045, T2 = 15Ú K
E4.9(a) 31°C E6.10(a) Δ r H 7 = +2.77 kJ mol −1, Δ rG 7 = −16.5 J K −1 mol −1
E4.10(a) +20.80 kJ mol −1 E6.11(a) K = (0.0831451 K −1) × Kc T
E4.11(a) (a) +34.08 kJ mol −1 (b) 350.5 K E6.12(a) (a) K(25°C) = 1.17 × 10 6, Kc(25°C) = 4.72 × 10 4
E4.12(a) 281.8 K or 8.7°C (b) K(100°C) = 9.95 × 10 5, Kc(100°C) = 3.21 × 10 4
E4.13(a) 25 g s−1 E6.13(a) +12.3 kJ mol −1
E4.14(a) (a) 1.7 × 10 3 g (b) 31 × 10 3 g (c) 1.4 g E6.14(a) 50 per cent
E4.15(a) (a) +49 kJ mol −1 (b) 21fi°C (c) +101 J K −1 mol −1 E6.15(a) x borneol = 0.9663, x iso = 0.0337
E4.16(a) 272.80 K E6.16(a) (a) Δ r H 7 = 52.89 kJ mol −1 (b) Δ r H 7 = −52.89 kJ mol −1
E4.17(a) 0.0763 = 7.63 per cent E6.17(a) −14.4 kJ mol −1
E6.18(a) 1110 K (837°C)
E6.19(a) −1108 kJ mol −1
Chapter 5 E6.21(a) (a) +1.10 V (b) +0.22 V (c) +1.23 V
E5.1(a) 886.8 cm 3 E6.22(a) (a) Cd2+(aq) + 2 Br −(aq) + 2 Ag(s) → Cd(s) + 2 AgBr(s) (c) −0.62 V
E5.2(a) 56 cm3 mol −1 E6.23(a) (a) 6.5 × 10 9 (b) 1.4 × 10 12
E5.3(a) 6.4 × 10 3 kPa E6.24(a) (a) 8.5 × 10 −17 (b) 9.2 × 10 −9 mol dm−3 or 2.2 μg dm−3
E5.4(a) 1.3 × 10 2 kPa
E5.5(a) 85 g mol −1
E5.6(a) 3.8 × 10 2 g mol −1 Chapter 7
E5.7(a) −0.09°C E7.1(a) 0.024 m s−1
E5.8(a) Δ mixG = −0.35 kJ, Δ mix S = +1.2 J K −1 E7.2(a) 332 pm
E5.9(a) +4.71 J K −1 mol −1 E7.3(a) 700 pm
E5.10(a) (a) xA = 12 (b) 0.8600
E5.11(a) (a) 3.4 × 10 −3 mol kg−1 (b) 3.37 × 10 −2 mol kg−1 E7.4(a) λ /nm E/J Em /(kJ mol −1)
E5.12(a) 0.17 mol dm−3
E5.13(a) 0.135 mol kg−1, 24.0 g anthracene (a) 600 3.31 × 10 −19 199
E5.14(a) 87 kg mol −1 (b) 550 3.61 × 10 −19 218
E5.15(a) aA = 0.833, γA = 0.93, aB = 0.125, γ B = 0.12fi, aB = 2.8 (c) 400 4.97 × 10 −19 299
E5.16(a) pA = 32.2 Torr, pB = xB KB = 6.1 Torr, ptotal = 38.3 Torr, yA = 0.840,
yB = 0.160
E5.17(a) aA = 0.498, aM = 0.667, γA = 1.24, γ M = 1.11
E5.18(a) 0.90 E7.5(a) λ /nm Ephoton / J v/(km s−1)
E5.19(a) (a) 2.73 g (b) 2.92 g
E5.20(a) I = 0.060, CaCl2: γ± = 0.56, a(Ca2+) = 0.0056, a(Cl+) = 0.011 (a) 600 3.31 × 10 −19 19.9
E5.21(a) B = 2.01 (b) 550 3.61 × 10 −19 20.8
E5.22(a) x1 = 0.92, x 2 = 0.08, y1 = 0.97, y2 = 0.03 (c) 400 4.97 × 10 −19 24.4
E5.23(a) xA = 0.267, x B = 0.733, ptotal = 58.6 kPa
E5.24(a) (a) solution is ideal (b) yA = 0.830, yB = 0.1703 E7.6(a) 21 m s−1
E5.25(a) (a) 20.6 kPa (b) 0.668 (c) 0.332 E7.7(a) (a) 2.77 × 10 18 (b) 2.77 × 10 20
E5.26(a) (a) yM = 0.36 (b) yM = 0.80 (i.e., yO = 0.20). E7.8(a) (a) no electron ejection (b) 837 km s−1
E5.29(a) xB ≈ 0.26 and its melting point is labeled T2 ≈ 200°C. E7.9(a) (a) 6.6 × 10 −19 J, 4.0 × 10 2 kJ mol −1 (b) 6.6 × 10 −20 J, 40 kJ mol −1
n n (c) 6.6 × 10 −34 J, 4.0 × 10 −13 kJ mol −1
E5.31(a) (a) 76 per cent (c) c = 1.11, c = 1.46
na na E7.10(a) (a) 6.6 × 10 −29 m (b) 6.6 × 10 −36 m (c) 99.7 pm
950 SOLUTIONS TO A) EXERCISES

A 1 D
1/2 a0
E9.10(a) 5.24
E7.11(a) N= B E Z
C 2π F
E9.11(a) r = 2a0 /Z
E7.12(a) (1/2π) dφ
E9.13(a) θ = π/2, θ = 0, θ = 0
1
E7.13(a) E9.14(a) (a) forbidden (b) allowed (c) allowed
2
E9.15(a) 0.999 999 944 × 680 nm
E7.15(a) Δvmin = 1.1 × 10 −28 m s−1, Δqmin = 1 × 10 −27 m E9.16(a) (a) 27 ps (b) 2.7 ps
E7.16(a) 6.96 keV E9.17(a) (a) 53 cm−1 (b) 0.53 cm−1
G d 1J 1 Gd J E9.19(a) (a) [Ar]3d8 (b) S = 1,0, MS = −1,0, +1, MS = 0
E7.17(a) (a) H , K = − 2 (b) H , x 2 K = 2x
I dx x L x I dx L E9.20(a) (a) 52 , 32 (b) 72 , 52
E9.21(a) l=1
E9.22(a) L = 2, S = 0, J = 2
Chapter 8 E9.23(a) (a) 1,0, 3,1 (b) 32 , 12 , and 12 , 4, 2, 2
3
E9.24(a) D3, 3D2, 3D1, 1D2
E8.1(a) (a) 1.81 × 10 −19 J, 1.13 eV, 9100 cm−1, 109 kJ mol −1 E9.25(a) (a) J = 0, (b) J = 0, (c) J = 2,1,0
(b) 6.6 × 10 −19 J, 4.1 eV, 33 000 cm−1, 400 kJ mol −1 E9.26(a) (a) 2S1/2 (b) 2P3/2 and 2P1/2
E8.2(a) (a) 0.04 (b) 0 E9.27(a) (a) allowed (b) forbidden (c) allowed
h2
E8.3(a)
4L2
L 2A1 1 D Chapter 10
E8.4(a) , L B − 2E
2 C 3 2π F
E10.1(a) {A(1)px(2) + A(2)px(1)} × {B(3)py(4) + B(4)px(3)}
h λ E10.2(a) {s(1)pz(2) + s(2)pz(1)} × {α (1)β (2) − α (2)β (1)}
E8.5(a) = C
81/2 mec 81/2 E10.5(a) (a) 1σ g2 , b = 1 (b) 1σ g21σ u2 , b = 0 (c) 1σ g21σ u21π u4, b = 2
L L 5L E10.6(a) (a) 1σ 2 2σ 21π4 3σ 2 (b) 1σ 2 2σ 23σ 21π 4 2π1 (c) 1σ 2 2σ 21π 4 3σ 2
E8.6(a) , and
6 2 6 E10.7(a) C2
E8.7(a) −17.4 per cent E10.10(a) A cos θ − B sin θ
2kTmL2 1 E10.11(a) 0
E8.8(a) −
h2 2 E10.12(a) 1.4 eV, 2.2 × 10 −19 J
E8.9(a) 4.30 × 10 −21 J E10.13(a) 10.9fl eV, 1.76 × 10 −18 J
E8.10(a) 278 N m−1 E10.14(a) ψ+ = 0.97χF + 0.25χXe, ψ− = 0.25χF − 0.97χXe
E8.11(a) 2.64 μm E10.15(a) E bond = −18.1 eV, Eanti = −12.0 eV, ψ bond = 1.01χF − 0.36χXe,
E8.12(a) 8.3673 × 10 −28 kg, 1.6722 × 10 −27 kg, ω D = 93.3 THz ψanti = 0.16χF + 0.96χXe
E8.13(a) (a) 3.3 × 10 −34 J (b) 3.3 × 10 −33 J E10.17(a) (a) 3α + 23/2β (b) 3α + 3β
E8.15(a) ±0.525α or ±1.65α E10.18(a) (a) a 2ue1g e 2u, 7α + 7β, 7α + 7β (b) a 2u
2 4 1
e 1g , 5α + 7β
2 3

E8.16(a) ±α E10.17(a) (a) 14α + 19.314β (b) 14α + 19.448β

E8.17(a) 5.61 × 10 −21 J
1/2
A 1 D
E8.18(a) B E Chapter 11
C 2π F
E11.2(a) (a) R3 (b) C2v (c) D3h (d) D∞h
E8.19(a) 3.32 × 10 −22 J
E11.3(a) (a) C2v (b) C∞v (c) C3v (d) D2h
E8.20(a) 3.2 × 10 34
E11.4(a) (a) C2v (b) C2h
E8.21(a) 2.11 × 10 −22 J
E11.7(a) σh, i
E8.22(a) 4.22 × 10 −22 J
E11.12(a) dxy
E8.23(a) 1.49 × 10 −34 J s
E11.14(a) 2A1 + B1 + E
E11.15(a) (a) either E1u or A2u (b) B3u(x-polarized), B2u(y-polarized),
B1u(z-polarized)
Chapter 9
E9.1(a) 9.118 × 10 −6 cm, 1.216 × 10 −5 cm
E9.2(a) # = 3.292 × 10 5 cm−1, λ = 3.038 × 10 −6 cm, ν = 9.869 × 10 15 Hz Chapter 12
E9.3(a) 14.0 eV E12.2(a) (c) CH4 is inactive
E9.4(a) (a) 1 (b) 9 (c) g = 25 E12.3(a) 7.173 × 10 −47 kg m2, I|| will not change
E9.5(a)
2
N = 3/2 E12.4(a) I|| = 5.60 × 10 −47 kg m2, I⊥ = 6.29 × 10 −46 kg m2, Ã = 5.00 cm−1,
a0 ì = 0.445 cm−1, A = 1.50 × 10 11 Hz, B = 1.33 × 10 10 Hz
E9.6(a) 4a0, 0 E12.5(a) 4.09 × 10 11 Hz
E9.7(a) r = 0.35a0 E12.6(a) (a) 2.642 × 10 −47 kg m2 (b) 127.4 pm
E9.8(a) 101 pm and 376 pm E12.7(a) I = 4.442 × 10 −47 kg m2, R = 165.9 pm
E9.9(a) 〈V 〉 = 2E1s, 〈T 〉 = −E1s, E12.8(a) 232.1 pm
 SOLUTIONS TO A) EXERCISES 951

E12.9(a) R = 106.5 pm, R′ = 115.6 pm E14.13(a) 6.7 × 10 2 s−1

E12.10(a) 20 475 cm−1 E14.17(a) 0.21 s
E12.11(a) 198.9 pm E14.18(a) 1.234
E12.12(a) óJ = 2.111 × 10 −4 cm−1, 0.1253 E14.19(a) B1 = 5.9 × 10 −4 T, 20 μs
E12.13(a) (a) 20 (b) 24 E14.20(a) (a) 2 × 10 2 T (b) 10 mT
E12.14(a) 1.6 × 10 2 N m−1 E14.21(a) 2.0022
E12.15(a) 1.089 per cent E14.22(a) a = 2.3 mT, g = 2.002fi
E12.16(a) 327.8 N m−1 E14.23(a) equal intensity, 330.2 mT, 332.2 mT, 332.8 mT, 334.8 mT
E12.17(a) (a) 0.067 (b) 0.20 E14.25(a) (a) 331.9 mT (b) 1.201 T
3
E14.26(a) I = 2
E12.18(a) HF HCl HBr HI E14.28(a) 1.9 × 10 8 s−1

#/cm−1 4141.3 2988.9 2649.7 2309.5

meff /mu 0.9570 0.9697 0.9954 0.9999 Chapter 15
k/(N m−1) 967.0 515.6 411.8 314.2
E15.1(a) 21621600
−1
E12.19(a) # = 1580.38 cm , xe = 7.644 × 10 −3 E15.2(a) 1
E12.20(a) 5.15 eV
E15.3(a) 524 K
2 19
xe( H F) E15.4(a) 35› K
E12.21(a) xe = 0.02101, = 0.5256 E15.5(a) (a) (i) 8.23 pm (ii) 2.60 pm (b) (i) 1.79 × 10 27 (ii) 5.67 × 10 28
xe(1H19F)
−1 E15.6(a) 2.83
E12.22(a) 2699.77 cm
E15.7(a) 2.4 × 10 25
E12.26(a) Raman active
E15.8(a) 72.2
E12.27(a) 4A1 + A2 + 2B1 + 2B2
E15.9(a) (a) 7.97 × 10 3 (b) 1.12 × 10 4
E15.10(a) 18 K
Chapter 13 E15.11(a) 37 K
E15.12(a) 4.5 K
E13.1(a) 80 per cent E15.13(a) (a) 1 (b) 2 (c) 2 (d) 12 (e) 3
E13.2(a) 6.28 × 10 3 dm3 mol−1 cm−1 E15.14(a) 660.6
E13.3(a) 1.5 mmol dm−3 E15.14(a) 4500 K
E13.4(a) 5.4 × 10 7 dm3 mol−1 cm−2 E15.16(a) 2.571
E13.5(a) 4.5 × 10 2 dm3 mol−1 cm−2 E15.17(a) 42.3
E13.6(a) 23 per cent E15.18(a) 3.1561
E13.7(a) (a) 0.87 m (b) 2.9 m E15.19(a) +2.46 kJ
E13.8(a) (a) 5 × 10 7 dm3 mol−1 cm−2 (b) 2.5 × 10 6 dm3 mol−1 cm−2 2μ Be−2μB βB 2μ Be−2μB βB
E13.9(a) 1σ 1g 1π 1u E15.20(a) 1 + e−2μ B βB, B −2μ βB , −μBB + B −2μ βB (a) 0.71 (b) 0.996
1+e B 1+e B
E13.10(a) 3, u
E15.21(a) (a) (1) 5 × 10 −5 (2) 0.4 (3) 0.905 (b) 1.4 (c) 22 J mol−1
E13.11(a) (a) allowed (b) allowed (c) forbidden (d) forbidden (e) allowed (d) 1.6 J K −1 mol−1 (e) 4.8 J K −1 mol −1
2 2 −2ax 20 /3 E15.22(a) 4303 K
E13.12(a) e
3 E15.23(a) (a) 138 J K −1 mol−1 (b) 146 J K −1 mol −1
E13.13(a) R branch has a band head, J = 7 E15.24(a) 5.20 J K −1 mol −1
E13.14(a) 30.4 cm−1 < ì′ < 40.5 cm−1 E15.25(a) (a) He gas (b) CO gas (d) H2O vapour
E13.17(a) Δ O = P − #, 14 × 10 3 cm−1
E13.18(a) (a) # ≈ 1800 cm−1
E13.19(a) λ = 60 cm (ν = 500 MHz) Chapter 16
E13.20(a) 20 ps, 70 MHz E16.1(a) 15.27 pm
E16.2(a) 2.8 × 10 26
E16.3(a) (a) 72 R (b) 3R (c) 7R
Chapter 14 E16.4(a) 15.24 K
E14.1(a) 28 GHz E16.5(a) (a) 19.6 (b) 34.3
E14.2(a) 8.9 × 10 −12 s E16.6(a) (a) 1 (b) 2 (c) 2 (d) 12 (e) 3
E14.3(a) 600 MHz E16.7(a) q R = 43.1, θ R = 22.36 K
E14.4(a) 154 MHz E16.8(a) 43.76 J K −1 mol −1
E14.5(a) ΔE = 3.98 × 10 −25 J, ΔE = 6.11 × 10 −26 J, larger for the proton E16.9(a) (a) 36.95, 80.08 (b) 36.7, 79.7
E14.7(a) (a) 1 × 10 −6 (b) 5.1 × 10 −6 (c) 3.4 × 10 −5 E16.10(a) 72.5
E14.8(a) (a) 1.86 T (b) 0 E16.11(a) closer, closer
E14.9(a) 13 E16.12(a) (a) 14.93 J K −1 mol −1 (b) 25.65 J K −1 mol −1
E14.10(a) (a) 11 μT (b) 110 μT E16.13(a) −13.8 kJ mol −1, −0.20 kJ mol −1
952 SOLUTIONS TO A) EXERCISES

E16.14(a) (a) 4.158 (b) 4.489 E19.3(a) d111 = 249 pm, d211 = 176 pm, d100 = 432 pm
E16.15(a) (a) 0.236 (b) 0.193 E19.4(a) 70.7 pm
E16.16(a) (a) −6.42 kJ mol −1 (b) −14.0 kJ mol −1 E19.5(a) sin θ110 = 16°, sin θ200 = 23°, sin θ211 = 28°
E16.17(a) 11.5 J K −1 mol −1 E19.6(a) 0.214 cm
E16.19(a) (a) 9.13 J K −1 mol −1 (b) 13.4 J K −1 mol −1 (c) 14.9 J K −1 mol −1 E19.7(a) fBr− = 36
E16.20(a) 3.70 × 10 −3 E19.8(a) 0.396 nm3
E19.9(a) N = 4, ρ = 4.01 g cm−3
E19.10(a) 190 pm
Chapter 17 E19.11(a) 111, 200, 311, cubic F
E17.1(a) CIF3, O3, H2O2 E19.12(a) θ100 = 8.17°, θ010 = 4.82°, θ111 = 11.75°
E17.2(a) 1.4 D E19.13(a) face-centred cubic
E17.3(a) 37D, 11.‡° E19.14(a) f
E17.4(a) 1.07 × 10 3 kJ mol −1 E19.18(a) 7.9 km s−1
E17.5(a) 5.0 μD E19.19(a) 252 pm
E17.6(a) 1.66 D, 1.01 × 10 −39 J −1 C2 m2, 9.06 × 10 −30 m3 E19.20(a) 0.9069
E17.7(a) 4.75 E19.21(a) (a) 0.5236 (b) 0.6802 (c) 0.7405
E17.8(a) 1.42 × 10 −39 J −1 C2 m2 E19.22(a) 0.41421
E17.9(a) 1.34 E19.23(a) (a) 58.0 pm (b) 102 pm
E17.10(a) 17.7 E19.24(a) expansion
E17.11(a) 0.071 J mol −1 E19.25(a) 3500 kJ mol −1
E17.12(a) 28· kJ mol −1 E19.26(a) 0.010
E17.13(a) 2.6 kPa E19.27(a) 9.3 × 10 −4 cm3
E17.14(a) 72.8 mN m−1 E19.29(a) 3.54 eV
E17.15(a) 728 kPa E19.30(a) 3 unpaired electrons
E19.31(a) −6.4 × 10 −5 cm3 mol −1
E19.32(a) 5
Chapter 18 E19.33(a) +1.6 × 10 −8 m3 mol −1
E19.34(a) 6.0 K
E18.1(a) 27 nm
E18.2(a) Rc = 3.08 μm, R rms = 30.8 nm
E18.3(a) 1.4 × 10 4
Chapter 20
E18.4(a) 0.017
E18.5(a) 6.4 × 10 −3 E20.1(a) (a) 9.975
E18.6(a) −19 mJ mol −1 K −1 E20.2(a) (a) 72 K (b) 94fl m s−1 (c) the temperature would not be
A Rg,constrained coil − Rg,random coil D different
E18.7(a) B E × 100% = +41.42%, E20.3(a) 9.06 × 10 −3
C Rg,random coil F 1/2 1/2 1/2
A 8D A RT D A 8D
A Vconstrained coil − Vrandom coil D E20.4(a) B3 − E B E , B1 − E c
B E × 100% = +182.8% C πF CMF C πF
C Vrandom coil F
E20.5(a) 0.0652 Pa
A Rg − Rg,random coil D E20.6(a) 0.97 μm
E18.8(a) B E × 100% = +895% when N = 1000,
C Rg,random coil F E20.7(a) 397 m s−1 (a) 5.0 × 1010 s−1 (b) 5.0 × 10 9 s−1 (c) 5.0 × 10 3 s−1
E20.8(a) (a) 6.7 nm (b) 67 nm (c) 6.7 cm
A V − Vg,random coil D
B E × 100% = +9.84 × 10 4 % when N = 1000 E20.9(a) 1.9 × 10 20
C Vg,random coil F
E20.10(a) 104 mg
E18.9(a) 1.3 × 10 4 pm E20.11(a) 415 Pa
E18.10(a) 3.7 × 10 −14 N E20.12(a) 42.4 g mol −1
E18.11(a) Jn = 70 kg mol −1, Jw = 69 kg mol −1 E20.13(a) 1.3 days
E18.12(a) (a) 18 kg mol −1 (b) 20 kg mol −1 E20.14(a) −0.013 J m−2 s−1
E18.13(a) 100 E20.15(a) 0.0562 nm2
E18.14(a) 64 kg mol −1 E20.16(a) 17 W
E18.15(a) 0.73 mm s−1 E20.17(a) 0.142 nm2
E18.16(a) 31 kg mol −1 dV πR 4
E18.17(a) 3.4 × 10 3 kg mol −1 E20.18(a) p1 = 205 kPa, = ( p12 − p 22 ) Poiseuille’s formula
dt 16η p0 l
E20.19(a) (a) 12‡ μP (b) 13¤ μP (c) 24‹ μP
E20.20(a) (a) κ = 5.4 mJ K −1 m−1 s−1, Jenergy = −0.81 W m−2,
Chapter 19 Rate of energy flow = −8.1 mW (b) κ = 29 mJ K −1 m−1 s−1,
E19.1(a) (1, 12 ,0), (1,0, 12 ), ( 12 , 12 , 12 ) Jenergy = −4.4 W m−2, Rate of energy flow = −44 mW
E19.2(a) (323) and (110) E20.21(a) 5.4 mJ m−1 s−1
 SOLUTIONS TO A) EXERCISES 953

E20.22(a) (a) D = 1.07 m2 s−1, J = 438 mol m−2 s−1 (b) D = 1.07 × 10 −5 m2 s−1, E22.3(a) (a) (i) 14% (ii) 1% (b) (i) 280%, 260 % (ii) 13%
J = 4.38 mmol m−2 s−1, (c) D = 1.07 × 10 −7 m2 s−1, E22.4(a) 1.03 × 10 −5 m3 mol −1 s−1 = 1.03 × 10 −2 dm3 mol −1 s−1
J = 43.8 μmol m−2 s−1 E22.5(a) 2.4 × 10 −4
E20.23(a) 7.63 mS m2 mol −1 E22.6(a) 3 × 10 10 dm3 mol −1 s−1
E20.24(a) 347 μm s−1 E22.7(a) (a) 6.61 × 10 9 dm3 mol −1 s−1 (b) 3.0 × 10 10 dm3 mol −1 s−1
E20.25(a) 13.83 mS m2 mol −1 E22.8(a) 7.4 × 10 9 dm3 mol−1 s−1, 6.7 × 10 −8 s
E20.26(a) u(Li +) = 4.01 × 10 −8 m2 V −1 s−1, u(Na+) = 5.19 × 10 −8 m2 V −1 s−1, E22.9(a) 0.79 nm2, 1.16 × 10 −3
u(K +) = 7.62 × 10 −8 m2 V −1 s−1 E22.10(a) 1.87 × 10 8 mol dm−3 s−1
E20.27(a) 1.90 × 10 −9 m2 s−1 E22.11(a) +69.66 kJ mol −1, −25.3 J K −1 mol −1
E20.28(a) F(10 cm) = 25 kN mol −1, F (20 cm) = ∞ E22.12(a) +73.4 kJ mol −1, +71.9 kJ mol −1
E20.29(a) 67.5 kN mol −1 E22.13(a) −91 J K −1 mol −1
E20.30(a) t = 1.3 × 10 3 s E22.14(a) −72 J K −1 mol −1
E20.31(a) a = 0.42 nm E22.15(a) (a) −46 J K −1 mol −1 (b) +5.0 kJ mol −1
E20.32(a) 27.3 ps (c) +18.7 kJ mol −1
E20.33(a) 〈r 2 〉1/2 = 113 μm, 〈r 2 〉1/2 = 56 μm E22.16(a) 7.1 dm6 mol−2 min−1
E22.17(a) 1.· × 10 −19 J, 1.2 eV
E22.18(a) 12.fi nm−1
Chapter 21
E22.19(a) 0.138 V
E21.1(a) no change in pressure E22.20(a) 2.82 mA cm−2
E21.2(a) 8.1 mol dm−3 s−1, 2.7 mol dm−3 s−1, 2.7 mol dm−3 s−1, E22.21(a) increases, factor of 50
5.4 mol dm−3 s−1 E22.22(a) (a) 1.7 × 10 −4 A cm−2
E21.3(a) v = 1.3fi mol dm−3 s−1, 4.0fi mol dm−3 s−1, 2.7 mol dm−3 s−1, (b) 1.7 × 10 −4 A cm−2
1.3fi mol dm−3 s−1 E22.23(a) (a) 0.31 mA cm−2
E21.4(a) dm3 mol −1 s−1, (b) 5.44 mA cm−2
(a) kr[A][B] (b) 3kr[A][B] (c) −2 × 10 42 mA cm−2
1 (a) 4.9 × 10 15 cm−2 s−1 (b) 1.6 × 10 16 cm−2 s−1 (c) 3.1 × 10 7 cm−2 s−1,
E21.5(a) v = kr[A][B][C], [kr] = dm6 mol −2 s−1 E22.24(a)
2 3.9 s−1, 12 s−1, 2.4 × 10 −8 s−1
E21.6(a) (a) [kr] = dm3 mol −1 s−1, [kr] = dm6 mol −2 s−1 E22.25(a) (a) 33 Ω (b) 3.3 × 10 10 Ω
(b) [kr] = kPa−1 s−1[kr] = kPa−2 s−1 E22.26(a) one can (barely) deposit zinc
E21.7(a) second-order
E21.8(a) n=2
E21.9(a) 1.03 × 10 4 s, (a) 498 Torr (b) 461 Torr Chapter 23
E21.10(a) (a) 16.¤ dm3 mol −1 h−1, 4.5 × 10 −3 dm3 mol −1 s−1 kb K[AH]2[B]
(b) 5.1 × 10 3 s, 2.1 × 10 3 s E23.1(a)
[BH+]
E21.11(a) (a) 0.098 mol dm−3 (b) 0.050 mol dm−3
E23.2(a) 1.50 mmol dm−3 s−1
E21.12(a) 1.11 × 10 5 s = 128 days
E23.3(a) kcat = 1.18 × 10 5 s−1, η = 7.9 × 10 6 dm3 mol −1 s−1
E21.13(a) 1.28 × 10 4 dm3 mol −1 s−1, 4.0 × 10 10 dm−3 mol s−1
E23.4(a) 2.0 × 10 −5 mol dm−3
E21.14(a) 64.9 kJ mol −1, 4.32 × 10 8 mol dm−3 s−1
E23.5(a) (a) (i) 1.07 × 10 21 cm−2 s−1 (ii) 1.4 × 10 14 cm−2 s−1
E21.15(a) 35 kJ mol −1
(b) (i) 2.30 × 10 20 cm−2 s−1 (ii) 3.1 × 10 13 cm−2 s−1
k 22[B]2 A 16k1′k1[A2] D
0.13 bar
E21.16(a) (i) k3 K 1/2[A2]1/2[B] (ii) B 1+ − 1E , E23.6(a)
4k1′ C k 22[B]2 F E23.8(a) 12 m2
k2 K 1/2[A2]1/2[B], 2k1[A2] E23.9(a) 33.6 cm3
E21.17(a) 1.9 × 10 −6 Pa−1 s−1, 1.9 MPa−1 s−1 E23.10(a) chemisorption, 50 s
E21.18(a) −3 kJ mol −1 E23.11(a) θ1 = 0.83, θ2 = 0.36
E21.19(a) 251, 0.996 E23.12(a) (a) 0.24 kPa (b) 25 kPa
E21.20(a) 0.125 E23.13(a) 15 kPa
E21.21(a) 3.3 × 10 18 E23.14(a) −12.› kJ mol −1
E21.22(a) 0.52 E23.15(a) Ed = 65⁄kJ mol −1, (a) 1.6 × 10 97 min (b) 2.8 × 10 −6 min
E21.23(a) 0.56 mol dm−3 E23.16(a) 61⁄ kJ mol −1
E21.24(a) 7.1 nm E23.17(a) (a) t1/2(400 K) = 9.1 ps, t1/2(1000 K) = 0.60 ps
(b) t1/2(400 K) = 4.1 × 10 6 s, t1/2(1000 K) = 6.6 μs
E23.18(a) (a) zeroth-order (b) first-order
Chapter 22
E22.1(a) 9.49 × 10 9 s−1, 1.15 × 10 35 s−1 m−3, 1.7 per cent
E22.2(a) (a) (i) 0.018, (ii) 0.30 (b) (i) 3.9 × 10 −18 (ii) 6.0 × 10 −6
Solutions to odd-numbered problems

A horizontal bar over the last digit in some answers denotes an P2.17 (a) 240 kJ mol −1 (b) 228 kJ mol −1
insignificant digit. P2.19 41.40 J K −1 mol −1
P2.21 +3.60 kJ
A 1D
P2.23 (a) (2x − 2y + 2)dx + (4y − 2x − 4)dy (b) −2 (c) B y + E dx + (x − 1)dy
Chapter 1 C xF
p A ∂V D
P2.27 (a) 1 + (b) 1 + p B E
P1.1 −233°N (∂U/∂V )p C ∂U F p
P1.3 −272.95°C P2.31 (a) −1.5 kJ (b) −1.6 kJ
P1.5 (a) 0.0245 kPa (b) 9.14 kPa (c) 0.0245 kPa P2.33 increase
P1.7 (a) 12.5 dm3 mol −1 (b) 12.3 dm3 mol −1 A p D A na D A ∂T D V − nb
P1.9 (a) 0.941 dm3 mol −1 (b) 2.69 dm3 mol −1, 2.67 dm3 mol −1 P2.35 T = B E × (V − nb) + B E × (V − nb), B E =
C nR F C RV 2 F C ∂p F V nR
(c) 5.11 dm3 mol −1
P1.11 (a) 0.1353 dm3 mol −1 (b) 0.6957 (c) 0.7158 A nbζ D
B1− E 2
P1.13 a = 5.649 dm6 atm mol −2, b = 59.4 cm3 mol −1, p = 21 atm V 27 A b D
P2.37 μCp = B E V, μ = 1.41 K atm−1, TI = Tc B 1 − E ,
P1.15 1.26 dm6 atm mol −2, 34.6 cm3 mol −1 C ζ−1 F 4 C Vm F
1
P1.17 TI = 1946 K
3 1 (3Vr − 1)2
P1.19 0.0866 atm−1, 2.12 dm3 mol −1 P2.39 =1− , Cp,m − CV,m = 9.2 J K −1 mol −1
λ 4TrV 3r
P1.23 0.011 2
aT 2 A 2apT D
P1.25 3.4 × 10 8 dm3 P2.41 (a) μ = (b) CV = Cp − R B 1 + E
P1.27 (a) 1.7 × 10 −5 (b) 0.72
Cp C R F
P1.31 0.0029 atm P2.43 (a) 16.2 kJ mol −1 (b) 114.8 kJ mol −1 (c) 122.0 kJ mol −1
P2.45 (a) 29.9 K MPa−1 (b) −2.99 K

Chapter 2
Chapter 3
P2.1 Total cycle
P3.1 (a) Δ trsS(1 → s, −5°C) = −21.3 J K −1 mol −1, ΔSsur = +21.7 J K −1 mol −1,
State p/atm V/dm 3
T/K ΔStotal = +0.4 J K −1 mol −1
(b) Δ trs S(1 → g, T) = +109.7 J K −1 mol −1, ΔSsur = −111.2 J K −1 mol −1,
1 1.00 22.44 273 ΔStotal = −1.5 J K −1 mol −1
2 1.00 44.8 546 P3.3 (a) q(Cu) = 43.9 kJ, q(H2O) = −43.9 kJ, ΔS(H2O) = −118.⁄ J K−1,
3 0.50 44.8 273 ΔS(Cu) = 145.· J K −1, ΔS(total) = 28 J K −1
(b) θ = 49.9°C = 323.1 K, q(Cu) = 38.4 kJ, ΔS(H2O) = −119.° J K −1,
Thermodynamic quantities calculated for reversible steps. ΔS(Cu) = 129.¤ J K −1, ΔS(total) = 9 J K −1

Step Process q/kJ w/kJ ΔU/kJ ΔH/kJ P3.5 Step1 Step2 Step3 Step4 Cycle

1→2 p constant = pex +5.67 −2.27 +3.40 +5.67 q +11.5 kJ 0 −5.74 kJ 0 −5.8 kJ
2→3 V constant −3.40 0 −3.40 −5.67 w −11.5 kJ −3.74 kJ +5.74 kJ +3.74 kJ −5.8 kJ
3→1 Isothermal, reversible −1.57 +1.57 0 0 ΔU 0 −3.74 kJ 0 +3.74 kJ 0
Cycle +0.70 −0.70 0 0 ΔH 0 −6.23 kJ 0 +6.23 kJ 0
ΔS +19.1 J K −1 0 −19.1 J K −1 0 0
ΔStot 0 0 0 0 0
P2.3 w = 0, ΔU = +2.35 kJ, ΔH = +3.03 kJ
ΔG −11.5 kJ ? +5.73 kJ ? 0
P2.5 (a) w = 0, ΔU = +6.19 kJ, q = +6.19 kJ, ΔH = +8.67 kJ
(b) q = 0, ΔU(b) = −6.19 kJ, ΔH(b) = −8.67 kJ, w = −6.19 kJ
(c) −4.29 kJ P3.7 (a) 200.7 J K −1 mol −1 (b) 232.0 J K −1 mol −1
P2.7 −89.03 kJ mol −1 P3.9 +22.6 J K −1
P2.9 Δ r H 7 = +17.7 kJ mol −1, Δ f H 7 (metallocene, 583 K) = +116.0 kJ mol −1 P3.11 (a) 63.88 J K −1 mol −1 (b) 66.08 J K −1 mol −1
P2.11 ΔT = +37 K, m = 4.09 kg P3.13 32.1 kJ mol −1
P2.13 n = 0.903, k = −73.7 kJ mol −1 P3.15 46.60 J K −1 mol −1
P2.15 Δc H 7 = −25 968 kJ mol−1, Δ f H 7(C60) = 2357 kJ mol −1 P3.17 (a) 7 mol −1 (b) +107 kJ mol −1
 SOLUTIONS TO ODD-NUMBERED PROBLEMS 955

A a D −a/RVmT P5.39 (a) R′ = 84 784.0 g cm K −1 mol −1 (b) M = 1.1 × 10 5 g mol −1

RB1 + Ee
R C RVmT F (d) B′ = 21.4 cm3 g−1, C′ = 211 cm6 g−2 (e) 19fl cm6 g−2
P3.23 (a) (b)
Vm − b Vm − b
A ∂V D A ∂T D A ∂S D A ∂p D Chapter 6
P3.25 B E =B E ,B E =B E
C ∂S F p C ∂p F S C ∂V F T C ∂T F V P6.1 (a) +4.48 kJ mol−1 (b) pIBr = 0.101 atm
p2 ΔB P6.3 Δ f H 7 = 32 R × (B − CT ), Δ rC p7 = 70.5 J K −1 mol −1
P3.29 πT ≈ × (a) 3.0 × 10 −3 atm (b) 0.30 atm P6.5 Δ rG 7 (T )/(kJ mol −1) = 78 − 0.161 × (T/K)
R ΔT
nap P6.7 K = 0.740, K = 5.71, −103 kJ mol −1
P3.31 πT = P6.9 +158 kJ mol −1
RTV
P3.33 T dS = CpdT − α TV dp, qrev = −αTV Δp, qrev = −0.50 kJ P6.11 (a) 1.2 × 10 8 (b) 2.7 × 10 3
P3.35 f = 0.9974 atm P6.13 (a) CuSO4, I = 4.0 × 10 −3, ZnSO4, I = 1.2 × 10 −2
P3.37 −21 kJ mol −1 (b) γ ±(CuSO4) = 0.74, γ ±(ZnSO4) = 0.60 (c) Q = 5.9
7
P3.39 13 per cent (d) E cell = +1.102 V (e) Ecell = +1.079 V
1/c P6.15 2.0
AV D
P3.43 η = 1 − B B E , ΔS2 = +33 J K −1, ΔSsur,2 = −33 J K −1, ΔS4 = −33 J K−1, P6.19 0.533
C VA F P6.21 pKa = 6.736, B = 1.997, k = −0.121
ΔSsur,4 = +33 J K −1 P6.23 Δ rG(T ′) = Δ rG(T ) + (T − T ′)Δ r S(T ) + α (T ′, T ) × Δa + β(T′, T) ×
P3.45 (a) 1.00 kJ (b) 8.4 kJ Δb + γ (T ′, T ) × Δc, Δ f G 7 (372 K) = −225.31 kJ mol −1
P6.27 (a) 41% (b) 75% (c) 55%
P6.29 (b) +0.206 V
Chapter 4 P6.31 trihydrate
P4.1 T3 = 196.0 K, p3 = 11.1 Torr
P4.3 (a) +5.56 × 10 3 Pa K −1 (b) 2.6 per cent
P4.5 (a) −1.63 cm3 mol −1 (b) +30.1 dm3 mol −1 (c) +6 × 10 2 J mol −1 Chapter 7
P4.7 22°C P7.1 (a) 1.6 × 10 −33 J m−3 (b) 2.5 × 10 −4 J m−3
P4.9 (a) 227.5°C (b) +53 kJ mol −1 C C
P4.11 (b) 178.18 K (c) T = 383.6 K, Δ vap H = 33.0 kJ mol −1 P7.3 (a) ν = 223⁄ K, V,m = 0.0315 (b) ν = 343 K, V,m = 0.897
3R 3R
P4.15 9.8 Torr P7.5 (a) 9.0 × 10 −6 (b) 1.2 × 10 −6
P4.17 Th = 363 K (90°C) P7.7 xmax = a
dp α 2 − α1 dp Cp,m2 − Cp,m1
P4.19 (1) = (2) = 8πkT
dT κT,2 − κT,1 dT TVm(α 2 − α1) P7.11
λ4
P4.21 n = 17 A4D
P4.23 (b) 112 K (c) 8.07 kJ mol −1 P7.13 B E σT 4
CcF
1/2
A2D 1 1 1
P7.15 (a) N = B E (b) N = (c) N = (d) N =
Chapter 5 CLF c(2L)1/2 (πa3)1/2 (32πa5)1/2
P5.1 KA = 15.58 kPa, KB = 47.03 kPa P7.17 (a) yes (b) no (c) yes (d) no (e) no
P5.3 VB = −1.4 cm3 mol −1, VA = 18.Ù cm3 mol −1 P7.19 (a) no, no (b) no, −k 2 (c) no, no
P5.5 V *E = 57.6 cm3, V *W = 45.6 cm3, ΔV ≈ +0.95 cm3 ($k)2
P7.23
P5.7 4 ions 2m
P5.11 (a) V1 = V 1* + a0 x 22 + a1(3x1 − x 2)x 22, V2 = V *2 + a0 x 12 + a1(x1 − 3x 2)x 12 P7.25 (a) 1.5a0 , 4.5a 02 (b) 5a0, 30a 02
(b) V1 = 75.63 cm3 mol −1, V2 = 99.06 cm3 mol −1 P7.31 5.35 pm
P5.13 371 bar P7.33 (a) 811 K (b) 2.88 μm (c) 7.72 × 10 −4 (d) 2.35 × 10 −7
P5.15 −4.64 kJ mol −1
P5.17 (b) 391.0 K (c) 0.532
P5.23 Mg = 16, Mg2Cu = 43 Chapter 8
nCa 2Si nSi nSi P8.1 E2 − E1 = 1.24 × 10 −39 J, n = 2.2 × 10 9, 1.8 × 10 −30 J
P5.25 (b) x Si = 0.13, = 0.5 (c) = 0.53, = 0.67
nliq nliq nCaSi2 P8.3 1.30 × 10 −22 J, $
P5.27 μA = μ *A + RT ln xA + gRTx 2B 4k12 k 22
P8.9 (a) T = | A3 | 2 = A3 × A*3 = 2 2
P5.29 73.96 cm3 mol −1 (a + b ) sinh2(k2 L) + b 2

冮
r
A φ − 1D where a 2 + b 2 = (k12 + k 22)(k 22 + k32) and b 2 = k 22(k1 + k3)2
P5.31 φ − φ(0) + B E dr 1/2
0C r F
A mk D
P8.11 g = 12 B 2 E
1 ΔT C$ F
P5.33 φ = 1 − A′b1/2, φ =
3 2bKf 3 2
P8.13 0, (2v + 2v + 1)α 4
P5.35 (1) 56 μg N2 (2) 14 μg N2 (3) 1.7 × 10 2 μg N2 4
956 SOLUTIONS TO ODD-NUMBERED PROBLEMS

P8.15 (b) 0.0786 P11.7 do not form a group

1/2 1/2 (a) all five d orbitals (b) all except A2 (dxy)
Av + 1D AvD P11.9
P8.17 αB E , αB E P11.11 (a) D2h (b) C2h, C2v
C 2 F C2F
P11.13 (a) 2A1 + A2 + 2B1 + 2B2 (b) A1 + 3E (c) A1 + T1 + T2
$ 2$ $ $
2 2 2 2
P8.21 (a) +$ (b) −2$ (c) 0 (d) $ cos 2χ, , , , (d) A2u + T1u + T2u
2I I 2I 2I
P11.15 4A1 + 2B1 + 3B2 + A 2
3$2 1/2
P8.23 (a) 0, 0, 0 (b) E = ,6 $ P11.17 (a) 7A 2 + 7B1, 12 (a − a′), 12 (b − b′), . . . , 12 (g − g′), 12 (a + a′), 12 (b + b′),
I . . . , 12 (g + g′)
6$2 A1g + B1g + Eu
(c) E = , 121/2$ P11.21
I P11.23 z-polarized transition is not allowed, x, y-polarized transitions are
ml allowed
P8.25 θ = arccos , 54°44′, 0
{l(l + 1)}1/2
$A ∂ ∂ D $A ∂ ∂ D $A ∂ ∂D $
P8.27 B y − z E , B z − x E , B x − y E , − Zz . Chapter 12
i C ∂z ∂y F i C ∂x ∂z F i C ∂y ∂x F i
P8.31 (a) 3.30 × 10 −19 J (b) 4.95 × 10 −14 s−1 (c) lower, increases P12.1 596 GHz, 19.9 cm−1, 0.503 mm, 9.941 cm−1
P8.33 2.68 × 10 14 s−1 P12.3 RCC = 139.6 pm, RCH = 108.fi pm
P8.35 (a) E ±5 = 7.89 × 10 −19 J, Jz = 5.275 × 10 −34 J s (b) 5.2 × 10 14 Hz P12.5 R(HCl) = 128.393 pm, R(2HCl) = 128.13 pm
P8.39 5.8 × 10 −11 N P12.7 R = 116.28 pm, R′ = 155.97 pm
P12.9 142.81 cm−1, D0 = 3.36 eV, 93.8 N m−1
P12.11 (a) 2143.26 cm−1 (b) 12.8195 kJ mol −1 (c) 1.85563 × 10 3 N m−1
Chapter 9 (d) 1.91 cm−1 (e) 113 pm
P12.17 (a) 7 (b) C2h, C2v, C2 (c) structure 2 is inconsistent with observation
P9.1 n2 → 6
1A D 1A 〈x 2 〉 D
RLi2+ = 987 663 cm−1, # = 137 175 cm−1, 185 187 cm−1, # = 122.5 eV
冬 冭
P9.3 1 1
P12.19 1/〈R〉2 = 1/R 2e , 1/〈R2 〉 = B E , 2 = 2 B1 + 3 2 E
P9.5 2
P1/2 and 2P3/2, 2D3/2 and 2D5/2, 2D3/2 R e C 1 + 〈x 〉/R e F R
2 2 2
Re C Re F
P9.7 3.3429 × 10 −27 kg, 1.000272 4ì3
P12.21 ó= 2
P9.9 (a) 0.9 cm−1 (b) small #
P9.11 (b) # = 4.115 × 10 5 cm−1, λ = 2.430 × 10 −6 cm, ν = 1.234 × 10 16 s−1 P12.27 230, 240, and 250 pm
23 3 43 P12.29 (a) ΔJ = 0 is forbidden (c) 30 m
(c) a 0, a 0, a 0
2 4 4 P12.31 ì = 2.031 cm−1, T = 2.35 K
P9.13 ±106 pm
P9.15 (b) ρnode = 3 + 3 and ρnode = 3 − 3, ρnode = 0 and
27a0 Chapter 13
ρnode = 4, ρnode = 0 (c) 〈r〉3S =
2 P13.1 49 36› cm−1
Z Z Z P13.5 A = 12 Δ# 1/2 εmax π/ln(2) , A = 1.3‚ × 10 6 dm3 mol −1 cm−2
P9.19 (a) (b) (c)
a0 4a0 4a0 P13.7 D0(B3 Σ u−) = 6808.2 cm−1 or 0.84411 eV, D0(X3 Σ g−) = 5.08 eV
P9.23 Δl = ±1 and Δml = 0 or ±1 P13.13 4 × 10 −10 s or 0.4 ns

P9.27 60 957.4 cm−1, 60 954.7 cm−1, 329 170 cm−1, 329 155 cm−1 P13.25 6.37, 2.12

P9.29 (a) receding, 1.128 × 10 −3 c, 3.381 × 10 5 ms−1 P13.27 Δ f H 7 (structure 2) − Δ f H 7 (structure 1) = +28 kJ mol −1

Chapter 10 Chapter 14
−(α O + α N) ± {(α O + α N)2 − 12α Oα N β 2}1/2 δN
P10.9 E= , P14.1 B0 = 10.3 T, ≈ 2.42 × 10 −5, β, (mI = − 12 )
2 N
Edeloc = {(α O − α N)2 + 12β 2}1/2 − {(α O − α N)2 + 4β 2}1/2 P14.3 300 × 10 6 Hz ± 10 Hz, 0.29 s
P10.11 (b) 1.518β, 8.913 eV P14.5 k = 4 × 10 2 s−1, E II − E I = 3.7 kJ mol −1, Ea = 16 kJ mol −1
P10.13 (b) ΔE/eV = 3.3534 + 1.3791 × 10 −4 #/cm−1 (c) 30 937 cm−1 P14.7 (b) 580 − 79 cos φ + 395 cos 2φ
2(k − Sj) P14.9 158 pm
P10.19 P14.11 6.9 mT, 2.1 mT
1 − S2
P14.13 0.10, 0.38 (a) 0.48 (b) 0.52, 3.8
P10.25 2
j0{c Aa(AB | AA) + cAa cBa (AB | AB) + cBa cAa (AB | BA) + c 2Ba(AB | BB)},
j0{c Aa(AA | AB) + cAa cBa (AA | BB) + cBa c Aa
2 2
(AB | AB) + c 2Ba(AB | BB)} e 2μ 0 Z
P14.15 = 1.78 × 10 −5 Z
P10.29 (a) linear relationship (b) −0.122 V (c) −0.174 V 12πmea0
1 Aτ
P14.19
2 1 + (ω0 − ω)2τ 2
Chapter 11 1 A1D
P14.21 ω 1/2 = , ω 1/2 = 2(ln 2)1/2 B E
P11.1 (a) D3d (b) D3d, C2v (c) D2h (d) D3 (e) D4d τ CτF
P11.3 C2σ h = i P14.27 29 μT m−1
 SOLUTIONS TO ODD-NUMBERED PROBLEMS 957

Chapter 15 P18.7 1.6 × 10 5 g mol −1

P18.9 (a) a = 0.71, K = 1.2 × 10 −2 cm3 g−1
P15.5 7.41 P18.11 Jn = 155 kg mol −1, B = 13.7 m3 mol −1
P15.7 (a) (i) 5.00 (ii) 6.26 (b) 1.00, 0.80, 6.58 × 10 −11, 0.122 1/2
A 8N D
P15.9 (a) 0.641, 0.359 (b) 8.63 × 10 −22 J, 0.520 kJ mol −1 P18.15 (a) Rrms = N 1/2l, Rrms = 9.74 nm (b) Rmean = B E l, Rmean = 8.98 nm
C 3π F
P15.11 (a) 1.049 (b) 1.548, p0 = (a) 0.953 (b) 0.645, p1 = (a) 0.044 (b) 0.230,
p2 = (a) 0.002 (b) 0.083 (c) R* = ( 23 N )1/2l, R* = 7.95 nm
P15.15 {4,2,2,1,0,0,0,0,0,0}, W = 3780 Rg = N
P18.17 6l
P15.17 (a) 1 + 3e−ε /kT (b) Em(T ) = 0.5245 RT, ε = 2.074 J K −1 mol −1, AND
3/2
16π
Sm = 10.55 J K −1 mol −1 P18.21 (a) B = NA(γ l)3 B E , 0.38 m3 mol −1
3 C6F
P15.19 pV = nRT
3/2
16π AND
(b) B = NA(γ l)3 B E , 1.1 m3 mol −1
3 C3F
Chapter 16 A ∂t D
P18.23 −SdT − ldt, −SdT + tdl, −T B E + t
P16.1 0.351, 0.079, 0.029 C ∂T F l
P16.3 CV,m = 4.2 J K −1 mol −1, Sm = 15 J K −1 mol −1 P18.29 65.6 kg mol −1
P16.5 19.90 P18.31 S = 5.40 Sv, M = 63.2 kg mol −1
P16.7 199.4 J mol −1 K −1 P18.37 (a) (1) [η] = 0.086 dm3 g−1, k′ = 0.37 (2) [η] = 0.042 dm3 g−1,
A 2πe 2mσm D 1 A σ D A h2β D 1/2 5 k′ = 0.35 (b) (1) J v = 2.4 × 10 2 kg mol −1 (2) J v = 2.6 × 10 2 kg mol −1
P16.13 R ln B E , ΔS m = R ln 2B m E × B E 6 (c) (1) rrms = 42 nm (2) rrms = 33 nm (d) (1) (2) 〈n〉 = 2.3 × 10 3,
C h2NA β F 3 C Vm F C 2πme F 7 〈n〉 = 2.5 × 10 3 (e) (1) Lmax = 5.8 × 10 2 nm, (2) Lmax = 6.2 × 10 2 nm
N$ω 1 x 2e x 5 N$ω
P16.15 U − U(0) = , CV = kN 2 x 6 , H − H(0) = x ,
e −1
x
3 (e − 1)2 7 e −1 (f ) Solvent 〈n〉 Rg /nm KR
r rms /nm rrms /nm
A x D
S = Nk B x − ln(1 − e−x)E , A − A(0) = NkT ln(1 − e−x ) Toluene 2.3‚ × 10 3 4.3 42 10.› or 7.4
Ce − 1 F Cyclohexane 2.3‚ × 10 3 4.4 33 10.° or 7.6
dB(T )
P16.17 μT = B(T ) − T .
dT
A≥D 1 ” A ≥ D 25 A≥ eq D
P16.19 (a) U − U(0) = nRT B E , CV = nR 2 − B E 6 , S = nR B + ln E
CqF 3q C q F 7 Cq NF Chapter 19
−1 −1
(b) 5.41 J K mol P19.1 118 pm
1/2 1/2 1/2
A 1.40RT D A 1.40RT D A 4RT D P19.3 face-centred cubic, a = 408.55 pm, ρ = 10.507 g cm−3
P16.25 (a) cs = B E (b) cs = B E (c) cs = B E ,
C M F C M F C 3M F P19.5 α volume = 4.8 × 10 −5 K −1, α linear = 1.6 × 10 −5 K −1
cs = 350 m s −1 P19.7 a = 834 pm, b = 606 pm, c = 870 pm
P16.29 45.76 kJ mol −1 P19.9 ρ = 1.385 g cm−3, ρOs = 1.578 g cm−3
P19.11 (a) tungsten has the bcc unit cell with a = 321 pm, 139 pm
(b) copper has the fcc unit cell with a = 362 pm, 128 pm
Chapter 17 P19.13 1.01 g cm−3
P19.15 −146 kJ mol −1
P17.1 (a) 1.1 × 10 8 V m−1 (b) 4 × 10 9 V m−1 (c) 4 kV m−1 P19.17 0.254 cm3 mol −1
P17.5 α ′ = 1.2 × 10 −23 cm3, μ = 0.86 D 2 2 2
1 AhD AkD A l D
P17.7 α ′ = 2.24 × 10 −24 cm3, μ = 1.58 D, P′m = 5.66 cm3 mol −1 P19.19 =B E +B E +B E
P17.9 ε = 1.51 × 10 −23 J, re = 265 pm d2 C a F C b F C c F
P17.11 Pm = 68.8 cm3 mol −1, εr = 4.40, nr = 2.10, Pm = 8.14 cm3 mol −1, P19.25 0
εr = 1.76, nr = 1.33 (N + 1)/2πβ
P19.29 (a) ρ(E) = −
6l 4q12 9l 4q12 G 2 1/2
P17.13 (a) (b) − AE−αD J
πε0r 5
4πε0r 5 H1 − B E K
I C 2β F L
P17.17 re = 1.3598 r0, A = 1.8531
1/2
P17.21 −1.8 × 10 −27 J = −1.1 × 10 −3 J mol −1 A 1 D
P19.35 1− B E , increases
P17.25 (a) 3.5 (b) slope = −1.49, intercept = −1.95 (c) 1.12 × 10 −2 C 4( p/K ) + 1 F
P19.37 3.61 × 10 5 g mol −1

Chapter 18
P18.3 (a) Rg = 2
a, Rg /nm = 0.046460 × {(υs /cm3 g−1) × (M/g mol −1)}1/3,
Chapter 20
5
1 1
Rg = 1.96 nm (b) Rg,|| = 2 a, Rg,⊥ = 12 l, Rg,|| = 0.35 nm, P20.3 (b) 1.8894 m (c) 1.8897 m
Rg,⊥ = 46 nm P20.5 7.3 mPa
P18.5 0.0716 dm3 g−1 P20.7 0.613 mS m2 mol −1
958 SOLUTIONS TO ODD-NUMBERED PROBLEMS

1/2
P20.9 13.82 μmol dm−3 A Ia D
P21.35 B E
P20.11
GH+
= 0.821,
GH+
= 0.00279 C kr F
all ions all ions
first-order, kr = 0.00765 min−1 = 0.459 h−1,
∑ ∑G
P21.37
Gi i
i i
t1/2 = 1.51 h = 91 min
P20.13 (b) four, one to two P21.39 v0 = 6 × 10 −14 mol dm−3 s−1, t1/2 = 4.› × 10 8 s = 14 yr

P20.15 (a) 0, (b) 0.0630 mol dm−3 P21.41 5.9 × 10 −13 mol dm−3 s−1

P20.17 Λ om(NaI) = 60.7 S cm2 mol −1, Λ om(KI) = 58.9 S cm2 mol −1,
λ (Na+) − λ (K +) = 1.8 S cm2 mol −1, Λ om(NaI) = 127 S cm2 mol −1,
Λ om(KI) = 150 S cm2 mol −1, λ (Na+) − λ (K +) = −23 S cm2 mol −1 Chapter 22
P20.19 0.83 nm P22.1 (a) 4.3fi × 10 −20 m2 (b) 0.15
A m D −mv2/2kT A πkT D
1/2
A πRT D
1/2
P22.3 1.6› × 10 11 mol−1 dm3 s−1, 3.7 ns
P20.21 f(v) = B E ve ,B E or B E
C kT F C 2m F C 2M F P22.9 0.78, 0.38
P22.13 0.50, 0.150 A m−2, 0.038 A m−2
P20.23 P = 0.61, (a) 39 per cent (b) 61 per cent (c) 53 per cent, 47 per cent
1/2 1/2 P22.17 q Tm /NA = 1.4 = 107, qR(nonlinear) ≈ 900, qR(linear) ≈ 200, qR ≈ qE ≈ 1
A 2πM D V A 2πM D V A = 6.3 × 10 9 dm3 mol −1 s−1, A = 3.3 × 10 4 dm3 mol −1 s−1 P = 2 × 10 −7
P20.25 p = p0 e−t /τ where τ = B E , t1/2 = τ ln(2) = B E ln(2)
C RT F A C RT F A v3 −Δ E0 /RT
P22.19 e , 2.7 × 10 −15 m2 s−1, 1.1 × 10 −14 m2 s−1
P20.27 〈x 4 〉1/4/〈x 2 〉1/2 = 31/4 (v‡)2
1 1 (1 − α)Λ m P22.21 (a) 1.37 × 10 6 dm3 mol −1 s−1 (b) 1.16 × 10 6 dm3 mol −1 s−1
P20.29 = + , Λ m, α =1 = Λ om − K (αc)1/2
Λ m Λ m, α =1 (αΛ m, α =1)2 P22.25 (a) 6.23 × 10 9 dm3 mol −1 s−1 (b) 4 × 10 −10 m
2 −1 −1 −1 −1
P20.31 D = 1.fl × 10 m s , κ = 0.34 J K m s
16 P22.27 1.15 eV
P20.33 (a) 5.4 × 10 −12 cm3 (b) 16 MK (c) 16 MK P22.29 9.5 × 10 4 dm3 mol −1 s−1
P20.35 1.7 × 10 −2 s

Chapter 23
Chapter 21 P23.1 νmax = 2.31 μmol dm−3 s−1, kb = 115 s−1, kcat = 115 s−1,
KM = 1.11 μmol dm−3, η = 104 dm3 μmol −1 s−1
P21.1 second-order, kr = 0.059› dm3 mol −1 min−1, 2.94 g P23.3 (b) pH = 7.0
P21.3 7.0 × 10 −5 s−1, 7.3 × 10 −5 dm3 mol −1 s−1 P23.5 Vtotal = −2.039 × 10 −18 J, Vtotal = −2.20 × 10 −19 J,
P21.5 55.4% Vtotal = −7.30 × 10 −19 J
P21.7 first-order, 1.7 × 10 −2 min−1 P23.7 (a) 1.61 × 10 15 cm−2 (b) 1.14 × 10 15 cm−2 (c) 1.86 × 10 15 cm−2
P21.9 first-order kinetics, 7.2 × 10 −4 s−1 P23.9 (a) c = 165, Vmon = 13.1 cm3 (b) c = 263, Vmon = 12.5 cm3
P21.11 kr K1 K2[HCl]3[CH3CH=CH2] P23.11 c1 = 0.16 g, c2 = 2.2
P21.13 16.7 kJ mol −1 P23.13 K = 0.138 mg g −1, n = 0.58
P21.15 steady-state approximation P23.15 n∞ = 5.78 mol kg −1, K = 7.02 MPa−1
1 1 kQ[Q]
P21.19 = + , 5.1 × 10 6 dm3 mol −1 s−1 [P] eat 1
If Iabs kf Iabs P23.17 (a) = (b + 1) (c) − ln(b)
[P]0 1 + beat a
P21.21 3.5 nm
A y D A 1 D A p+y D
kr′([A]0 + [B]0) + (kr[A]0 − kr′[B]0)e−(kr+kr′)t (d) A0(A0 + P0)kt = B E+B E ln B E,
P21.23 [A] = , C 1 − y F C 1 − p F C p(1 − y)F
kr + kr′
A k′ D A k D (A0 + P0)2ktmax = 12 − p − ln 2p
[A]∞ = B r E × ([A]0 + [B]0), [B]∞ = B r E × ([A]0 + [B]0),
C kr + kr′ F C kr + kr′ F A y D A 1 D A p+y D
(e) A0(A0 + P0)kt = B E+B E ln B E,
[B]∞ kr C p(p + y) F C 1 + p F C p(1 − y)F
= 2−p 2
[A]∞ kr′ + (A0 + P0)2ktmax = ln
2p p
2x(A0 − x) A 2x D A 1 D A A 0 − 2x D
P21.25 (a) krt = (b) B 2 E + B E ln B E νmax
A20(A 0 − 2x)2 C A 0(A 0 − 2x) F C A20 F C A 0 − x F P23.19 ν= , k a′ >> kb
1
P21.27 steady-state intermediate 1+
K[S]0
k1k2 k3[A]0
P21.29 P23.23 it is described by the BET isotherm, 3.96, 75.8 cm3
k1′k 2′ + k1′k3 + k2 k3 P23.25 (a) R values in the range 0.975 to 0.991 (b) ka = 3.68 × 10 −3,
1/2
2 1/2 p M1 Δ ad H = −8.67 kJ mol −1, kb = 2.62 × 10 −5 ppm−1,
P21.31 (〈M 2 〉N − 〈M〉 N ) = , M1{kt[A]0(1 + kt[A]0)}1/2
1−p Δ b H = −15.7 kJ mol −1
P21.33 kr[·M][I]−1/2 P23.27 (b) KF = 0.164 mg g R−1, n = 1.14 (c) 0.164c eq−0.46