Atkins Elements 4e Answers

Atkins & De Paula: Elements of Physical Chemistry: 4e
NUMERICAL ANSWERS TO END OF CHAPTER EXERCISES
Question Numerical answer

Introduction
0.5 2.6 kJ
0.10 59 J
(a) 825 Torr;
(b) 0.984 atm;
0.14
(c) 0.212 atm;
(d) 9.64 × 104 Pa
0.15 1.24 × 108 Pa ( = 1.22 × 103 atm)
0.16 1.6 × 10 −2
0.17 1.5 × 103 Pa ( = 1.5 × 10 −2 atm)
0.19 −459.67 °F
0.21 671.67 °R
0.22 3.74 × 1019 molecules
0.23 0.97 or 97%
Chapter 1
1.5 89.2 kPa
1.6 4.22 × 10 −2 atm
1.7 2.52 × 10 −3 mol
1.8 6.64 × 103 kPa
1.9 10.0 atm
1.10 418 kPa
1.11 173 kPa
1.12 29.5 K
1.13 388 K
1.14 (a) 3.6 m3; (b) 178 m3
1.15 0.50 m3
1.16 3.2 × 10 −2 atm
1.17 (a) 1.32 L; (b) 61.2 kPa
1.18 713 Torr
OXFORD H i g h e r Education
© Oxford University Press, 2006. All rights reserved.
1.19 132 g mol −1

1.20 16.4 g mol −1
(a) p(H2) = 2.0 atm, p(N2) = 1.0 atm;
1.21
(b) 3.0 atm
(a) (i) 693 m s −1, (ii) 1363 m s −1, (iii) 2497 m s −1;
1.22
(b) (i) 346 m s −1, (ii) 681 m s −1, (iii) 1247 m s −1
1.26 0.91%
1.27 0.065 Pa
1.28 2.4 × 106 Pa
1.29 0.97 µm
(a) 5.3 × 1010;
1.30 (b) 5.3 × 109 collisions;
(c) 5.3 × 104
(a) 6.4 × 1033 collisions;
1.31 (b) 6.4 × 1031 collisions;
(c) 6.4 × 1021 collisions
1.32 4.5 × 108 collisions/s
1.33 (a) 6.8 nm; (b) 68 nm; (c) 7 mm
1.34 independent of temperature
(a) 8.3 × 102 atm;
1.35
(b) (i) 0.99 atm,(ii) 1.7 × 103atm
1.36 4.37 MPa
RT ⎡ B C ⎤
1.37 p= ⎢1 + 1 + 2 + ...⎥
Vm ⎣ Vm Vm ⎦
1.38 1.26 L2 atm mol −2
1.39 1.02 × 103 K
Chapter 2
2.5 (a) 98 J; (b) 16 J
2.6 39 J
2.7 2.6 kJ
2.8 3.03 J
2.12 −14 J
2.13 −1.0 × 102 J
2.14 (a) 895 J; (b) 899 J
2.15 (a) −88 J; (b) −167 J
2.16 +123 J
2.17 +2.99 kJ
2.18 −1.25 kJ
2.21 23.7 J K −1
2.22 42 kJ
2.23 4.4 × 104 J
2.24 38 J K −1 mol −1
2.25 6.1 × 102 s
2.26 1.86 × 103 J
2.27 773 J
2.28 −8.0 J
2.29 29.3 J
(a) 2.479 kJ mol −1;
2.31
(b) decreased
2.32 80 J K −1
2.33 q = +2.2 kJ; ∆H = +2.2 kJ; ∆U = +1.6 kJ
2.34 20.83 J K −1 mol −1
2.35 458 J mol −1
2.36 818 J mol −1
Chapter 3
3.6 2.53 × 104 kJ
3.8 39.8 kJ mol −1
q = +39.0 kJ; w = −3.12 kJ; ∆H = +39.0 kJ (constant pressure);
3.9
∆U = 35.9 kJ
3.10 301 kJ
3.11 478 kJ
3.16 (a) 388 kJ mol −1; (b) smaller

3.17 (a) 16 kJ mol −1; (b) −3028 kJ mol −1
3.18 −46.11 kJ
3.19 (a) −1560 kJ mol −1; (b) −2340 kJ
3.20 −4564.7 kJ mol −1
3.21 −85 kJ mol −1
3.22 −432 kJ mol −1
3.23 +79 kJ mol −1
3.24 0.769 K
(a) −2.80 MJ mol −1 ;
3.25 (b) −2.80 MJ mol −1;
(c) −1.28 MJ mol −1
(a) −1333 kJ mol −1 ;
3.26 (b) −1331 kJ mol −1;
(c) −815 kJ mol −1
3.27 +84.40 kJ mol −1
3.28 −383 kJ mol −1
3.29 +1.9 kJ mol −1
3.30 +30.6 kJ mol −1
3.31 7.5 m
(a) −2205 kJ mol −1;
3.32
(b) −2200 kJ mol −1
(a) exothermic, ∆rHo = negative;
(b) endothermic, ∆Ho = positive;
3.33 (c) endothermic, ∆vapHo = positive;
(d) endothermic, ∆fusHo = positive;
(e) endothermic, ∆subHo = positive
(a) −57.20 kJ mol −1; (b) −28.6 kJ mol −1;
3.34 (c) −138.2 kJ mol −1; (d) −32.88 kJ mol −1;
(e) −55.84 KJ mol −1
3.35 +11.3 kJ mol −1

3.36 −56.98 kJ mol −1
3.38 (a) decrease; (b) decrease; (c) increase
3.39 (a) increase; (c) increase
3.40 Higher
Chapter 4
4.4 (a) positive; (b) negative; (c) positive
4.5 0.410 J K −1
4.6 −0.12 kJ K −1
4.7 −161 J K −1
4.8 q = −45.1 kJ; ∆S = −161 J K −1
4.9 +9.1 J K −1 mol −1
4.10 2.91 L
4.11 56 J K −1
4.12 23.6 J K −1
4.13 −7.9 J K −1
4.14 0.630 Ti
4.16 4.0 × 10 −4 J K −1 mol −1
4.18 5.11 J K −1
4.19 0.95 J K −1 mol −1
4.20 (a) +87.8 J K −1 mol −1; (b) −87.8 J K −1 mol −1
4.22 (a) +85 J K −1 mol −1; (b) +34 kJ K −1 mol −1
(a) −386.1 J K−1 mol−1; (b) +92.6 J K−1 mol−1;
4.23 (c) −153.1 J K−1 mol−1; (d) −21.0 J K−1 mol−1;
(e) +512.0 J K−1 mol−1
4.24 (a) −0.75 J K −1; (b) +0.15 J K −1
4.25 −5.03 kJ K −1
(a) −86 kJ mol −1; (b) Yes, ∆G is negative; (c) +0.28 kJ K −1
4.26
mol −1
4.27 0.41 g
4.28 (a) Yes; (b) 0.46 mol ATP

4.29 8.1 × 1023 molecules of ATP
Chapter 5
5.2 (a) lowered; (b) raise
5.5 rhombic sulfur
5.6 No
5.7 (a) +2.03 kJ mol −1; (b) +1.50 J mol −1
5.8 +19 kJ mol −1
5.9 (a) +1.7 kJ mol −1; (b) −20 kJ mol −1
5.10 +4.3 kJ mol −1
pf
(a) ∆Gm = RT ln + b( p f − pi ) ;
5.11 pi
(b) greater; (c) 0.68%
5.12 (a) yes; (b) 7 × 102 K
5.13 −5.2 kJ mol −1
5.15 (a) 2.37 kg; (b) 41.9 kg; (c) 1.87 kg
5.16 (a) −134.6 bar K −1; (b) 134.6 bar
5.18 28.85 kJ mol −1
5.20 1.53 Pa
5.21 36.7 kJ mol −1
5.22 356 K
5.23 Yes; 3 Torr or more
Chapter 6
6.5 5.04 g
6.6 5.04 g
6.7 0.460 g
6.8 2.41 × 10 −3
6.9 269 g sucrose
6.10 x1 = x2 = 0.500
6.11 0.451; 0.549
6.12 886.8 cm3
6.13 96 cm3
6.14 Vethanol = 53.1 mL mol −1; xethanol = 0.072
VW/(mL mol −1) = 18.067 + 6.556 × 10 −3 b2 − 1.018 × 10 −3 b3
6.16
(a) ∆Gm = −1.31 kJ mol −1; spontaneous;

6.18
(b) ∆Sm = +4.38 J K −1 mol −1
∆Gm = −1.40 kJ mol −1; spontaneous;
6.19
∆Sm = +4.71 J K −1 mol −1
6.20 4.99 kPa
6.21 2.49 kPa
6.22 6.4 × 103 kPa
6.23 4.8 × 10 −3
6.25 (a) 1.3 mmol kg −1; (b) 33 mmol kg −1
6.26 5.1 × 10 −4 mol kg −1 in N2, 27 mmol kg −1 in O2
6.27 0.101 mol L −1
p = xA p•A+ (1 − xA) p•B
If A = toluene and B = o−xylene
6.28 xA = 0.920, xB = 0.080
The composition of the vapor is given by
yA = 0.968, yB 0.032
6.29 53.8 g mol −1
6.30 −0.27 °C
6.31 207 g mol −1
r ( P * − P)
1−
K= cP
6.32 2
⎛ 2 r ( P * − P) ⎞
c ⎜1 − ⎟
⎝ cP ⎠
6.33 −0.09 °C
6.34 88.3 kg mol −1
6.35 13.94 kg mol −1
6.36 (a) 0.36; (b) 0.81
6.43 (a) no
Chapter 7
[G][Pi ]
(a) Q =
[G6P]
[Gly - Ala]
(b) Q =
[Gly][Ala]
7.5
[MgATP2 - ]
(c) Q =
[Mg 2 + ][ATP4 - ]
6
[ pCO 2 ]
(d) Q = 5
[ pCO 2 ][CH 3COCOOH]2
7.6 −14.38 kJ mol −1

pCOCl pCl
(a)
pCO pCl 2
p 2SO 3
(b)
pO 2 p 2SO 3
7.7
p 2 HBr
(c)
pH 2 pBr2
p 2O3
(d)
p 3O 2
7.8 4.46
7.9 (a) 1.2 × 109; (b) 1.8 × 102
7.10 2.42 kJ mol −1
7.11 3.01
7.13 −294 kJ mol −1
7.14 K=1
7.15 K(G1P) = 3.5 × 103, K(G6P) = 2.3 × 102, K(G3P) = 36
7.16 (a) −48.3 kJ mol −1; (b) 66.1 kJ mol −1
7.17 6.8 kJ mol −1
7.18 397 K (124 °C)
7.19 1.5 × 103 K
7.22 (a) exergonic; (b) endergonic; (c) endergonic; (d) exergonic
(a) −91.14 kJ mol −1; (b) +594.6 kJ mol −1;

7.23 (c) −66.82 kJ mol −1; (d) +99.82 kJ mol −1;
(e) −415.80 kJ mol −1
(a) −522.1 kJ mol −1, K > 1;
(b) +25.78 kJ mol −1, K < 1;
7.24 (c) −178.6 kJ mol −1, K > 1;
(d) −212.55 kJ mol −1 , K > 1;
(e) −5798 kJ mol −1, K > 1
7.25 (a) 5.5 × 104 kJ; (b) −5.1 × 104 kJ
(a) −1.4 × 104 kJ; (b) −1.57 × 104 kJ or 1.57 × 104 kJ of non
7.26
−expansion work
(a) total work done = 1.68 × 104 kJ;
7.27
(b) total work done = 1.67 × 104 kJ
7.28 −49.8 kJ mol −1
7.29 817.90 kJ mol −1
7.30 −25.0 kJ mol −1
7.31 +26 kJ mol −1
7.34 −16.9 J K −1 mol −1
7.37 +12.3 kJ mol −1
7.38 xI = 0.096, xB = 0.904
7.39 xNH3 = 0.632, xN2 = 0.010, xH2 = 0.358
7.40 5.4 × 10 −4
7.41 2.6 × 10 −4 bar
[PCl3] = [Cl2] = 1.58 × 10 −2 mol L −1 , [PCl5] = 2.3 × 10 −2 m
7.42
ol L −1; (b) 42%
7.43 pN2 = 0.020 bar, pH2 = 0.020 bar
7.45 −41.0 kJ mol −1
7.46 (b) and (d)
7.47 (a) +53 kJ mol −1; (b) −53 kJ mol −1
7.48 (a) 9.24, 31.08; (b) −12.9 kJ mol −1;
(c) +161 kJ mol −1; (d) + 248 J K −1 mol −1

Chapter 8
(a) CH3CH(OH)COOH + H2O =
CH3CH(OH)COO − + H3O+
(b) HOOCH2C(NH2)COOH + H2O =
HOOCH2C(NH2)COO − + H3O+
8.6 HOOCH2C(NH2)COO − + H20 =
−
OOCH2C(NH2)COO − + H3O+
(c) NH2CH2COOH + H2O = +NH3CH2COO − +H2O
(d) −HOOCCOOH + H2O = HOOCCOO − + H3O+
HOOCCOO − + H20 = −OOCCOO − + H3O+
8.7 (a) 6.8; (b) 6.8
(a) D2O + D2O D3O + OD− ;
(b) 14.87;
8.8 (c) 3.67 × 10−8 mol L −1
(d) pD = 7.43 = pOD;
(e) pD + pOD = pKw(D2O) = 14.87
−3
(a) 9.50 × 10 mol L −1, pH = 2.02;
8.11 (b) 0.025 mol L −1, 12.40
(c) 5.35 × 10 −2 M, pH = 1.27
8.12 (a) acidic; (b) basic; (c) basic; (d) neutral; (e) acidic; (f) acidic
8.13 (a) 9.14; (b) 4.83; (c) none
−4
8.14 (a) pKa = 3.08, Ka = 8.3 × 10 ; (b) 2.8
8.15 (a) 13.48 (b) 34 mL
8.16 (a) 1.6%; (b) 0.33%; (c) 2.4%
(a) pH = 2.00, pOH = 12.00, fraction = 0.083;
8.17 (b) pH = 4.85, pOH = 9.15, fraction = 0.10;
(c) pH = 1.1, pOH = 12.9, fraction = 0.73
8.22 2.71
8.23 (a) 6.54, (b) 2.12 (c) 1.49
8.24 pH = pKa
8.25 (a) 1.58 × 10 −5; (b) 1; (c) 5.0
(a) 0.060 mol L −1;
(b) H2S = 0.065 mol L −1,
8.26 HS − = 9.2 × 10 −5 mol L −1 = H3O+,
S2 − = 7.1 × 10 −15 mol L −1,
OH − = 1.1 × 10 −10 mol L −1
8.27 (a) 2.87; (b) 4.56; (c) 12.5 mL; (d) 4.75; (e) 25.0 mL; (f) 8.72
8.28 (a) 4.75 (b) 5.05 (c) 4.14
8.29 (a) 2 −4; (b) 3 −5; (c) 11.5 −13.5; (d) 6 −8; (e) 5 −7
−5
8.30 pKa = 4.66, Ka = 19 × 10 , pH = 3.24
8.31 (a) 5.04; (b) 8.96; (c) 2.78
8.32 7.94
(a) H3PO4 and NaH2PO4;
8.34
(b) NaH2PO4 and Na2HPO4
(a) Ks = [Ag+] [1 −];
(b) Ks = [Hg2+2] [S2 −];
8.35
(c) Ks = [Fe3+] [OH −]3;
(d) Ks = [Ag+]2 [CrO42 −]
(a) 1.1 × 10 −10 ; (b) 6.2 × 10 −12; (c) 2.0 × 10 −39;
8.36
(d) 1.3 × 10 −18
(a) 5.5 × 10 −10 mol L −1; (b) 3.2 × 10 −3 mol L −1;
8.37
(c) 1.6 × 10 −7 mol L −1; (d) 2.45 × 10 −7
mol L −1
−5
8.38 1.25 × 10 mol L −1
Chapter 9
(a) I(KCl) = b/bo
9.5 (b) I(FeCl3) = 6b/bo
(c) I(CuSO4) = 4b/bo
9.6 0.90
9.7 (a) 2.73 g; (b) 2.92 g
9.8 γ± = (γ+γ−2)1/3
9.9 0.12
9.10 2.01
9.11 13.83 mS m2 mol−1
9.12 7.63 × 10−3 S m2 mol−1
9.13 347 µm s−1
Κm°= 12.6 mS m2 mol−1; κ = 7.30 mS m2 mol−1 M1/2
(a) 11.96 mS m2 mol−1
9.14
(b) 119.6 mS m−1
(c) 172.5 Ω
9.15 1.36 × 10−5 mol L−1
9.17 Yes
9.18 CH3COCO2 − + NADH + H+ → CH3CH(OH)CO2 − + NAD+
9.22 +1.14V, −44.0 kJ mol −1
9.23 41 mV
9.24 21 mV
9.25 Standard potential = −1.18V
(a)
R: Ag+(aq, bR) + e − → Ag(s)
L: Ag+(aq, bL) + e − → g(s)
R −L: Ag+(aq, bR) → Ag+ (aq, bL)
(b)
R: 2H+(aq) + 2e − → H2(g, PR)
9.26 L: 2H+(aq) + 2e − → H2(g, PL)
R−L: H2(G, PL) → H2(g, PR)
(c)
R: MnO2(s) + 4H+(aq) + 2e − → Mn2+(aq) + 2H2O
L: [Fe(CN)6]3 − = e − → Fe(CN)6]4 −
R−L: MnO2(s) + 4H+(aq) + 2[Fe(CN6)4− (aq) →
Mn2+(aq) + 2[Fe(CN6)3− (aq)
(d)
R: Βr2(g) +2e − → 2Br −(aq)
L: Cl2(g) +2e − → 2Cl −(aq)
R−L: Br2(l) +2Cl − (aq) → Cl2(g) + 2Br −(aq)
(e)
R: Sn 4+ (aq) + 2e − → Sn2+(aq)
L: 2Fe3+(aq) + 2e − → 2Fe2+(aq)
R −L: Sn 4+ (aq) + 2Fe2+(aq) → Sn2+(aq) + 2Fe3+(aq)
(f)
R: −L: MnO2(s) + 4H+(aq) → Mn2+ (aq) + 2H2O(l)
L: Fe2+ (aq) + 2e − → Fe(s)
R−L: Fe(s) + MnO2(s) + 4H+(aq) → Fe2+ (aq) + Mn2+ (aq) + 2H2O(l)

(a) E = E2 − RT/F ln bL/bR
9.27
(b) E = E2 − RT/2F ln pR/pL
(a) Fe(s)|FeSO4(aq)|PbSO4(s)|Pb(s) v=2
(b) Pt|H2(g)|H+(aq)|Hg2Cl2(s)|Hg(|) v=2
(c) Pt|H2(g)|H+(aq), H2O|O2(g)|Pt v=4
9.28
(d) Pt|H2(g)|H+(aq), H2O|O2(aq)|O2(g)|Pt v=2
(e) Pt|H2(g)|H+(aq), | −(aq)||2(s)|Pt v=2
(f) CuCl2(aq) | CuCl(aq)|Cu(s) v=2
(a) Pt|CH3CH2OH(aq), CH3CHO(aq), H+(aq)||NAD+(aq),
NADH(aq)|Pt v=2
9.29
(b) Mg(s)|ATP4 −(aq), MgATP2 −||MG2+(aq)|Mg(s) v=2
(c) Pt|Cy −c (red, aq), Cyt −c(ox,aq)||CH3CH(OH)CO2 −(aq),
CH3COCO2 −(aq)|Pt
(a) 0; (b) 0; (c) + 0.87 V; (d) − 0.27 V; (e) −0.62 V;
9.30
(f) +1.67 V
(a) +0.08 V; (b) +0.27 V; (c) +1,23 V; (d) +0.695 V;
9.31
(e) +0.54 V; (f) +0.366 V
(a) Eo (NAD+, NADH) − Eo (CH3,CH3CH2OH);

(b) Eo (Mg2+, Mg) − Eo (Mg, MgATP4−);
9.32
(c) EoCH3COCO2−, CH3CH(OH)CO2− − Eo (Cyt−c(ox),
Cyt−c(red))
9.34 + 0.94 V
(a) E decreases, |E| increases; (b) E increases, |E| increases;
9.36 (c) E increases, |E| increases; (d) E increases, |E| decreases;
(e) E increases, |E| decreases; (f) E decreases, |E| decreases
(a) decreases E; (b) decreases E; (c) increases E;
9.37
(d) decreases E; (e) decreases E; (f) has no effect on E
(a) cell potential decreases; (b) cell potential increases;
9.38
(c) cell potential decreases
9.39 (a) −1.20 V (b) −1.18 V
(a) −394 kJ mol −1; (b) same as (a);
9.40 (c) +75 kJ mol −1; (d) −291 kJ mol −1;
(e) as (d); (f) −498 kJ mol −1
9.41 (a) − 44.0 kJ mol −1; (b) 29.7 kJ mol −1; (c) − 316 kJ mol −1
9.42 (a) + 0.324 V; (b) + 0.45 V
9.43 0.72 V
9.44 −0.46 V, + 89.7 kJ mol −1146 kJ mol −1, + 87.9 kJ mol −1
9.45 −606 kJ mol −1
9.46 +0.24 V
(a) + 0.3108 V; (b) +1.14 V;
9.47
(c) E = Eo − ln; (d) 207 m V; (e) 10.3
−8
9.48 (a) 1.6 × 1 [mol kg −1]; (b) + 0.12 V
(a) 6.5 × 109; (b) 1.2 × 107; (c) 4 × 1069; (d) 1.0 × 1025;
9.49 −7
(e) 8.2 × 10
1.80 × 10−10 → 1.78 × 10−10,
9.50
9.04 × 10−7→ 5.1 × 10−7,
9.51 E = Eo − ln
9.52 0.78
9.53 E=0
−17 −9
9.54 8.5 × 10 , 9.19 × 10 mol L −1
9.55 0.95 V
Chapter 10
A= 1.5 mol L −1 s −1
10.9 B = 0.73 mol L −1 s −1
D = 0.73 mol L −1 s −1
(a) (i) second-order, m3s −1
(ii) third-order, m6s −1
10.11
(b) (i) second-order, Қ Pa −1 s −1
(ii) third-order, Қ Pa −2 s −1
10.12 (a) 1; (b) 4.89 × 103 s −1
10.13 (a) 1; (b) 2.33 × 109 L2 mol −2 s −1
10.14 2.05 × 104 s; (a) 500 Torr; (b) 515 Torr
10.15 1.12 × 10 −4 s −1
10.16 4.2 × 10 −5 s −1
10.17 1.09 × 10 −3 L mol −1 s −1
10.18 1.12 × 10 −4 s −1
10.19 3.19 × 10 −6 Pa −1 s −1 (for pseudosecond-order process)
10.20 (a) 0.014 kPa s −1; (b) 1.5 × 103s
10.24 First-order, 5.6 × 10 −4 s −1
10.27 1330 s
10.28 3.1 × 103 y
10.29 (a) 0.63µg; (b) 0.16µg
10.30 (a) 0.138 mol L −1; (b) 0.095 mol L −1
10.31 2.79 × 104s
Ea = 85.6 kJ mol −1;
10.32
A = 3.66 × 1011 mol L −1 s −1
10.33 299 K
10.35 21.6 kJ mol −1
10.37 120 kJ mol −1
10.38 −21.6 kJ mol −1
10.39 48 kJ mol −1
10.40 5.4 × 104 s
−1
10.41 1.08 × 106 L mol s −1
10.42 2.1 mm2
10.43 126 kJ mol −1
−1
10.44 4.4 J K mol −1
Chapter 11
11.5 3.1 × 105 L mol −1 s −1
11.10 41.6d
(a) 6.61 × 106 m3 mol s−1
11.12
(b) 3.0 × 107 m3 mol s−1
11.20 1.5 × 1015
11.21 First-order in H202 and in Br −, and second-order overall
11.22 rate = keff[A2]1/2[B]
rate equation = k [A] [B]
11.23 k1k2
rate constant , k =
k1′
k1k2 [O3 ] 2
11.24 rate =
k1′[O 2 ] + k2 [O3 ]
k1[AH][B]
[A - ] =
k2 [BH + ] + k3[AH]
11.26
k1k3[AH]2 [B]
Rate of formation of products =
k2 [BH + ] + k3[AH]
11.28 1.62 × 10 −3 mol L −1 s −1

11.29 [S] = KM
11.31 0.38 s −1
11.32 1.1 × 102 s −1

1/ 2
⎛k ⎞
11.34 − k1[R 2 ] − k2 ⎜⎜ 1 ⎟⎟ [R 2 ]3 / 2
⎝ k4 ⎠
Chapter 12
12.5 1.0 × 10 −6 m
12.6 8.4 × 1011
12.7 4.5 × 103 K, this radiation is not thermal radiation
12.8 4.6 × 103 W
12.9 6.29 × 10 −34 Js
(a) 4.0 × 102 kJ mol −1; (b) 20 kJ mol −1; (c) 7.9 × 1013 kJ
12.10
mol −1
12.11 (a) 1.7 × 1018 s −1; (b) 1.7 × 1020 s −1
12.12 6.90 × 1029 s −1
12.13 (a) no ejection occurs; (b) 4.52 × 10 −19 J, 996 km s −1
−1
12.14 1.32 × 106 m s
(a) 6.6 × 10 −31 m; (b) 6.6 × 10 −39 m;
12.15
(c) 99.7 pm
12.16 (a) 1.23 nm; (b) 39 pm; (c) 3.88pm
(a) 9.14 × 10 −28 kg m s −1; (b) 8.8 × 10 −24 kg m s −1; (c) 3.3 ×
12.18
10 −35 kg m s −1
12.20 2.2 × 10 −24 m s −1
12.21 (a) 3.34 × 10 −6 N; (b) 3.34 × 10 −12 Pa; (c) 83 h
12.22 50.6 nm
12.23 1.11 × 10 −15 J
12.24 (a) 4.6 × 10 −5; (b) 6.0 × 10 −2
12.27 90 nm
12.28 2.1 × 10 −29 m s −1
12.29 1 × 10 −26 m
12.30 5.8 × 10 −5 m s −1
12.31 9.85 × 10 −23 J
12.32 L/4 or 3L/4

12.33 (a) 2.17 × 10 −20 J; (b) 9.16 × 10 −6 m
12.34 4 = (1 / L)1/2
12.35 1.24 × 10 −6 m
12.36 (a) 4.34 × 10 −4T kg m2; (b) 1.55 mm
12.37 0.04 N m −1
12.38 (a) 6.89 × 1013 s −1; (b) 4.35 mm
Chapter 13
13.5 434 nm
13.6 n=6
13.7 (a) 6842 cm −1; (b) 1.36 × 10 −19
J
13.8 2.24 × 103 cm −1
13.9 4p → 2s
13.10 122.31 e V
13.11 16
13.12 n2 → 6
13.13 3092 nm
13.14 (a) 397.13nm; (b) 3.40 eV
RLi2+ = 987663 cm −1
13.15 137175 cm −1 185187 cm −1
122.5eV
13.16 r = 0.693 Å (36.7 pm)
13.17 (a) 40 pm or 13 pm; (b) 29 or 24 pm
13.18 1/6
13.19 1.1 × 10 −5
(a) 2.7 × 10 −8 pm −3;
13.21
(b) 9.9 × 10 −8 pm3; (c) 0
13.22 5.2a0
13.24 (a) 101 pm and 376; (b) 99 pm, 349 ppm, and 821 pm
13.25 0°, 180°; 90° 270°
13.27 (a) g = 1; (b) g = 9; (c) g = 49

13.28 (a) 2; (b) 14; (c) 22
13.30 14.0 eV
13.33 Fe 2+
1
13.34 F3; 3F4,3F3, 3F2; 1D2; 3D3, 3D2, 3D1; 1P1, 3P1, 3P0
13.35 2,1 and 0
13.36 (a) 1; (b) 3; (c) 1; (d) 3
(a) forbidden; (b) allowed; (c) allowed;
13.37
(d) forbidden; (e) allowed
13.38 all d and g orbitals
Chapter 14
14.7 3.11 × 10 −18 J
14.12 1 − 1 = 0 [orthogonality]
1/ 2
⎛ 1 ⎞
14.13 N =⎜ 2 ⎟
⎝ 1 + 2 λ S = λ ⎠
14.15 N(0.844A − 0.145Β)
14.16 978 and 22 respectively
14.17 −µe4/12π3ε20ħ2
14.20 (c) 45°
14.22 (a) b = 1; (b) b = 0; (c) b = 2
14.23 (a) b = 1/2; (b) b = 3; (c) b = 2
14.24 (a) b = 3; (b) b = 5/2; (c) b = 3
14.25 C2
C2 and CN stabilized by anion formation; NO, O2 and F2 stabili
14.26
zed by cation formation
14.28 no
14.29 (a) g; (b) inapplicable; (c) g; (d) u
14.30 g, u, g, u
14.31 g, u, g, u; (b) for v even, g; for v odd, u
14.33 N2
14.34 F2+ < F2 < F2 −

14.35 O2+, O, O2−, Ο22−
14.36 (a) 7a + 7b; (b) 5a = 7b
(a) C6H6−: a22u e41g e12u ; E = 7α + 7β
14.37
(b) C6H6+: a22u e31g ; E = 5α + 5β
14.38 2.7 eV
Chapter 15
15.5 (a) n-type; (b) p-type
15.6 metallic conductor
15.10 3888 kJ mol −1
15.11 2258 kJ mol −1
qNzeπ
15.12 V=
48ε 0 d
15.13 1.06
15.17 (326), (11), (122), (322)
15.20 (111) = 307 pm, (211) = 217 pm, (100) = 532 pm
15.21 (123) = 0.129 nm, (236) = 0.0671 nm
15.22 66.1 pm
15.23 0.215 cm
15.24 bcc
15.25 8.97 g cm −3
15.26 (a) 0.9069; (b) 0.5236
15.28 0.740 g cm −3
(a) eight nearest neighbours, 433 nm;
15.29
(b) six next-nearest neighbours, 500 nm
(a) 12 nearest neighbours, 354 nm;
15.30
(b) six next-nearest neighbours, 500 nm
15.31 (a) less dense; (b) 92%
V = 3.96 × 10 −28 m3;
15.32
D = 2.40 × 106 g m−3
15.33 N = 4, 4.01 g cm−3

15.34 (a) (321) = 220 pm; (b) (642) = 110 pm
15.35 rock salt structure
Chapter 16
(a) 2.88 × 10−23 m−2 s−1; 5.75 × 1017 m−2 s−1
16.5
(b) 3.81 × 10−24 m−2 s−1; 7.60 × 1017 m−2 s−1
16.6 1.3 × 104 Pa
16.7 3.4 × 105 s−1
16.10 18.8 m2
16.11 (a) 0.21 kPa; (b) 22 kPa
16.13 0.37 Torr s−1
16.15 ∆adHo = −(0.904 × 103 K) × R = −7.52kJ mol−1
(a) 164, 13.1 cm3
16.19
(b) 264, 12.5 cm3
16.20 200 s
Ed = 610 kJ mol−1, τ0 = 1.13 × 10−13 s,
16.21
A = 6.15 × 1012 s−1
650 kJ mol−1, (a) 1.1 × 1097 min;
16.22
(b) 2.6 × 10−6 min;
16.23 0 on gold, 1 on platinum
(a) 0.31 mA cm−2
16.27 (b) 5.41 mA cm−2
(c) −2.19 mA cm−2
(a) 4.9 × 1015 cm−2 s−1, 3.8 s−1
16.28 (b) 1.6 × 1016 cm−2 s−1, 12 s−1
(c) 3.1 × 107 cm−2 s−1, 2.4 × 108 s−1
16.29 0.38, 0.78 mA cm−2
16.30 0.50, 0.150 A m−2, 0.038 A m
j0 = 2.00 × 10−5 mA m−2, α = 0.498; R = 0.9990. There are no
16.31
significant deviations.
Chapter 17
17.5 dipole moment = 0.9D, 3.0 × 10 −30 C m
17.6 SF4 is polar
(a) ortho-xylene = 0.7D; (b) meta-xylene = 0.4D;
17.7
(c) para-xylene = 0; the para-xylene value is exact by symmetry
(a) 1,2,3-trimethylbenzene = 0.8D;
(b) 1,2,4-trimethylbenzene = 0.2D;
17.8
(C) 1,3,5-
trimethylbenzene = 0; (c) should cancel exactly by symmetry
17.9 1.4D
17.10 (a) 1.50 D; (b) 2.6 D; (c) 1.13 D; (d) 1.80 D
17.11 3.10 D
17.13 (a) 100 pm = 1070 kJ mol −1; (b) 300 pm = 119 kJ mol −1
(a) E = 3/2 RT = 3.7 kJ mol −1 at 298K;
17.15
(b) 0.14 J; the kinetic theory of gases is justifiable
17.17 196 pm
17.18 7.7 × 10 −5 J mol −1
17.19 4.2 × 10 −3 J mol −1
17.20 8.2 kJ mol −1
17.21 r = 21/6v
17.25 (a) VO = 11.6 kJ mol −1; (c) 4 × 1012 s −1
Chapter 18
18.10 70 kg mol−1, 71 kg mol−1,
(a) 18 kg mol−1,
18.11
(b) 20 kg mol−1,
18.13 n = 244
18.14 3.4 Mg mol−1,
18.15 3500 r.p.m.
18.17 24 nm
18.18 3.08µm, 3.08 nm
18.19 1.4 × 104

(a) lN1/2, 9.74 nm;
(b) (8N/3π)1/2l, 8.97 nm;
18.20
(c) (2N/3)1/2l, 7.95 nm;
Serum albumin and bushy stunt virus resemble spheres; DNA

18.22
does not.
Chapter 19
19.5 (a) 4.47 × 1014 s −1; (b) 1.49 × 104 cm −1
19.6 (a) 3.07 × 10 −3 cm −1
; (b) 3.26 m
19.7 75.1%
19.8 1.35 × 103 L mol −1 cm −1
19.9 log = −E m [J]0
19.10 450 L mol −1 cm −1
19.11 159 L mol −1 cm −1, 23%
19.12 (a) 0.9 m; (b) 3 m
0.999 999 918 × 660 mm,
19.13
green at 6.36 × 107m s −1
19.14 8.4 × 105 K
19.15 (a) 0.1 cm −1 = 53ps; (b) 5 ps; (c) 0.18ps
19.16 0.27cm −1
19.17 4 × 1033
(a) 1H2 = 4.601 × 10 −48 kg m2;
(b) 2H2 = 9.196 × 10 −48 kg m2;
19.18
(c) 12C16O2 = 6.67 × 10 −46 kg m2;
(d) 13C16O2 = 6.67 × 10 −46 kg m2
(a) 1.825 × 1012 Hz;
19.19 (b) 9.128 × 1011 Hz;
(c) 1.26 × 1010 Hz;
(d) 1.26 × 1010 Hz

19.20 (a) I = 4mBR2; (b) 1.583 × 109 Hz
19.21 (a) I|| = 4mR2, I⊥2mR2
(a) 5.152 × 109 Hz;
19.22
(b) microwave spectroscopy could not be used
19.23 (a), (b), (c) and (d)
19.24 all
19.25 one state with J = 10
19.26 20 states and 10 energy levels
(a) 636 GHz, 1272 GHz, 1908 GHz …
19.28
(b) 21.21 cm −1, 42.42 cm −1, 63.63 cm −1 . . .
19.30 lower
19.31 1.162 × 10 −10m = 116.2 pm
19.32 separation of lines = 194 GHz
19.34 R(CO) = 116.28 pm, R(CS) = 155.97 pm
19.35 (a) 12C = 16O = 4.49 × 1013Hz; (b) 13C16O = 4.39 × 1013 Hz
19.36 329 Nm −1
19.37 HF = 967.1, HCl = 515.6, HBr = 411.8. HI = 314.2
2
19.38 HF = 3002, 2HCl = 2144, 2HBr = 1886, 2HI = 1640
19.39 2699.77 cm −1
19.40 (b) HCl, (c) CO2, (d) H2O, (e) CH3CH3, (f) CH4 and (g) CH3Cl
19.41 (a) 3; (b) 4; (c) 48; (d) 54
19.42 Raman active
19.43 (a) Raman active
Chapter 20
20.3 Lengthen; to blue
20.11 (a) 1.01 × 104 L mol −1 cm −1; (b) 0.965%
20.12 33 mg L −1
20.13 8.0 × 10 −19 J
20.14 2.3 × 10 −19 J
1/ 2
d[A] ⎛ I ⎞
20.17 = − I − k 2 ⎜⎜ ⎟⎟ [ A]
dt ⎝ k3 ⎠
20.18 3.3 × 1018
20.19 0.518
20.20 5.1 × 106 L mol −1 s −1,
quencing rate constant = 9.2 × 109 L mol −1 s −1, half −life
20.22
1.9 × 10 −7 s
20.23 3.52 nm
20.24 (a) Iabs = I0(1–10–ε[J]l)
Chapter 21
−
21.8 1.625 × 10 −26 J × mr
21.9 (a) T −1 Hz; (b) A s kg −1
21.10 2.263
21.12 9.248 GHz
21.14 328.6 MHz
21.15 46.15 MHz
21.16 12.92 T
21.17 2.66 kHz
21.18 46 mT
21.19 (a) 300 MHz = 2.4 KHz; (b) 550 MHz = 4.4 KHz
21.20 1: 7: 21: 35: 35: 21: 7: 1
21.21 (a) quintet 1: 2: 3: 2: 1; (b) septet 1: 3: 6: 7: 6: 3: 1
21.28 2.0022
21.29 2.3 mT, 2.003
21.30 (a) 1:3:3:1; (b) 1:3:6:7:6:3:1
21.31 (a) 331.9 mT; (b) 1.201 T
21.32 1
(7) ρ(3) = ρ(6) = 0.005, ρ(4) = ρ(5) = 0.076;
21.33 (8) ρ(2) = ρ(4) = 0.200, ρ(3) = 0.048. ρ(6) = 0.121;
(9) all ρ = 0.050
Chapter 22
22.7 0.37
22.8 (a) 0.9999895; (b) 0.9998955
22.9 0.99849
22.10 3.475
22.11 0.487
22.12 (a) 1 + 5e −e/kT + 3e −3e/KT; (b) T = 0, q = 1; (c) T = `, q= 9
22.13 (a) 1.29; (b) 7.82
22.14 (a) 9; (b) 6.731
22.15 1.072
22.16 (a) 3.2 × 104; (b) 6.2 × 1027
22.17 (a) 19.5; (b) 265
Nhv
22.19
e −1
hv / kT
R(70.77 K )e −2359 K / T + R(3129 K )e −6258 k / T

(a) E =
22.21 1 + 3e − 2359 K / T + 5e − 6258 K / T
(b) 339 J mol −1
−2280 K / T
K )e −3259 k / T
(a) E = R(6840K )e −2280 K / T + 3259
−3259 K / T
22.22 5 + 3e +e
(b) 0.993 kJ mol −1
22.25 11.5 J K −1 mol −1
22.27 191.4 J K −1 mol −1
22.28 40 kJ K 1 mol −1
−
22.29 1.37 × 10 −25

22.30 1.97 × 10 −11

Atkins Elements 4e Answers

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Atkins Elements 4e Answers

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Atkins & De Paula: Elements of Physical Chemistry: 4e

NUMERICAL ANSWERS TO END OF CHAPTER EXERCISES

Question Numerical answer

1.19 132 g mol −1

3.16 (a) 388 kJ mol −1; (b) smaller

3.35 +11.3 kJ mol −1

4.28 (a) Yes; (b) 0.46 mol ATP

(a) ∆Gm = −1.31 kJ mol −1; spontaneous;

7.6 −14.38 kJ mol −1

(a) −91.14 kJ mol −1; (b) +594.6 kJ mol −1;

(c) +161 kJ mol −1; (d) + 248 J K −1 mol −1

R−L: Fe(s) + MnO2(s) + 4H+(aq) → Fe2+ (aq) + Mn2+ (aq) + 2H2O(l)

(a) Eo (NAD+, NADH) − Eo (CH3,CH3CH2OH);

11.28 1.62 × 10 −3 mol L −1 s −1

11.32 1.1 × 102 s −1

12.32 L/4 or 3L/4

13.27 (a) g = 1; (b) g = 9; (c) g = 49

14.34 F2+ < F2 < F2 −

15.33 N = 4, 4.01 g cm−3

18.19 1.4 × 104

Serum albumin and bushy stunt virus resemble spheres; DNA

(d) 1.26 × 1010 Hz

R(70.77 K )e −2359 K / T + R(3129 K )e −6258 k / T

22.29 1.37 × 10 −25

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