Atkins Solutions (A)

Atkins & de Paula: Atkins’ Physical Chemistry 10e
Solutions to a) exercises
Foundations
Topic A
EA.1(a)
Example Element Ground-state Electronic Configuration

(i) Group 2 Ca, calcium [Ar]4s2
(ii) Group 7 Mn, manganese [Ar]3d54s2
(iii) Group 15 As, arsenic [Ar]3d104s24p3
EA.2(a) (i) Chemical formula and name: MgCl2, magnesium chloride

ions: Mg2+ and Cl–
oxidation numbers of the elements: magnesium, +2; chlorine, –1
(ii) Chemical formula and name: FeO, iron(II) oxide

ions: Fe2+ and O2–
oxidation numbers of the elements: iron, +2; oxygen, –2
(iii) Chemical formula and name: Hg2Cl2, mercury(I) chloride

ions: Cl– and Hg22+ (a polyatomic ion)
oxidation numbers of the elements: mercury, +1; chlorine, –1
EA.8(a) (i) CO2 is a linear, nonpolar molecule. (ii) SO2 is a bent, polar molecule. (iii)
N2O is linear, polar molecule. (iv) SF4 has a seesaw molecule and it is a polar
molecule.
EA.9(a) In the order of increasing dipole moment: CO2, N2O, SF4, SO2
EA.10(a) (i) Mass is an extensive property. (ii) Mass density is an intensive property.
(iii) Temperature is an intensive property. (iv) Number density is an intensive property.
EA.11(a) (i) 0.543 mol (ii) 3.27 × 1023 molecules
EA.12(a) (i) 180. g (ii) 1.77 N
EA.13(a) 0.43 bar
EA.14(a) 0.42 atm
EA.15(a) 1.47 × 105 Pa
EA.16(a) T = 310.2 K
© Oxford University Press, 2014.

EA.17(a) θ / °C = 5 9 × (θ F / °F − 32 ) or θ F 173 °F
θ F / °F = 9 5 × θ / °C + 32 , =
EA.18(a) 105 kPa
EA.19(a) S8
EA.20(a) 1.8 MPa
EA.21(a) 4.6 × 105 Pa , 6.9 × 105 Pa
Topic B
EB.1(a) (i) 9.81 m s −1 , 48 mJ (ii) 29.4 m s −1 , 0.43 J
zeE
EB.2(a) sterminal =
6πη R
EB.4(a) (i) 2.25 × 10−20 J (ii) 9.00 × 10−20 J
EB.5(a) (i) 1.88 × 108 m s −1 , 100 keV
EB.6(a) 1.15 × 10−18 J , 1.48 × 10−20 J
EB.7(a) −2.40 V
EB.8(a) 24.1 kJ , 28.8 °C
EB.9(a) 27.2 K or 27.2 °C
EB.10(a) 128 J
EB.11(a) 2.4194 J K −1 g −1
EB.12(a) 75.3 J K −1 mol−1
EB.13(a) 8.3145 kJ mol−1
EB.14(a) S H2 O(g) > S H2 O(l)
EB.15(a) S Fe(3000 K) > SFe(300 K)
−17
EB.17(a) (i) 1.6 × 10 (ii) 0.021
EB.19(a) 4.631× 10−6
EB.21(a) 1.07
EB.22(a) 1.25

EB.23(a) 0.47 kJ
EB.24(a) (i) 1.38 kJ (ii) 4.56 kJ
EB.25(a) 12.47 J mol−1 K −1
EB.26(a) (i) 20.79 J mol−1 K −1 (ii) 24.94 J mol−1 K −1
Topic C
EC.1(a) 2.26 × 108 m s −1
EC.2(a) 4.00 μm , 7.50 × 1013 Hz
Chapter 1
Topic 1A
E1A.1(a) 24 atm, no
E1A.2(a) (i) 3.42 bar (ii) 3.38 atm
E1A.3(a) 30 lb in-2
E1A.4(a) 4.20 × 10-2
E1A.5(a) 0.50 m3
E1A.6(a) 102 kPa
E1A.7(a) 8.3147 J K-1 mol-1
E1A.8(a) S8
E1A.9(a) 6.2 kg
E1A.10(a) (i) 0.762, 0.238, 0.752 bar, 0.235 bar (ii) 0.782, 0.208, 0.0099 bar, 0.772 bar,
0.205 bar
E1A.11(a) 169 g mol-1
E1A.12(a) 273oC
E1A.13(a) (i) 0.67, 0.33 (ii) 2.0 atm, 1.0 atm (iii) 3.0 atm
Topic 1B
E1B.1(a) (i) 9.975

E1B.2(a) 1.90 × 103 m s-1 = 1.90 km s-1, 458 m s-1
E1B.3(a) 0.00687
E1B.4(a) 333 m s-1, 375 m s-1, 596 m s-1
E1B.5(a) (i) 475 m s-1 (ii) 8.3 × 10-8 m (iii) 8.1 × 10-9 s-1
E1B.6(a) � Pa
0.195
E1B.7(a) 1.4 × 10-6 m
Topic 1C
E1C.1(a) (i) 1.0 atm (ii) 1.8 × 103 atm
E1C.2(a) 7.61× 10−2 kg m5 s −2 mol−2 , 2.26 × 10−5 m3 mol−1
E1C.3(a) (i) 0.88 (ii) 1.2 dm3 mol-1, attractive
E1C.4(a) 140 atm
E1C.5(a) (i) 50.7 atm (ii) 35.1 atm, 0.692
E1C.6(a) 1.78 dm6 atm mol–2, 0.0362 dm3 mol–1, 0.122nm
E1C.7(a) (i) 1.41 × 103 K (ii) 0.139nm
E1C.8(a) (i) 3.64 × 103 K, 8.7 atm (ii) 2.62 × 103 K, 4.5 atm (iii) 47K,
0.18 atm
E1C.9(a) 0.46 × 10−4 m3 mol−1 , 0.66
Chapter 2
Topic 2A
−1 −1
E2A.1(a) (i) 72 R , 8.671 kJ mol (ii) 3R , 7.436 kJ mol (iii) 7R , 17.35 kJ mol−1
E2A.2(a) (i) Pressure, (ii) temperature, and (iv) enthalpy are state functions.
E2A.3(a) −75 J
E2A.4(a) (i) ∆U =∆H =0 , −2.68 kJ , +2.68 kJ (ii) ∆U =∆H =0 , −1.62 kJ , +1.62 kJ (iii)
∆U =∆H =0 w=0, 0
E2A.5(a) 1.33atm , +1.25 kJ , w = 0 , +1.25 kJ
E2A.6(a) (i) −88 J (ii) −167 J

Topic 2B
−1 −1
E2B.1(a) 30 J K–1 mol–1, 22 J K mol
E2B.2(a) (i) 1.07 × 104 J = +10.7 kJ , −0.624 × 103 J = −0.624 kJ , +10.1kJ (ii) +10.7 kJ ,
+10.1 kJ , w = 0 , +10.1 kJ
E2B.3(a) +2.2 kJ , +2.2 kJ , +1.6 kJ
Topic 2C
E2C.1(a) 22.5 kJ , −1.6 kJ , 20.9 kJ
E2C.2(a) −4564.7 kJ mol-1
E2C.3(a) +53kJ mol−1 , −33kJ mol−1
E2C.4(a) −167 kJ/mol−1
E2C.5(a) −5152 kJ mol−1 , 1.58 kJ K −1 , +3.08 K
E2C.6(a) (i) −114.40 kJ mol−1 , −111.92 kJ mol−1 (ii) −92.31kJ mol−1 , −241.82 kJ mol-1
E2C.7(a) −1368 kJ mol−1
E2C.8(a) (i) +131.29 kJ mol−1 , +128.81kJ mol−1 (ii) +134.14 kJ mol−1 , +130.17 kJ mol−1
E2C.9(a) −803.07 kJ mol−1
E2C.10(a) −1892 kJ mol−1
Topic 2D
E2D.1(a) 5.03 mbar
E2D.2(a) +130.1 J mol−1 , +7.52 × 103 J mol−1 , −7.39 × 103 J mol−1
E2D.3(a) 1.31× 10−3 K −1
E2D.4(a) 2.0 × 103 atm
E2D.5(a) −7.2 J atm −1 mol−1 , +6.1kJ

Topic 2E
E2E.1(a) Closer , closer
E2E.2(a) 13 1 K
E2E.3(a) 0.00846 m3 , 257 K , −0.89 × 103 J
E2E.4(a) −194 J
E2E.5(a) 9.7 kPa
Chapter 3
Topic 3A
E3A.1(a) Not spontaneous.
E3A.2(a) Tc = 191.2 K
E3A.3(a) (i) 366 J K −1 (ii) 309 J K −1
E3A.4(a) I2(g)
E3A.5(a) 3.1 J K −1
E3A.6(a) 30.0 kJ/mol−1
E3A.7(a) 152.67 J K −1 mol−1
E3A.9(a) ∆H =
0 , +2.7 J K −1 , ∆H tot =
0
E3A.10(a) (i) +2.9 J K −1 , −2.9 J K −1 , 0 (ii) +2.9 J K −1 , 0, +2.9 J K −1 (iii) 0, 0, 0
E3A.11(a) (i) +87.8 J K −1 mol−1 (ii) −87.8 J K −1 mol−1
E3A.12(a) ∆S =92.2 J K −1
Topic 3B
E3B.1(a) (i) 9.13 J K–1 mol–1 (ii) 13.4 J K–1 mol–1 (iii) 14.9 J K–1 mol–1
E3B.2(a) (i) −386.1J K −1 mol−1 (ii) +92.6 J K −1 mol−1 (iii) −153.1J K −1 mol−1

Topic 3C
E3C.1(a) (i) -521.5 kJ mol−1 (ii) +25.8 kJ mol-1 (iii) −178.7kJ mol−1
E3C.2(a) −480.98 kJ mol−1
E3C.3(a) 817.90 kJ mol−1
E3C.4(a) (i) −522.1kJ mol−1 (ii) +25.78 kJ mol −1 (iii) −178.6 kJ mol−1
E3C.5(a) −340 kJ mol−1
Topic 3D
E3D.1(a) −17 J
E3D.2(a) −36.5 J K −1
E3D.3(a) +10 kJ , 1.6 kJ mol−1
E3D.4(a) +11 kJ mol−1
Chapter 4
Topic 4A
E4A.1(a) (a) Single phase (b) two phases (c) three phases (d) two
phases
E4A.2(a) 0.71 J
E4A.3(a) 4
Topic 4B
E4B.1(a) −1.0 × 10−4 K
E4B.2(a) 5.2 × 103 J mol−1 = 5.2 kJ mol−1
E4B.3(a) 70 J mol−1
E4B.4(a) 2.71 kPa
E4B.5(a) +45.23J K −1 mol−1 , +16 kJ mol−1
E4B.6(a) 304 K, 31°C

E4B.7(a) +20.80 kJ mol−1
E4B.8(a) (i) +34.08 kJ mol−1 (ii) 350.5 K
E4B.9(a) 281.8 K or 8.7°C
E4B.10(a) 25 g s −1
E4B.11(a) (i) 1.7 × 103 g (ii) 31× 103 g (iii) 1.4 g
E4B.12(a) (i) +4.9 × 104 J mol−1 = +49 kJ mol−1 (ii) 215°C , +101 J K −1 mol−1
E4B.13(a) 272.80 K
E4B.14(a) 0.0763
Chapter 5
Topic 5A
E5A.1(a) 0, (35.6774 − 0.91846 x + 0.051975 x 2 ) cm3 mol−1
E5A.2(a) 17.5 cm3 mol–1, 18.07 cm3 mol−1
E5A.3(a) −1.2 J mol−1
E5A.4(a) −0.35 kJ , +1.2 J K −1
E5A.5(a) +4.70 J K −1 mol−1
E5A.6(a) 6.7 kPa
E5A.7(a) 886.8 cm3
E5A.8(a) 56 cm3 mol−1
E5A.9(a) 6.4×103 kPa
E5A.10(a) 3.67 × 10−3 mol dm −3
E5A.11(a) (i) 3.4 × 10−3 mol kg −1 (ii) 3.37 × 10−2 mol kg −1
E5A.12(a) 0.17 mol dm–3
Topic 5B
E5B.1(a) 1.3×102 kPa

E5B.2(a) 85 g mol−1
E5B.3(a) 3.8 × 102 g mol−1
E5B.4(a) –0.09°C
E5B.5(a) −3.10 kJ , +10.4 J K −1 , 0
E5B.6(a) (i) 1 (ii) 0.8600

2
E5B.7(a) 0.135 mol kg-1, 24.0 g anthracene
E5B.8(a) 87 kg mol-1
E5B.9(a) 32.2 Torr, 6.1 Torr, 38.3 Torr, 0.840 , 0.160
E5B.10(a) 0.92, 0.08, 0.97, 0.03
E5B.11(a) 0.267, 0.733, 58.6 kPa
E5B.12(a) (i) solution is ideal (ii) 0.830, 0.1703
E5B.13(a) (i) 20.6 kPa (ii) 0.668, 0.332
Topic 5C
E5C.1(a) (i) yM = 0.36 (ii) yM = 0.80 (i.e., yO = 0.20)
E5C.4(a) 0.25, 193oC
E5C.6(a) (i) 76% (ii) 52% (iii) 1.11, 1.46
E5C.7(a) (ii) 620 Torr (iii) 490 Torr (iv) 0.50, 0.72 (v) 0.50, 0.30
Chapter 6
Topic 6A
E6A.1(a) 0.9 mol, 1.2 mol
E6A.2(a) −0.64 kJ
E6A.3(a) 5.80 × 105
E6A.4(a) 2.85 × 10−6
E6A.5(a) (i) 0.141 (ii) 13.5
E6A.6(a) (i) −68.26 kJ mol−1 , 9.13 × 1011 (ii) 1.32 × 109 , −69.8 kJ mol−1

E6A.7(a) = K c × ( c O RT / p O )
K
E6A.8(a) (i)
A B C D Total
Initial amounts / mol 1.00 2.00 0 1.00 4.00
Stated change / mol +0.90
Implied change / mol –0.60 –0.30 +0.90 +0.60
Equilibrium amounts / mol 0.40 1.70 0.90 1.60 4.60
Mole fractions 0.087 0.370 0.196 0.348 1.001
(ii) 0.33 (iii) 0.33 (iv) +2.8 kJ mol−1
E6A.9(a) +12.3 kJ mol−1
E6A.10(a) −14.4 kJ mol−1 , toward the ammonia product
E6A.11(a) −1108 kJ mol−1
Topic 6B
E6B.1(a) 0.045 , 1500 K
E6B.2(a) +2.77 kJ mol−1 , − 16.5 J K −1 mol−1
E6B.3(a) 50%
E6B.4(a) 0.9039 , 0.0961
E6B.5(a) (i) 52.89 kJ mol−1 (ii) −52.89 kJ mol−1
E6B.6(a) 1110 K
E6B.7(a) 70.2 kJ mol−1 , 110 kJ mol−1 K −1 , −6.3 kJ mol−1 , 3.0
Topic 6C
E6C.2(a) (i) +1.10 V (ii) +0.22 V (iii) +1.23 V
E6C.3(a) (i) Cd2+(aq) + 2Br–(aq) + 2 Ag(s) → Cd(s) + 2 AgBr(s) (iii) −0.62 V
Topic 6D
E6D.1(a) (i) 6.5 × 109 (ii) 1.4 × 1012
E6D.2(a) (i) 8.47×10–17 (ii) 9.20 × 10−9 mol dm −3 or 2.16 μg dm −3

Chapter 7
Topic 7A
E7A.1(a) (i) 6.6 × 10−19 J , 4.0 × 102 kJ mol−1 (ii) 6.6 × 10−20 J , 40 kJ mol−1 (iii)
6.6 × 10−34 J , 4.0 × 10−13 kJ mol−1
E7A.2(a)
λ / nm E / aJ Em / (kJ mol–1)
(i) 600 331 199
(ii) 550 361 218
(iii) 400 497 299
E7A.3(a)
λ / nm Ephoton / aJ v / (km s–1)
(i) 600 331 19.9
(ii) 550 361 20.8
(iii) 400 497 24.4
E7A.4(a) 21 m s −1
E7A.5(a) (i) 2.77 × 1018 (ii) 2.77 × 1020
E7A.6(a) (i) no electron ejection (ii) 3.19 × 10−19 J , 837 km s −1
E7A.7(a) 6.96 keV , 6.96 keV
E7A.8(a) 7.27 × 106 m s −1 , 150 V
E7A.9(a) 0.024 m s −1
E7A.10(a) 332 pm
E7A.11(a) (i) 6.6 × 10−29 m (ii) 6.6×10−36 m (iii) 99.7 pm
Topic 7B

1/ 2
 1 
E7B.3(a) N = 
 2π 
E7B.4(a) (1 / 2π ) dφ
1
E7B.5(a)
2
Topic 7C
E7C.1(a) Vˆ = 1
2 kf x 2
L
E7C.5(a)
2
−27 −1
E7C.7(a) 1.1×10−28 m s , 1.1×10 m
E7C.8(a) 700 pm
1
E7C.9(a) (i) − (ii) 2x
x2
Chapter 8
Topic 8A
E8A.1(a) 5 × 10−20 J
E8A.2(a) Aeikx
E8A.3(a) (i) 1.81× 10−19 J , 1.13 eV , 9100 cm −1 , 109 kJ mol−1 (ii) 6.6 × 10−19 J ,
4.1 eV , 33 000 cm −1 , 400 kJ mol−1
E8A.4(a) (i) 0.04 (ii) 0
h2
E8A.5(a)
4 L2
1 1 
E8A.6(a) L2  − 2 
 3 2π 
h λ
E8A.7(a) = C
81/ 2 me c 81/2
L L 5L
E8A.8(a) , and
6 2 6

E8A.9(a) −17.4%
2kTmL2 1
E8A.10(a) −
h2 2
E8A.11(a) n1=1, n2=4
E8A.12(a) 3
E8A.13(a) 0.8
Topic 8B
E8B.1(a) 4.30 × 10−21 J
E8B.2(a) 278 N m −1
E8B.3(a) 2.64 µ m
E8B.4(a) 8.3673 × 10−28 kg , 1.6722 × 10−27 kg , 93.3 THz
E8B.5(a) (i) 3.3 × 10−34 J (ii) 3.3 × 10−33 J
E8B.6(a) 5.61× 10−21 J
E8B.7(a) ±0.525α or ±1.65α
E8B.8(a) ±α
E8B.9(a) 0.056, 0.112
Topic 8C
E8C.1(a) 0, ±
1/ 2
 1 
E8C.2(a)  
 2π 
E8C.3(a) 3.32 × 10−22 J
E8C.4(a) 2.11× 10−22 J
E8C.5(a) 4.22 × 10−22 J
E8C.6(a) 21/2, 1.49×10–34 J s
E8C.8(a) 7

Chapter 9
Topic 9A
E9A.1(a) (i) g = 1 (ii) g = 9 (iii) g = 25
2
E9A.2(a) N=
a03 2
E9A.3(a) 4a0 , r = 0.
E9A.4(a) r = 0.35a0
E9A.5(a) 101 pm and 376pm
E9A.6(a) 2 E1s , − E1s
a0
E9A.7(a) 5.24
Ζ
E9A.8(a) r = 2a0 / Z
E9A.10(a) 6a0 / Z , xy plane, θ = π/2, yz, θ = 0, xz, θ = 0
Topic 9B
E9B.2(a) (i) [Ar]3d8 (ii) S = 1, 0 , M S = −1, 0, + 1 , M S = 0
Topic 9C
E9C.1(a) 9.118 × 10−6 cm , 1.216 × 10−5 cm
E9C.2(a) 3.292 × 105 cm-1 , 3.038 × 10−6 cm , 9.869 × 1015 s-1
E9C.3(a) 14.0 eV
E9C.4(a) (i) Forbidden (ii) allowed (iii) allowed
E9C.5(a) (i) 52 , 32 (ii) 72 , 52
E9C.6(a) l =1
E9C.7(a) L =2, S =0, J =2
E9C.8(a) (i) 1, 0 , 3,1 (ii) 32 , 12 , and 12 , 4, 2, 2

3
E9C.9(a) D3 , 3 D 2 , 3 D1 , 1D 2 , 3 D set of terms are the lower in energy
E9C.10(a) (i) J = 0 , 1state (ii) J = 32 , 12 , 4, 2 states respectively (iii) J = 2,1, 0 , 5, 3,

1 states respectively
E9C.11(a) (i) 2 S1/ 2 (ii) 2 P3/ 2 and 2P1/ 2
E9C.12(a) (i) Allowed (ii) forbidden (iii) allowed
Chapter 10
Topic 10A
E10A.1(a) {s(1)pz(2)+s(2)pz(1)} × {α(1)β(2)–α(2)β(1)}
E10A.2(a) ψ =aψ VB + bψ H F + cψ H F
− + + −
–1/2 –1/2
E10A.6(a) N=3 ,ψ=3 (s + 21/2p)
Topic 10B
1/ 2
 1 
E10B.1(a) N = 2 
 1 + 2λ S + λ 
E10B.2(a) N = 1.12, ψ1 = 0.163A + 0.947B, b = 0.412, a = –1.02, ψ2 = –1.02A + 0.412B
E10B.3(a) 1.9 eV, 130 pm
E10B.4(a) u, g
Topic 10C
E10C.1(a) (i) 1σg2, b=1 (ii) 1σg21σu2, b=0 (iii) 1σg21σu21πu4, b=2
E10C.2(a) C2
E10C.3(a) F2+
E10C.4(a) b=1, b=0, b=1, b=2, b=3, b=2, b=1
E10C.5(a) 1σg, 1σu, 1πu, 1πu, 2σg, 1πg, 1πg, 1σu, 1πu, 1πu, 2σg, 1πg, 1πg, 2σu
E10C.6(a) 4 × 105 m s −1
E10C.7(a) (i) 2.1×10–10 m = 0.21 nm (ii) 1.0×10–10 m = 0.10 nm

Topic 10D
E10D.1(a) (i) 1σ22σ21π43σ2 (ii) 1σ22σ23σ21π42π1 (iii) 1σ22σ21π43σ2
E10D.3(a) NO+
E10D.5(a) 7.2, 8.3
E10D.6(a) −6.6 or − 8.9
E10D.7(a) –5.0 or –10.7 eV
Topic 10E
E10E.2(a) (i) a2u2e1g4e2u1, 7α + 7β (ii) a2u2e1g3, 5α + 7β
E10E.3(a) (i) 7β, 0 (ii) 7β, 2β
E10E.5(a) (i) 14α + 19.314β (ii) 14α + 19.448β
Chapter 11
Topic 11A
E11A.1(a) Identity E, C3 axis, three vertical mirror planes σv
E11A.2(a) D2h, 3C2 axes, a centre of inversion, 3σh mirror planes
E11A.3(a) (i) R3 (ii) C2v (iii) D3h (iv) D∞h
E11A.4(a) (i) C2v (ii) C∞v (iii) C3v (iv) D2h
E11A.5(a) (i) C2v (ii) C2h
E11A.6(a) (i) pyridine (ii) nitroethane
E11A.7(a)
Isomers and Point Groups of m,n-Dichloronaphthalene
m,n 1,2 1,3 1,4 1,5 1,6 1,7 1,8 2,3 2,6 2,7
Point Group Cs Cs C2v C2h Cs Cs C2v C2v C2h C2v

E11A.8(a) i, σ h
Topic 11B
 −1 0 0 0 
 
 0 −1 0 0 
E11B.1(a) D(σ h ) =
 0 0 −1 0 
 
 0 0 0 −1
 −1 0 0 0 
 
E11B.2(a)  0 0 −1 0  = D( S )
 0 0 0 −1 3
 
 0 −1 0 0 
Topic 11C
E11C.4(a) no N orbitals, d xy
E11C.6(a) 2A1 + B1 + E
E11C.7(a) (i) Either E1u or A2u (ii) B3u ( x -polarized) , B2u ( y -polarized) , B1u ( z − polarized)
E11C.8(a) zero
Chapter 12
Topic 12A
E12A.1(a) (i) 0.0469 J m −3 s (ii) 1.33 × 10−13 J m −3s (iii) 4.50 × 10−28 J m −3 s
E12A.2(a) 82.9 %
E12A.3(a) 5.34 × 103 dm3 mol−1 cm −1
E12A.4(a) 1.09 mmol dm −3

E12A.5(a) 450 dm3 mol–1 cm–2
E12A.6(a) 159 dm3 mol−1 cm −1 , 23 per cent
E12A.7(a) (i) 0.87 m (ii) 2.9 m
E12A.8(a) 1.3 × 108 dm3 mol−1 cm −2
E12A.9(a) (i) 5 × 107 dm3 mol−1 cm −2 (ii) 2.5 × 106 dm3 mol−1 cm −2
E12A.10(a) 0.9999 × λ
E12A.11(a) (i) 27 ps (ii) 2.7 ps
E12A.12(a) (i) δν = 53 cm −1 (ii) δν = 0.53 cm −1
Topic 12B
E12B.1(a) 6.33 × 10−46 kg m 2 , 0.4421 cm −1
E12B.3(a) (i) Asymmetric (ii) oblate symmetric (iii) spherical (iv) prolate symmetric
E12B.4(a) 106.5 pm , 115.6 pm
−4 −1
E12B.5(a) 2.073 × 10 cm , 0.1253
Topic 12C
E12C.2(a) 3.07 × 1011 Hz
E12C.3(a) 127.4 pm
E12C.4(a) 4.442 × 10−47 kg m 2 , 165.9 pm
E12C.5(a) (i) 20 (ii) 23
E12C.6(a) (iii) CH4 is inactive, (i), (ii), and (iv) are active.
E12C.7(a) 20 475cm −1
E12C.8(a) 198.9 pm
5
E12C.9(a)
3
Topic 12D

E12D.1(a) 1.6 × 102 N m −1
E12D.2(a) 1.077 %
E12D.3(a) 328.7 N m −1
E12D.4(a) 967.0, 515.6, 411.8, 314.2
E12D.5(a) (i) 0.067 (ii) 0.20
E12D.6(a) 1580.38 cm −1 , 7.644 × 10−3
E12D.7(a) 5.13 eV
Topic 12E
E12E.3(a) 127
E12E.4(a) 1
2 ( v1 + v2 + v3 )
E12E.6(a) Raman active
E12E.7(a) 4A1 + A 2 +2B1 + 2B2
E12E.8(a) A1 , B1 and B2 are infrared active, all modes are Raman active
Chapter 13
Topic 13A
E13A.1(a) 3, u
E13A.2(a) (i) Allowed (ii) allowed (iii) forbidden (iv) forbidden (v) allowed
2 2 −2 ax02 /3
E13A.3(a) e
3
2
1  4
E13A.4(a) 3+ 
32  π
E13A.5(a) 1
2 ( B '+ B ) / ( B '− B )
E13A.6(a) 1
2 ( B '+ B ) / ( B '− B ) − 1 , 7
E13A.7(a) 30.4 cm −1 < B ' < 40.5 cm −1 , greater
∆ O = P − v , 14 × 10 cm
3 –1
E13A.8(a)

1/ 2
3  a3 
E13A.9(a)  
8  b − 12 a 
E13A.10(a) 1
4 e −1/16 a
Topic 13B
13B.1(a) (i) Lower, v ≈ 1800 cm −1 (ii) no information
Topic 13C
E13C.1(a) λ = 2.0 cm (v = 15.0 GHz)
E13C.2(a) 20 ps , 70 MHz
Chapter 14
Topic 14A
E14A.1(a) s-1 T -1
E14A.2(a) ±54.74
9.133 × 10−35 J s , ±5.273 × 10−35 J s , ±0.9553 rad =
E14A.3(a) 574 MHz
E14A.4(a) −1.473 × 10−26 J × mI
E14A.5(a) 165 MHz
E14A.6(a) (i) 3.98 × 10−25 J (ii) 6.11× 10−26 J , (a).
E14A.7(a) (i) 1× 10−6 (ii) 5.1× 10−6 (iii) 3.4 × 10−5
E14A.8(a) 13
E14A.9(a) 2 × 102 T , 10 mT
Topic 14B
E14B.1(a) (i) Independent (ii) 13

E14B.2(a) (i) 11µ T (ii) 110µ T
E14B.5(a) 753 MHz
E14B.9(a) 0.39 ms, 2.6 × 103 s −1
Topic 14C
E14C.1(a) 9.40 × 10−4 T , 6.25 μs
E14C.2(a) 0.21 s
E14C.3(a) 1.234
Topic 14D
E14D.1(a) 2.0022
E14D.2(a) 2.3 mT , 2.0025
E14D.3(a) Equal intensity , 330.2 mT, 332.2 mT, 332.8 mT, 334.8 mT
E14D.5(a) (i) 332.3 mT (ii) 1.206 T
E14D.6(a) I= 3
2
Chapter 15
Topic 15A
E15A.1(a) 21621600
E15A.2(a) (i) 40320 (ii) 5.63×103 (iii) 3.99×104
E15A.3(a) 1
E15A.4(a) 524 K
E15A.5(a) 7.43
E15A.6(a) 354 K
Topic 15B

E15B.1(a) (i) 8.23 × 10−12 m , 8.23 pm , 2.60 × 10−12 m , 2.60 pm (ii) 1.79 × 1027 , 5.67 × 1028
E15B.2(a) 0.3574
E15B.3(a) 72.2
E15B.4(a) (i) 7.97 × 103 (ii) 1.12 × 104
E15B.5(a) 18 K
E15B.6(a) 37 K
E15B.7(a) 4.5 K
E15B.8(a) (i) 1 (ii) 2 (iii) 2 (iv) 12 (v) 3
E15B.9(a) 660.6
E15B.10(a) 4500 K
E15B.11(a) 2.571
E15B.12(a) 42.3
E15B.13(a) 4.292 , 0.0353 to 0.0377 to 1
Topic 15C
E15C.1(a) 8.16 × 10−22 J
E15C.2(a) 18.5 K
E15C.3(a) 25 K
E15C.4(a) 4.5 K
E15C.5(a) 4600 K
E15C.6(a) 10500 K
E15C.7(a) 6500 K
E15C.8(a) 4.033 × 10−21 J
Topic 15D
E15D.1(a) He gas, CO gas, H2O vapour

Topic 15E
E15E.1(a) (i) 72 R (ii) 3R (iii) 7R
E15E.2(a) Closer, closer
E15E.3(a) (i) 4.158 (ii) 4.489
E15E.4(a) (i) 14.93 J K–1 mol–1 (ii) 25.65 J K–1 mol–1
E15E.5(a) (i) 126 J K −1 mol−1 (ii) 169 J K −1 mol−1
E15E.6(a) 2.35 × 103 K
E15E.7(a) 43.1 , 22.36 K , 43.76 J K −1 mol−1
E15E.8(a) 11.5 J K −1 mol−1
E15E.9(a) (i) 34.72 J K–1 mol–1 (ii) 119.06 J K–1 mol–1
Topic 15F
E15F.1(a) −13.8 kJ mol−1 , −0.20 kJ mol−1
E15F.2(a) (i) −6.42 kJ mol−1 (ii) −14.0 kJ mol−1
E15F.3(a) 3.70 × 10−3
Chapter16
Topic 16A
E16A.1(a) CIF3, O3 , H2O2
E16A.2(a) 1.4 D
E16A.3(a) 37 D , 11.7°
E16A.4(a) 1.66 D , 1.01× 10−39 J −1 C2 m 2 , 9.06 × 10−30 m3
E16A.5(a) 4.75
E16A.6(a) 1.42 × 10−39 J −1 C2 m 2
E16A.7(a) 1.34
E16A.8(a) 17.7

Topic 16B
E16B.1(a) 1.07 × 103 kJ mol−1
6l 4 Q12
E16B.2(a)
πε 0 r 5
E16B.3(a) 0.071 J mol−1
E16B.4(a) 289 kJ mol−1
Topic 16C
E16C.1(a) 2.6 kPa
E16C.2(a) 72.8 mN m −1
E16C.3(a) 728 kPa
Chapter 17
Topic 17A
E17A.1(a) 27 nm
E17A.2(a) 3.08 μm , 30.8 nm
E17A.3(a) 2.4 × 103
E17A.4(a) 0.017
E17A.5(a) 6.4 × 10−3
E17A.6(a) +41.42% , +182.8%
E17A.7(a) 1000 , +9.84 × 104 % when N =

+895 % when N = 1000
E17A.8(a) 1.6 × 102 pm
Topic 17B
E17B.1(a) −19 mJ mol−1 K −1
E17B.2(a) 3.7 × 10−14 N

Topic 17C
E17C.1(a) 3.43
Topic 17D
E17D.1(a) 70 kg mol−1 , 71 kg mol−1
E17D.2(a) (i) 18 kg mol−1 (ii) 20 kg mol−1
E17D.3(a) 100
E17D.4(a) 64 kg mol−1
E17D.5(a) 0.73 mm s −1
E17D.6(a) 31 kg mol−1
E17D.7(a) 3.4 × 103 kg mol−1
Chapter 18
Topic 18A
E18A.1(a) N = 4 , 4.01 g cm −3
E18A.2(a) (323) and (110)
E18A.3(a) 229 pm , 397 pm , 115 pm
E18A.4(a) 220 pm
E18A.5(a) 70.7 pm
E18A.6(a) 10.1 , 14.4 , 17.7
E18A.7(a) 8.16° , 4.82° , 11.75°
E18A.8(a) f Br − = 36
E18A.9(a) f Br − = 36
E18A.10(a) f
E18A.11(a) 3 f for h + k even and − f for h + k odd
E18A.15(a) 6.1 km s −1

E18A.16(a) 233 pm
Topic 18B
E18B.1(a) 0.9069
E18B.2(a) (i) 0.5236 (ii) 0.6802 (iii) 0.7405
E18B.3(a) (i) 74.9 pm (ii) 132 pm
E18B.4(a) Expansion
E18B.5(a) 3500. kJ mol−1
Topic 18C
E18C.1(a) 9.3 × 10−4 cm 3
E18C.2(a) n-type; the dopant, arsenic, belongs to Group 15 whereas germanium belongs to
Group 14.
E18C.3(a) Three unpaired spins
E18C.4(a) −6.4 × 10−5 cm 3 mol −1 = −6.4 × 10−11 m3 mol−1
E18C.5(a) 4.326 , 5
E18C.6(a) +1.6 × 10−8 m3 mol−1
Topic 18D
E18D.1(a) 3.54 eV
Chapter 19
Topic 19A
E19A.1(a) 7.6 × 10−3 J K −1 m −1 s −1
E19A.2(a) (i) D = 1.5 m2 s−1 , Jz/NA = −61 mol m−2 s−1 (ii) D = 1.5×10−5 m2 s−1, Jz/NA =
−6.1×10−4 mol m−2 s−1 (iii) D = 1.5×10−7 m2 s−1, Jz/NA = −6.1×10−6 mol m−2 s−1
E19A.3(a) −0.078 J m −2 s −1

E19A.4(a) 0.0795 nm 2
E19A.5(a) 103 W
E19A.6(a) 0.201 nm 2
E19A.7(a) (i) η = 178 µP (ii) η = 186 µP (iii) η = 342 µP
E19A.8(a) 1.9 × 1020
E19A.9(a) 104 mg
E19A.10(a) 2.15 × 103 Pa
E19A.11(a) 42.4 g mol−1
E19A.12(a) 1.3 days
Topic 19B
E19B.1(a) 16.8 J mol−1
E19B.2(a) 7.63 × 10−3 S m 2 mol−1
E19B.3(a) 283 μm s −1
E19B.4(a) 13.87 mS m 2 mol−1
E19B.5(a) 4.01× 10−8 m 2 V −1 s −1 , 5.19 × 10−8 m 2 V −1 s −1 , 7.62 × 10−8 m 2 V −1 s −1
E19B.6(a) 420 pm
E19B.7(a) 1.90 × 10−9 m 2 s −1
Topic 19C
E19C.1(a) 6.2 × 103 s
E19C.2(a) (i) 0.00 mol dm −3 (ii) 0.0121 mol dm −3
E19C.3(a) 25 kN mol−1 , ∞
E19C.4(a) 67.5 kN mol−1
E19C.5(a) 1.3 × 103 s
E19C.6(a) 0.42 nm

E19C.7(a) 27.3 ps
E19C.8(a) 113 μm , 56 μm
Chapter 20
Topic 20A
E20A.1(a) No change in pressure
E20A.2(a) 8.1 mol dm–3 s–1, 2.7 mol dm–3 s–1, 2.7 mol dm–3 s–1, 5.4 mol dm–3 s–1
E20A.3(a) 1.35 mol dm −3 s −1 , 4.05 mol dm −3 s −1 , 2.7 mol dm–3 s–1, 1.35 mol dm −3 s −1
E20A.4(a) dm3 mol–1 s–1, (i) kr[A][B] (ii) 3kr[A][B]
1
E20A.5(a) kr [A][B][C] , dm 6 mol−2 s −1
2
E20A.6(a) (i) [kr] = dm3 mol–1 s–1, [kr] = dm6 mol–2 s–1 (ii) [kr] = kPa–1 s–1, [kr] = kPa–2 s–1
Topic 20B
E20B.1(a) n=2
E20B.2(a) 1.03 × 104 s , (i) 498Torr (ii) 461Torr
E20B.3(a) (i) 0.098 mol dm −3 (ii) 0.050 mol dm −3
E20B.4(a) 1.11× 105 s , 1.28 days
Topic 20C
E20C.1(a) 7.1×105 s–1, 1.28 × 104 dm3 mol−1 s −1
Topic 20D
E20D.1(a) 1.08 × 105 J mol−1 = 108 kJ mol−1 , 6.50×1015 dm3 mol–1 s–1, 6.50×1015 dm3 mol–1 s–1
E20D.2(a) 35 kJ mol−1

Topic 20E
k2 2 [B]2  16k1′k1[A 2 ] 
E20E.1(a) (i) k2 K 1/ 2 [A 2 ]1/ 2 [B] (ii)  1 + − 1 , k2 K 1/ 2 [A 2 ]1/ 2 [B] , 2k1[A 2 ]

4k1′  k 2
2
[B]2

E20E.2(a) –3 kJ mol–1
Topic 20F
E20F.1(a) 1.9 × 10−6 Pa −1 s −1 , 1.9 MPa–1 s–1
E20F.2(a) 251 , 0.996
E20F.3(a) 0.125
Topic 20G
E20G.1(a) 3.3 × 1018
E20G.2(a) 0.56 mol dm −3
Topic 20H
kb K [AH]2 [B]
E20H.1(a)
[BH + ]
E20H.2(a) 1.50 mmol dm −3 s −1
E20H.3(a) 2.0 × 10−5 mol dm −3
Chapter 21
Topic 21A
E21A.1(a) 1.13 × 1010 s −1 , 1.62 × 1035 s −1 m −3 , 1.7%
E21A.2(a) (i) 1.04×10–3, 0.069 (ii) 1.19×10–15, 1.57×10–6
E21A.3(a) (i) 22%, 3% (ii) 170%, 16%
E21A.4(a) 1.03 × 10−5 m3 mol−1 s −1 , 1.03 × 10−2 dm3 mol−1 s −1

E21A.5(a) 0.79 nm 2 , 1.16 × 10−3
E21A.6(a) 0.73
E21A.7(a) 5.1× 10−7
Topic 21B
E21B.1(a) 4.5 × 107 m3 mol−1 s −1 , 4.5 × 1010 dm3 mol−1 s −1
E21B.2(a) (i) 6.61× 106 m3 mol−1 s −1 , 6.61× 109 dm3 mol−1 s −1 (ii) 3.0 × 107 m3 mol−1 s −1 ,
3.0 × 1010 dm3 mol−1 s −1
E21B.3(a) 8.0 × 106 m3 mol−1 s −1 , 8.0 × 109 dm3 mol−1 s −1 , 4.2 × 10−8 s
E21B.4(a) 1.81× 108 mol dm −3 s −1
Topic 21C
E21C.1(a) +69.7 kJ mol–1, −25 J K −1 mol−1
E21C.2(a) +73.4 kJ mol–1, +71.9 kJ mol–1
E21C.3(a) −91 J K −1 mol−1
E21C.4(a) −74 J K −1 mol−1
E21C.5(a) (i) −46 J K −1 mol−1 (ii) +5.0 kJ mol–1 (iii) +18.7 kJ mol–1
E21C.6(a) 7.1 dm6 mol–2 min–1
Topic 21D
E21D.1(a) Reactant is high in translational energy and low in vibrational energy, product is high
in vibrational energy and relatively lower in translational energy
Topic 21E
E21E.1(a) 4×10–21 J, 2 kJ mol–1
E21E.2(a) 12.5 nm −1
Topic 21F

E21F.1(a) 0.138 V
E21F.2(a) 2.82 mA cm–2
E21F.3(a) Increases, factor of 50
E21F.4(a) (i) 1.7×10–4 A cm–2 (ii) 1.7×10–4 A cm–2
E21F.5(a) (i) 0.31 mA cm–2 (ii) 5.44 mA cm–2 (iii) –2×1042 mA cm–2
E21F.6(a) 4.9 × 1015 cm −2 s −1 , 1.6 × 1016 cm −2 s −1 , 3.1× 107 cm −2 s −1 , 3.9 s–1, 12 s–1, 2.4×10–8 s–1
E21F.7(a) (i) 33 Ω (ii) 3.3 × 1010 Ω
E21F.8(a) One can (barely) deposit zinc
Chapter 22
Topic 22A
22A.1(a) (i) 1.4 × 1014 cm–2 s–1 (ii) 3.1 × 1013 cm–2 s–1
22A.2(a) 0.13 bar
Topic 22B
E22B.1(a) 33.6 cm3
E22B.2(a) Chemisorption , 50 s
E22B.3(a) 0.83 , 0.36
E22B.4(a) (i) 0.24 kPa (ii) 25 kPa
E22B.5(a) 15 kPa
E22B.6(a) −12.4 kJ mol−1
E22B.7(a) 65 1 kJ mol−1 (i) 1.6 × 1097 min (ii) 2.8 × 10–6 min
E22B.8(a) 61 1 kJ mol−1
E22B.9(a) (i) 9.1 ps , 0.60 ps (ii) 4.1× 106 s , 6.6 µs
E22B.10(a) Zeroth-order , first-order

Topic 22C
E22C.1(a) 12 m 2

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Atkins & de Paula: Atkins’ Physical Chemistry 10e

Example Element Ground-state Electronic Configuration

EA.2(a) (i) Chemical formula and name: MgCl2, magnesium chloride

(ii) Chemical formula and name: FeO, iron(II) oxide

(iii) Chemical formula and name: Hg2Cl2, mercury(I) chloride

EA.11(a) (i) 0.543 mol (ii) 3.27 × 1023 molecules

EA.12(a) (i) 180. g (ii) 1.77 N

EA.13(a) 0.43 bar

EA.14(a) 0.42 atm

EA.15(a) 1.47 × 105 Pa

© Oxford University Press, 2014.

EA.18(a) 105 kPa

EA.20(a) 1.8 MPa

EA.21(a) 4.6 × 105 Pa , 6.9 × 105 Pa

EB.1(a) (i) 9.81 m s −1 , 48 mJ (ii) 29.4 m s −1 , 0.43 J

EB.4(a) (i) 2.25 × 10−20 J (ii) 9.00 × 10−20 J

EB.5(a) (i) 1.88 × 108 m s −1 , 100 keV

EB.6(a) 1.15 × 10−18 J , 1.48 × 10−20 J

EB.8(a) 24.1 kJ , 28.8 °C

EB.9(a) 27.2 K or 27.2 °C

EB.12(a) 75.3 J K −1 mol−1

EB.13(a) 8.3145 kJ mol−1

EB.14(a) S H2 O(g) > S H2 O(l)

EB.15(a) S Fe(3000 K) > SFe(300 K)

EB.19(a) 4.631× 10−6

© Oxford University Press, 2014.

EB.24(a) (i) 1.38 kJ (ii) 4.56 kJ

EB.25(a) 12.47 J mol−1 K −1

EB.26(a) (i) 20.79 J mol−1 K −1 (ii) 24.94 J mol−1 K −1

EC.1(a) 2.26 × 108 m s −1

EC.2(a) 4.00 μm , 7.50 × 1013 Hz

E1A.2(a) (i) 3.42 bar (ii) 3.38 atm

E1A.4(a) 4.20 × 10-2

E1A.6(a) 102 kPa

E1A.7(a) 8.3147 J K-1 mol-1

E1A.11(a) 169 g mol-1

E1B.1(a) (i) 9.975

© Oxford University Press, 2014.

E1B.2(a) 1.90 × 103 m s-1 = 1.90 km s-1, 458 m s-1

E1B.4(a) 333 m s-1, 375 m s-1, 596 m s-1

E1B.7(a) 1.4 × 10-6 m

E1C.1(a) (i) 1.0 atm (ii) 1.8 × 103 atm

E1C.2(a) 7.61× 10−2 kg m5 s −2 mol−2 , 2.26 × 10−5 m3 mol−1

E1C.3(a) (i) 0.88 (ii) 1.2 dm3 mol-1, attractive

E1C.4(a) 140 atm

E1C.5(a) (i) 50.7 atm (ii) 35.1 atm, 0.692

E1C.6(a) 1.78 dm6 atm mol–2, 0.0362 dm3 mol–1, 0.122nm

E1C.7(a) (i) 1.41 × 103 K (ii) 0.139nm

E1C.9(a) 0.46 × 10−4 m3 mol−1 , 0.66

E2A.5(a) 1.33atm , +1.25 kJ , w = 0 , +1.25 kJ

E2A.6(a) (i) −88 J (ii) −167 J

© Oxford University Press, 2014.

E2B.3(a) +2.2 kJ , +2.2 kJ , +1.6 kJ

E2C.1(a) 22.5 kJ , −1.6 kJ , 20.9 kJ

E2C.2(a) −4564.7 kJ mol-1

E2C.3(a) +53kJ mol−1 , −33kJ mol−1

E2C.4(a) −167 kJ/mol−1

E2C.5(a) −5152 kJ mol−1 , 1.58 kJ K −1 , +3.08 K

E2C.7(a) −1368 kJ mol−1