Peter Atkins Julio de Paula Ron Friedman Physical Chemistry Quanta (0970-1010)

PART 4 Data
947
Table 0.2 (Continued)
Nuclide m/mu Abundance/%

34S 33.9679 4.22
Cl 35Cl 34.9688 75.53
37Cl 36.9651 24.4
Br 79Br 78.9183 50.54
81Br 80.9163 49.46
I 127I 126.9045 100
* Exact value.
Table 19.1 Effective nuclear charge, Zeff = Z − σ
H He
1s 1 1.6875
Li Be B C N O F Ne
1s 2.6906 3.6848 4.6795 5.6727 6.6651 7.6579 8.6501 9.6421
2s 1.2792 1.9120 2.5762 3.2166 3.8474 4.4916 5.1276 5.7584
2p 2.4214 3.1358 3.8340 4.4532 5.1000 5.7584
Na Mg Al Si P S Cl Ar
1s 10.6259 11.6089 12.5910 13.5745 14.5578 15.5409 16.5239 17.5075
2s 6.5714 7.3920 8.3736 9.0200 9.8250 10.6288 11.4304 12.2304
2p 6.8018 7.8258 8.9634 9.9450 10.9612 11.9770 12.9932 14.0082
3s 2.5074 3.3075 4.1172 4.9032 5.6418 6.3669 7.0683 7.7568
3p 4.0656 4.2852 4.8864 5.4819 6.1161 6.7641
Data: E. Clementi and D.L. Raimondi, Atomic screening constants from SCF functions.
IBM Res. Note NJ-27 (1963). J. Chem. Phys. 38, 2686 (1963).
Table 20.2 First and second ionization energies, I/(kJ mol−1)
H He
1312.0 2372.3
5250.4
Li Be B C N O F Ne
513.3 899.4 800.6 1086.2 1402.3 1313.9 1681 2080.6
7298.0 1757.1 2427 2352 2856.1 3388.2 3374 3952.2
495.8 737.7 577.4 786.5 1011.7 999.6 1251.1 1520.4
4562.4 1450.7 1816.6 1577.1 1903.2 2251 2297 2665.2
2744.6 2912
K Ca Ga Ge As Se Br Kr
418.8 589.7 578.8 762.1 947.0 940.9 1139.9 1350.7
3051.4 1145 1979 1537 1798 2044 2104 2350
2963 2735
Rb Sr In Sn Sb Te I Xe
403.0 549.5 558.3 708.6 833.7 869.2 1008.4 1170.4
2632 1064.2 1820.6 1411.8 1794 1795 1845.9 2046
2704 2943.0 2443
Cs Ba Tl Pb Bi Po At Rn
375.5 502.8 589.3 715.5 703.2 812 930 1037
2420 965.1 1971.0 1450.4 1610
2878 3081.5 2466
Data: E.
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948 Resource section
Table 20.3 Electron affinities, Eea/(kJ mol−1)
H He
72.8 −21
Li Be B C N O F Ne
59.8 ≤0 23 122.5 −7 141 322 −29
−844
52.9 ≤0 44 133.6 71.7 200.4 348.7 −35
−532
48.3 2.37 36 116 77 195.0 324.5 −39
46.9 5.03 34 121 101 190.2 295.3 −41
Cs Ba Tl Pb Bi Po At Rn
45.5 13.95 30 35.2 101 186 270 −41
Data: E.
Table 24.1 Bond lengths, Re/pm
(a) Bond lengths in specific molecules

Br2 228.3
Cl2 198.75
CO 112.81
F2 141.78
H2+ 106
H2 74.138
HBr 141.44
HCl 127.45
HF 91.680
HI 160.92
N2 109.76
O2 120.75
(b) Mean bond lengths from covalent radii*

H 37
C 77(1) N 74(1) O 66(1) F 64
67(2) 65(2) 57(2)
60(3)
Si 118 P 110 S 104(1) Cl 99
95(2)
Ge 122 As 121 Se 104 Br 114
Sb 141 Te 137 I 133
* Values are for single bonds except where indicated otherwise (values in parentheses). The length
of an A − B covalent bond (of given order) is the sum of the corresponding covalent radii.
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PART 4 Data 949
Table 24.2a Bond dissociation enthalpies, ΔH <(A–B)/(kJ mol−1) at 298 K*
Diatomic molecules
H–H 436 F–F 155 Cl–Cl 242 Br–Br 193 I–I 151
O=O 497 C=O 1076 N≡N 945
H–O 428 H–F 565 H–Cl 431 H–Br 366 H–I 299
Polyatomic molecules
H–CH3 435 H–NH2 460 H–OH 492 H–C6H5 469
H3C–CH3 368 H2C = CH2 720 HC ≡ CH 962
HO–CH3 377 Cl–CH3 352 Br–CH3 293 I–CH3 237
O = CO 531 HO–OH 213 O2N–NO2 54
* To a good approximation bond dissociation enthalpies and dissociation energies are related by ΔH < = De + 23 RT with De = D0 + 1 ω .
2
For precise values of D0 for diatomic molecules, see Table 43.1.
Data: HCP, KL.
Table 24.2b Mean bond enthalpies, ΔH <(A–B)/(kJ mol−1)*
H C N O F Cl Br I S P Si
H 436
C 412 348(i)
612(ii)
838(iii)
518(a)
N 388 305(i) 163(i)
613(ii) 409(ii)
890(iii) 946(iii)
O 463 360(i) 157 146(i)
743(ii) 497(ii)
F 565 484 270 185 155
Cl 431 338 200 203 254 242
Br 366 276 219 193
I 299 238 210 178 151
S 338 259 496 250 212 264
P 322 201
Si 318 374 466 226
* Mean bond enthalpies are such a crude measure of bond strength that they need not be distinguished from dissociation energies.
(i) Single bond, (ii) double bond, (iii) triple bond, (a) aromatic.
Data: HCP and L. Pauling, The nature of the chemical bond. Cornell University Press (1960).
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Table 25.1 Pauling (italics) and Mulliken electronegativities
H He
2.20
3.06
Li Be B C N O F Ne
0.98 1.57 2.04 2.55 3.04 3.44 3.98
1.28 1.99 1.83 2.67 3.08 3.22 4.43 4.60
0.93 1.31 1.61 1.90 2.19 2.58 3.16
1.21 1.63 1.37 2.03 2.39 2.65 3.54 3.36
0.82 1.00 1.81 2.01 2.18 2.55 2.96 3.0
1.03 1.30 1.34 1.95 2.26 2.51 3.24 2.98
0.82 0.95 1.78 1.96 2.05 2.10 2.66 2.6
0.99 1.21 1.30 1.83 2.06 2.34 2.88 2.59
Cs Ba Tl Pb Bi
0.79 0.89 2.04 2.33 2.02
Data: Pauling values: A.L. Allred, J. Inorg. Nucl. Chem. 17, 215 (1961); L.C. Allen and J.E. Huheey, ibid., 42,
1523 (1980). Mulliken values: L.C. Allen, J. Am. Chem. Soc. 111, 9003 (1989). The Mulliken values have been
scaled to the range of the Pauling values.
Table 34.1 Magnitudes of dipole moments (μ), polarizabilities (α), and

polarizability volumes (α′)
μ/(10−30 C m) μ/D α′/(10−30 m3) α/(10−40 J−1 C2 m2)

Ar 0 0 1.66 1.85
C2H5OH 5.64 1.69
C6H5CH3 1.20 0.36
C6H6 0 0 10.4 11.6
CCl4 0 0 10.3 11.7
CH2Cl2 5.24 1.57 6.80 7.57
CH3Cl 6.24 1.87 4.53 5.04
CH3OH 5.70 1.71 3.23 3.59
CH4 0 0 2.60 2.89
CHCl3 3.37 1.01 8.50 9.46
CO 0.390 0.117 1.98 2.20
CO2 0 0 2.63 2.93
H2 0 0 0.819 0.911
H2O 6.17 1.85 1.48 1.65
HBr 2.67 0.80 3.61 4.01
HCl 3.60 1.08 2.63 2.93
He 0 0 0.20 0.22
HF 6.37 1.91 0.51 0.57
HI 1.40 0.42 5.45 6.06
N2 0 0 1.77 1.97
NH3 4.90 1.47 2.22 2.47
1,2-C6H4(CH3)2 2.07 0.62
Data: HCP and C.J.F. Böttcher and P. Bordewijk, Theory of electric polarization. Elsevier, Amsterdam
(1978).
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PART 4 Data 951
Table 35.2 Lennard-Jones (12,6) potential parameters
(ε/k)/K r0/pm
Ar 111.84 362.3
C2H2 209.11 463.5
C2H4 200.78 458.9
C2H6 216.12 478.2
C6H6 377.46 617.4
CCl4 378.86 624.1
Cl2 296.27 448.5
CO2 201.71 444.4
F2 104.29 357.1
Kr 154.87 389.5
N2 91.85 391.9
O2 113.27 365.4
Xe 213.96 426.0
Source: F. Cuadros, I. Cachadiña, and W. Ahamuda, Molec. Engineering 6,
319 (1996).
Table 36.1 Second virial coefficients, B/(cm3 mol−1) Table 36.2 Boyle temperatures
of gases
100 K 273 K 373 K 600 K
Air −167.3 −13.5 3.4 19.0 TB/K
Ar −187.0 −21.7 −4.2 11.9 Ar 411.5
CH4 −53.6 −21.2 8.1 CH4 510.0
CO2 −142 −72.2 −12.4 CO2 714.8
H2 −2.0 13.7 15.6 H2 110.0
He 11.4 12.0 11.3 10.4 He 22.64
Kr −62.9 −28.7 1.7 Kr 575.0
N2 −160.0 −10.5 6.2 21.7 N2 327.2
Ne −6.0 10.4 12.3 13.8 Ne 122.1
O2 −197.5 −22.0 −3.7 12.9 O2 405.9
Xe −153.7 −81.7 −19.6 Xe 768.0
Data: AIP, JL. The values relate to the expansion in eqn 36.4b of Topic 36; convert Data: AIP, KL.
to eqn 36.4a using B′ = B/RT.
For Ar at 273 K, C =1200 cm6 mol−1.
Table 36.3 van der Waals parameters
a/(atm dm6 mol−2) b/(10−2 dm3 mol−1) a/(atm dm6 mol−2) b/(10−2 dm3 mol−1)
Ar 1.337 3.20 H2S 4.484 4.34
C2H4 4.552 5.82 He 0.0341 2.38
C2H6 5.507 6.51 Kr 5.125 1.06
C6H6 18.57 11.93 N2 1.352 3.87
CH4 2.273 4.31 Ne 0.205 1.67
Cl2 6.260 5.42 NH3 4.169 3.71
CO 1.453 3.95 O2 1.364 3.19
CO2 3.610 4.29 SO2 6.775 5.68
H2 0.2420 2.65 Xe 4.137 5.16
H2O 5.464 3.05
Data: HCP.
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Table 36.5 Critical constants of gases
pc/atm Vc/(cm3 mol−1) Tc/K

Ar 48.0 75.3 150.7
Br2 102 135 584
C2H4 50.50 124 283.1
C2H6 48.20 148 305.4
C6H6 48.6 260 562.7
CH4 45.6 98.7 190.6
Cl2 76.1 124 417.2
CO2 72.9 94.0 304.2
F2 55 144
H2 12.8 34.99 33.23
H2O 218.3 55.3 647.4
HBr 84.0 363.0
HCl 81.5 81.0 324.7
He 2.26 57.8 5.2
HI 80.8 423.2
Kr 54.27 92.24 209.39
N2 33.54 90.10 126.3
Ne 26.86 41.74 44.44
O2 50.14 78.0 154.8
Xe 58.0 118.8 289.75
Table 38.2 Ionic radii, r/pm*
Li+(4) Be2+(4) B3+(4) N3− O2−(6) F−(6)

59 27 12 171 140 133
Na+(6) Mg2+(6) Al3+(6) P3− S2−(6) Cl−(6)
102 72 53 212 184 181
K+(6) Ca2+(6) Ga3+(6) As3−(6) Se2−(6) Br−(6)
138 100 62 222 198 196
Rb+(6) Sr2+(6) In3+(6) Te2−(6) I−(6)
149 116 79 221 220
Cs+(6) Ba2+(6) Tl3+(6)
167 136 88
d-block elements (high-spin ions)

Sc3+(6) Ti4+(6) Cr3+(6) Mn3+(6) Fe2+(6) Co3+(6) Cu2+(6) Zn2+(6)
73 60 61 65 63 61 73 75
* Numbers in parentheses are the coordination numbers of the ions. Values for ions without a coordination number stated are
estimates.
Data: R.D. Shannon and C.T. Prewitt, Acta Cryst. B25, 925 (1969).
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PART 4 Data 953
Table 38.4 Lattice enthalpies, ΔHL< /(kJ mol−1) at 298 K
F Cl Br I
Halides
Li 1037 852 815 761
Na 926 787 752 705
K 821 717 689 649
Rb 789 695 668 632
Cs 750 676 654 620
Ag 969 912 900 886
Be 3017
Mg 2524
Ca 2255
Sr 2153
Oxides
MgO 3850 CaO 3461 SrO 3283 BaO 3114
Sulfides
MgS 3406 CaS 3119 SrS 2974 BaS 2832
Entries refer to MX(s) → M+ (g) + X− (g).
Data: Principally D. Cubicciotti, et al., J. Chem. Phys. 31, 1646 (1959).
Table 39.1 Magnetic susceptibilities at 298 K
χ/10−6 χm/(10−10 m3 mol−1)

H2O(l) −9.02 −1.63
C6H6(l) −8.8 −7.8
C6H12(l) −10.2 −11.1
CCl4(l) −5.4 −5.2
NaCl(s) −16 −3.8
Cu(s) −9.7 −0.69
S(rhombic) −12.6 −1.95
Hg(l) −28.4 −4.21
Al(s) +20.7 +2.07
Pt(s) +267.3 +24.25
Na(s) +8.48 +2.01
K(s) +5.94 +2.61
CuSO4 . 5H2O(s) +167 +183
MnSO4 . 4H2O(s) +1859 +1835
NiSO4 . 7H2O(s) +355 +503
FeSO4(s) +3743 +1558
Source: Principally HCP, with χm = χVm= χρ/M.
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Table 43.1 Properties of diatomic molecules
␯ / cm −1 θV/K B / cm −1 θR/K Re/pm kf/(N m−1) Do/(kJ mol−1) σ

1H + 2321.8 3341 29.8 42.9 106 160 255.8 2
2
1H 4400.39 6332 60.864 87.6 74.138 574.9 432.1 2
2
2H 3118.46 4487 30.442 43.8 74.154 577.0 439.6 2
2
1H19F 4138.32 5955 20.956 30.2 91.680 965.7 564.4 1
1H35Cl 2990.95 4304 10.593 15.2 127.45 516.3 427.7 1
1H81Br 2648.98 3812 8.465 12.2 141.44 411.5 362.7 1
1H127I 2308.09 3321 6.511 9.37 160.92 313.8 294.9 1
14N 2358.07 3393 1.9987 2.88 109.76 2293.8 941.7 2
2
16O 1580.36 2274 1.4457 2.08 120.75 1176.8 493.5 2
2
19F 891.8 1283 0.8828 1.27 141.78 445.1 154.4 2
2
35Cl 559.71 805 0.2441 0.351 198.75 322.7 239.3 2
2
12C16O 2170.21 3122 1.9313 2.78 112.81 1903.17 1071.8 1
79Br81Br 323.2 465 0.0809 0.116 283.3 245.9 190.2 1
Data: AIP.
Table 44.1 Typical vibrational Table 45.1 Colour, wavelength, frequency, and energy of light
wavenumbers, ␯ /cm−1
Colour λ/nm ν/(1014 Hz) ␯ /(104 cm−1) E/eV E/(kJ mol−1)
C–H stretch 2850–2960 Infrared >1000 <3.00 <1.00 <1.24 <120
C–H bend 1340–1465
Red 700 4.28 1.43 1.77 171
C–C stretch, bend 700–1250
Orange 620 4.84 1.61 2.00 193
C = C stretch 1620–1680
Yellow 580 5.17 1.72 2.14 206
C ^ C stretch 2100–2260 Green 530 5.66 1.89 2.34 226
O–H stretch 3590–3650 Blue 470 6.38 2.13 2.64 254
H-bonds 3200–3570 Violet 420 7.14 2.38 2.95 285
C = O stretch 1640–1780 Ultraviolet <400 >7.5 >2.5 >3.10 >300
C ≡ N stretch 2215–2275
Data: J.G. Calvert and J.N. Pitts, Photochemistry. Wiley, New York (1966).
N–H stretch 3200–3500
C–F stretch 1000–1400
C–Cl stretch 600–800
C–Br stretch 500–600
C–I stretch 500
CO2−
3 1410–1450
NO3− 1350–1420
NO2− 1230–1250
SO2−
4 1080–1130
Silicates 900–1100
Data: L.J. Bellamy, The infrared spectra of complex
molecules. Chapman and Hall (1975). Advances in
infrared group frequencies. Chapman and Hall (1968).
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PART 4 Data 955
Table 45.2 Absorption characteristics of some groups and molecules
Group ␯ max/(104 cm−1) λmax/nm ε/(dm3 mol−1 cm−1)
C = C (π* ← π) 6.10 163 1.5 × 104

5.73 174 5.5 × 103
C = O (π* ← n) 3.7–3.5 270–290 10–20
–N = N– 2.9 350 15
>3.9 <260 Strong
–NO2 3.6 280 10
4.8 210 1.0 × 104
C6H5– 3.9 255 200
5.0 200 6.3 × 103
5.5 180 1.0 × 105
[Cu(OH2)6]2+(aq) 1.2 810 10
[Cu(NH3)4 ]2+(aq) 1.7 600 50
H2O (π* ← n) 6.0 167 7.0 × 103
Table 47.2 Nuclear spin properties
Nuclide Natural Spin, I Magnetic g-value γ /(107 T−1s−1) NMR frequency

abundance, % Moment, μ/μN at 1 T, ␯/MHz
1n* 1 −1.9130 −3.8260 −18.324 29.164
2
1H 99.9844 1 2.792 85 5.5857 26.752 42.576
2
2H 0.0156 1 0.857 44 0.857 44 4.1067 6.536
3H* 1 2.978 96 −4.2553 −20.380 45.414
2
10B 19.6 3 1.8006 0.6002 2.875 4.575
11B 80.4 3 2.6886 1.7923 8.5841 13.663
2
13C 1.108 1 0.7024 1.4046 6.7272 10.708
2
14N 99.635 1 0.403 56 0.403 56 1.9328 3.078
17O 0.037 5 −1.893 79 −0.7572 −3.627 5.774
2
19F 100 1 2.628 87 5.2567 25.177 40.077
2
31P 100 1 1.1316 2.2634 10.840 17.251
2
33S 0.74 3 0.6438 0.4289 2.054 3.272
2
35Cl 75.4 3 0.8219 0.5479 2.624 4.176
2
37Cl 24.6 3 0.6841 0.4561 2.184 3.476
2
* Radioactive.
μ is the magnetic moment of the spin state with the largest value of mI: μ = g Iμ NI and μ N is the nuclear magneton (see inside front cover).
Data: KL and HCP.
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Table 50.1 Hyperfine coupling constants for atoms,

Table 52.1 Rotational and vibrational temperatures:
a/mT
see Table 43.1
Nuclide Spin Isotropic Anisotropic
coupling coupling
1H 1 50.8(1s) Table 52.2 Symmetry numbers: see Table 43.1
2
2H 1 7.8(1s)
13C 1 113.0(2s) 6.6(2p)
2
14N 1 55.2(2s) 4.8(2p)
19F 1
2 1720(2s) 108.4(2p)
31P 1
2 364(3s) 20.6(3p)
35Cl 3
2 168(3s) 10.0(3p)
37Cl 3
2 140(3s) 8.4(3p)
Data: P.W. Atkins and M.C.R. Symons, The structure of inorganic

radicals. Elsevier, Amsterdam (1967).
Table 56.1 Temperature variation of molar heat capacities†
a b/(10−3 K−1) c/(105 K2)

Monatomic gases
20.78 0 0
Other gases
Br2 37.32 0.50 −1.26
Cl2 37.03 0.67 −2.85
CO2 44.22 8.79 −8.62
F2 34.56 2.51 −3.51
H2 27.28 3.26 0.50
I2 37.40 0.59 −0.71
N2 28.58 3.77 −0.50
NH3 29.75 25.1 −1.55
O2 29.96 4.18 −1.67
Liquids (from melting to boiling)

C10H8, naphthalene 79.5 0.4075 0
I2 80.33 0 0
H2O 75.29 0 0
Solids
Al 20.67 12.38 0
C (graphite) 16.86 4.77 −8.54
C10H8, naphthalene −110 936 0
Cu 22.64 6.28 0
I2 40.12 49.79 0
NaCl 45.94 16.32 0
Pb 22.13 11.72 0.96
†ForCp,m/(J K−1 mol−1) = a + bT + c/T 2.
Source: Mostly LR.
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PART 4 Data 957
Table 56.2 Inversion temperatures, normal freezing and boiling

points, and Joule–Thomson coefficients at 1 atm and 298 K
TI/K Tf/K Tb/K μ/(K atm−1)

Air 603 0.189 at 50 °C
Argon 723 83.8 87.3
Carbon dioxide 1500 194.7s 1.11 at 300 K
Helium 40 4.22 −0.062
Hydrogen 202 14.0 20.3 −0.03
Krypton 1090 116.6 120.8
Methane 968 90.6 111.6
Neon 231 24.5 27.1
Nitrogen 621 63.3 77.4 0.27
Oxygen 764 54.8 90.2 0.31
s: sublimes.
Data: AIP, JL, and M.W. Zemansky, Heat and thermodynamics. McGraw-Hill, New York (1957).
Table 57.2 Standard enthalpies of fusion and vaporization at the transition temperature, Δtrs H < /(kJ mol−1)
Tf/K Fusion Tb/K Vaporization Tf/K Fusion Tb/K Vaporization

Elements Inorganic compounds
Ag 1234 11.30 2436 250.6 CO2 217.0 8.33 194.6 25.23s
Ar 83.81 1.188 87.29 6.506 CS2 161.2 4.39 319.4 26.74
Br2 265.9 10.57 332.4 29.45 H2O 273.15 6.008 373.15 40.656
Cl2 172.1 6.41 239.1 20.41 44.016 at 298 K
F2 53.6 0.26 85.0 3.16 H2S 187.6 2.377 212.8 18.67
H2 13.96 0.117 20.38 0.916 H2SO4 283.5 2.56
He 3.5 0.021 4.22 0.084 NH3 195.4 5.652 239.7 23.35
Hg 234.3 2.292 629.7 59.30
I2 386.8 15.52 458.4 41.80
Organic compounds
N2 63.15 0.719 77.35 5.586 CH4 90.68 0.941 111.7 8.18
Na 371.0 2.601 1156 98.01 CCl4 250.3 2.47 349.9 30.00
O2 54.36 0.444 90.18 6.820 C2H6 89.85 2.86 184.6 14.7
Xe 161 2.30 165 12.6 C6H6 278.61 10.59 353.2 30.8
K 336.4 2.35 1031 80.23 C6H14 178 13.08 342.1 28.85
C10H8 354 18.80 490.9 51.51
CH3OH 175.2 3.16 337.2 35.27
37.99 at 298 K
C2H5OH 158.7 4.60 352 43.5
Data: AIP; s denotes sublimation.
Atkins09819.indb 957 9/11/2013 8:55:31 AM

Table 57.3 Thermodynamic data for organic compounds at 298 K
M/(g mol−1) ΔfH</(kJ mol−1) ΔfG</(kJ mol−1) < /(JK −1 mol −1 ) C< −1 −1 ΔcH</(kJ mol−1)
Sm p,m /(JK mol )
C(s) (graphite) 12.011 0 0 5.740 8.527 −393.51

C(s) (diamond) 12.011 +1.895 +2.900 2.377 6.113 −395.40
CO2(g) 44.040 −393.51 −394.36 213.74 37.11
Hydrocarbons
CH4(g), methane 16.04 −74.81 −50.72 186.26 35.31 −890
CH3(g), methyl 15.04 +145.69 +147.92 194.2 38.70
C2H2(g), ethyne 26.04 +226.73 +209.20 200.94 43.93 −1300
C2H4(g), ethene 28.05 +52.26 +68.15 219.56 43.56 −1411
C2H6(g), ethane 30.07 −84.68 −32.82 229.60 52.63 −1560
C3H6(g), propene 42.08 +20.42 +62.78 267.05 63.89 −2058
C3H6(g), cyclopropane 42.08 +53.30 +104.45 237.55 55.94 −2091
C3H8(g), propane 44.10 −103.85 −23.49 269.91 73.5 −2220
C4H8(g), 1-butene 56.11 −0.13 +71.39 305.71 85.65 −2717
C4H8(g), cis-2-butene 56.11 −6.99 +65.95 300.94 78.91 −2710
C4H8(g), trans-2-butene 56.11 −11.17 +63.06 296.59 87.82 −2707
C4H10(g), butane 58.13 −126.15 −17.03 310.23 97.45 −2878
C5H12(g), pentane 72.15 −146.44 −8.20 348.40 120.2 −3537
C5H12(l) 72.15 −173.1
C6H6(l), benzene 78.12 +49.0 +124.3 173.3 136.1 −3268
C6H6(g) 78.12 +82.93 +129.72 269.31 81.67 −3302
C6H12(l), cyclohexane 84.16 −156 +26.8 204.4 156.5 −3920
C6H14(l), hexane 86.18 −198.7 204.3 −4163
C6H5CH3(g), methylbenzene 92.14 +50.0 +122.0 320.7 103.6 −3953
(toluene)
C7H16(l), heptane 100.21 −224.4 +1.0 328.6 224.3
C8H18(l), octane 114.23 −249.9 +6.4 361.1 −5471
C8H18(l), iso-octane 114.23 −255.1 −5461
C10H8(s), naphthalene 128.18 +78.53 −5157
Alcohols and phenols
CH3OH(l), methanol 32.04 −238.66 −166.27 126.8 81.6 −726
CH3OH(g) 32.04 −200.66 −161.96 239.81 43.89 −764
C2H5OH(l), ethanol 46.07 −277.69 −174.78 160.7 111.46 −1368
C2H5OH(g) 46.07 −235.10 −168.49 282.70 65.44 −1409
C6H5OH(s), phenol 94.12 −165.0 −50.9 146.0 −3054
Carboxylic acids, hydroxy acids, and esters
HCOOH(l), formic 46.03 −424.72 −361.35 128.95 99.04 −255
CH3COOH(l), acetic 60.05 −484.5 −389.9 159.8 124.3 −875
CH3COOH(aq) 60.05 −485.76 −396.46 178.7
CH3CO2− (aq ) 59.05 −486.01 −369.31 +86.6† −6.3
(COOH)2(s), oxalic 90.04 −827.2 117 −254
C6H5COOH(s), benzoic 122.13 −385.1 −245.3 167.6 146.8 −3227
CH3CH(OH)COOH(s), lactic 90.08 −694.0 −1344
CH3COOC2H5(l), ethyl acetate 88.11 −479.0 −332.7 259.4 170.1 −2231
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Atkins09819.indb 958 9/11/2013 8:55:33 AM

PART 4 Data 959
M/(g mol−1) ΔfH</(kJ mol−1) ΔfG</(kJ mol−1) < /(JK −1 mol −1 ) C< −1 −1 ΔcH</(kJ mol−1)
Sm p,m /(JK mol )
Alkanals and alkanones

HCHO(g), methanal 30.03 −108.57 −102.53 218.77 35.40 −571
CH3CHO(l), ethanal 44.05 −192.30 −128.12 160.2 −1166
CH3CHO(g) 44.05 −166.19 −128.86 250.3 57.3 −1192
CH3COCH3(l), propanone 58.08 −248.1 −155.4 200.4 124.7 −1790
Sugars
C6H12O6(s), α-d-glucose 180.16 −1274 −2808
C6H12O6(s), β-d-glucose 180.16 −1268 −910 212
C6H12O6(s), β-d-fructose 180.16 −1266 −2810
C12H22O11(s), sucrose 342.30 −2222 −1543 360.2 −5645
Nitrogen compounds
CO(NH2)2(s), urea 60.06 −333.51 −197.33 104.60 93.14 −632
CH3NH2(g), methylamine 31.06 −22.97 +32.16 243.41 53.1 −1085
C6H5NH2(l), aniline 93.13 +31.1 −3393
CH2(NH2)COOH(s), glycine 75.07 −532.9 −373.4 103.5 99.2 −969
Data: NBS, TDOC. † Standard entropies of ions may be either positive or negative because the values are relative to the entropy of the hydrogen ion.
Table 57.4 Thermodynamic data for elements and inorganic compounds at 298 K
< /(JK −1 mol −1 ) † C< −1 −1
M/(g mol−1) ΔfH</(kJ mol−1) ΔfG</(kJ mol−1) Sm p,m /(JK mol )
Aluminium (aluminum)
Al(s) 26.98 0 0 28.33 24.35
Al(l) 26.98 +10.56 +7.20 39.55 24.21
Al(g) 26.98 +326.4 +285.7 164.54 21.38
Al3+(g) 26.98 +5483.17
Al3+(aq) 26.98 −531 −485 −321.7
Al2O3(s, α) 101.96 −1675.7 −1582.3 50.92 79.04
AlCl3(s) 133.24 −704.2 −628.8 110.67 91.84
Argon
Ar(g) 39.95 0 0 154.84 20.786
Antimony
Sb(s) 121.75 0 0 45.69 25.23
SbH3(g) 124.77 +145.11 +147.75 232.78 41.05
Arsenic
As(s, α) 74.92 0 0 35.1 24.64
As(g) 74.92 +302.5 +261.0 174.21 20.79
As4(g) 299.69 +143.9 +92.4 314
AsH3(g) 77.95 +66.44 +68.93 222.78 38.07
Barium
Ba(s) 137.34 0 0 62.8 28.07
Ba(g) 137.34 +180 +146 170.24 20.79
Ba2+(aq) 137.34 −537.64 −560.77 +9.6
BaO(s) 153.34 −553.5 −525.1 70.43 47.78
BaCl2(s) 208.25 −858.6 −810.4 123.68 75.14
(continued)
Atkins09819.indb 959 9/11/2013 8:55:34 AM

< /(JK −1 mol −1 ) † C< −1 −1

Beryllium
Be(s) 9.01 0 0 9.50 16.44
Be(g) 9.01 +324.3 +286.6 136.27 20.79
Bismuth
Bi(s) 208.98 0 0 56.74 25.52
Bi(g) 208.98 +207.1 +168.2 187.00 20.79
Bromine
Br2(l) 159.82 0 0 152.23 75.689
Br2(g) 159.82 +30.907 +3.110 245.46 36.02
Br(g) 79.91 +111.88 +82.396 175.02 20.786
Br−(g) 79.91 −219.07
Br−(aq) 79.91 −121.55 −103.96 +82.4 −141.8
HBr(g) 90.92 −36.40 −53.45 198.70 29.142
Cadmium
Cd(s, γ) 112.40 0 0 51.76 25.98
Cd(g) 112.40 +112.01 +77.41 167.75 20.79
Cd2+(aq) 112.40 −75.90 −77.612 −73.2
CdO(s) 128.40 −258.2 −228.4 54.8 43.43
CdCO3(s) 172.41 −750.6 −669.4 92.5
Caesium (cesium)
Cs(s) 132.91 0 0 85.23 32.17
Cs(g) 132.91 +76.06 +49.12 175.60 20.79
Cs+(aq) 132.91 −258.28 −292.02 +133.05 −10.5
Calcium
Ca(s) 40.08 0 0 41.42 25.31
Ca(g) 40.08 +178.2 +144.3 154.88 20.786
Ca2+(aq) 40.08 −542.83 −553.58 −53.1
CaO(s) 56.08 −635.09 −604.03 39.75 42.80
CaCO3(s) (calcite) 100.09 −1206.9 −1128.8 92.9 81.88
CaCO3(s) (aragonite) 100.09 −1207.1 −1127.8 88.7 81.25
CaF2(s) 78.08 −1219.6 −1167.3 68.87 67.03
CaCl2(s) 110.99 −795.8 −748.1 104.6 72.59
CaBr2(s) 199.90 −682.8 −663.6 130
Carbon (for ‘organic’ compounds of carbon, see Table 57.3)
C(s) (graphite) 12.011 0 0 5.740 8.527
C(s) (diamond) 12.011 +1.895 +2.900 2.377 6.113
C(g) 12.011 +716.68 +671.26 158.10 20.838
C2(g) 24.022 +831.90 +775.89 199.42 43.21
CO(g) 28.011 −110.53 −137.17 197.67 29.14
CO2(g) 44.010 −393.51 −394.36 213.74 37.11
CO2(aq) 44.010 −413.80 −385.98 117.6
H2CO3(aq) 62.03 −699.65 −623.08 187.4
HCO3− (aq ) 61.02 −691.99 −586.77 +91.2
CO2−
3 (aq ) 60.01 −677.14 −527.81 −56.9
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Atkins09819.indb 960 9/11/2013 8:55:35 AM

PART 4 Data 961
< /(JK −1 mol −1 ) † C< −1 −1

Carbon (for ‘organic’ compounds of carbon, see Table 57.3) (continued)

CCl4(l) 153.82 −135.44 −65.21 216.40 131.75
CS2(l) 76.14 +89.70 +65.27 151.34 75.7
HCN(g) 27.03 +135.1 +124.7 201.78 35.86
HCN(l) 27.03 +108.87 +124.97 112.84 70.63
CN−(aq) 26.02 +150.6 +172.4 +94.1
Chlorine
Cl2(g) 70.91 0 0 223.07 33.91
Cl(g) 35.45 +121.68 +105.68 165.20 21.840
Cl−(g) 34.45 −233.13
Cl−(aq) 35.45 −167.16 −131.23 +56.5 −136.4
HCl(g) 36.46 −92.31 −95.30 186.91 29.12
HCl(aq) 36.46 −167.16 −131.23 56.5 −136.4
Chromium
Cr(s) 52.00 0 0 23.77 23.35
Cr(g) 52.00 +396.6 +351.8 174.50 20.79
CrO2−
4 (aq ) 115.99 −881.15 −727.75 +50.21
Cr2O2−
7 (aq ) 215.99 −1490.3 −1301.1 +261.9
Copper
Cu(s) 63.54 0 0 33.150 24.44
Cu(g) 63.54 +338.32 +298.58 166.38 20.79
Cu+(aq) 63.54 +71.67 +49.98 +40.6
Cu2+(aq) 63.54 +64.77 +65.49 −99.6
Cu2O(s) 143.08 −168.6 −146.0 93.14 63.64
CuO(s) 79.54 −157.3 −129.7 42.63 42.30
CuSO4(s) 159.60 −771.36 −661.8 109 100.0
CuSO4·H2O(s) 177.62 −1085.8 −918.11 146.0 134
CuSO4·5H2O(s) 249.68 −2279.7 −1879.7 300.4 280
Deuterium
D2(g) 4.028 0 0 144.96 29.20
HD(g) 3.022 +0.318 −1.464 143.80 29.196
D2O(g) 20.028 −249.20 −234.54 198.34 34.27
D2O(l) 20.028 −294.60 −243.44 75.94 84.35
HDO(g) 19.022 −245.30 −233.11 199.51 33.81
HDO(l) 19.022 −289.89 −241.86 79.29
Fluorine
F2(g) 38.00 0 0 202.78 31.30
F(g) 19.00 +78.99 +61.91 158.75 22.74
F−(aq) 19.00 −332.63 −278.79 −13.8 −106.7
HF(g) 20.01 −271.1 −273.2 173.78 29.13
Gold
Au(s) 196.97 0 0 47.40 25.42
Au(g) 196.97 +366.1 +326.3 180.50 20.79
Helium
He(g) 4.003 0 0 126.15 20.786
(continued)
Atkins09819.indb 961 9/11/2013 8:55:37 AM

< /(JK −1 mol −1 ) † C< −1 −1

Hydrogen (see also deuterium)

H2(g) 2.016 0 0 130.684 28.824
H(g) 1.008 +217.97 +203.25 114.71 20.784
H+(aq) 1.008 0 0 0 0
H+(g) 1.008 +1536.20
H2O(s) 18.015 37.99
H2O(l) 18.015 −285.83 −237.13 69.91 75.291
H2O(g) 18.015 −241.82 −228.57 188.83 33.58
H2O2(l) 34.015 −187.78 −120.35 109.6 89.1
Iodine
I2(s) 253.81 0 0 116.135 54.44
I2(g) 253.81 +62.44 +19.33 260.69 36.90
I(g) 126.90 +106.84 +70.25 180.79 20.786
I−(aq) 126.90 −55.19 −51.57 +111.3 −142.3
HI(g) 127.91 +26.48 +1.70 206.59 29.158
Iron
Fe(s) 55.85 0 0 27.28 25.10
Fe(g) 55.85 +416.3 +370.7 180.49 25.68
Fe2+(aq) 55.85 −89.1 −78.90 −137.7
Fe3+(aq) 55.85 −48.5 −4.7 −315.9
Fe3O4(s) (magnetite) 231.54 −1118.4 −1015.4 146.4 143.43
Fe2O3(s) (haematite) 159.69 −824.2 −742.2 87.40 103.85
FeS(s, α) 87.91 −100.0 −100.4 60.29 50.54
FeS2(s) 119.98 −178.2 −166.9 52.93 62.17
Krypton
Kr(g) 83.80 0 0 164.08 20.786
Lead
Pb(s) 207.19 0 0 64.81 26.44
Pb(g) 207.19 +195.0 +161.9 175.37 20.79
Pb2+(aq) 207.19 −1.7 −24.43 +10.5
PbO(s, yellow) 223.19 −217.32 −187.89 68.70 45.77
PbO(s, red) 223.19 −218.99 −188.93 66.5 45.81
PbO2(s) 239.19 −277.4 −217.33 68.6 64.64
Lithium
Li(s) 6.94 0 0 29.12 24.77
Li(g) 6.94 +159.37 +126.66 138.77 20.79
Li+(aq) 6.94 −278.49 −293.31 +13.4 68.6
Magnesium
Mg(s) 24.31 0 0 32.68 24.89
Mg(g) 24.31 +147.70 +113.10 148.65 20.786
Mg2+(aq) 24.31 −466.85 −454.8 −138.1
MgO(s) 40.31 −601.70 −569.43 26.94 37.15
MgCO3(s) 84.32 −1095.8 −1012.1 65.7 75.52
MgCl2(s) 95.22 −641.32 −591.79 89.62 71.38
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Atkins09819.indb 962 9/11/2013 8:55:38 AM

PART 4 Data 963
< /(JK −1 mol −1 ) † C< −1 −1

Mercury
Hg(l) 200.59 0 0 76.02 27.983
Hg(g) 200.59 +61.32 +31.82 174.96 20.786
Hg2+(aq) 200.59 +171.1 +164.40 −32.2
Hg 2+
2 (aq ) 401.18 +172.4 +153.52 +84.5
HgO(s) 216.59 −90.83 −58.54 70.29 44.06
Hg2Cl2(s) 472.09 −265.22 −210.75 192.5 102
HgCl2(s) 271.50 −224.3 −178.6 146.0
HgS(s, black) 232.65 −53.6 −47.7 88.3
Neon
Ne(g) 20.18 0 0 146.33 20.786
Nitrogen
N2(g) 28.013 0 0 191.61 29.125
N(g) 14.007 +472.70 +455.56 153.30 20.786
NO(g) 30.01 +90.25 +86.55 210.76 29.844
N2O(g) 44.01 +82.05 +104.20 219.85 38.45
NO2(g) 46.01 +33.18 +51.31 240.06 37.20
N2O4(g) 92.1 +9.16 +97.89 304.29 77.28
N2O5(s) 108.01 −43.1 +113.9 178.2 143.1
N2O5(g) 108.01 +11.3 +115.1 355.7 84.5
HNO3(l) 63.01 −174.10 −80.71 155.60 109.87
HNO3(aq) 63.01 −207.36 −111.25 146.4 −86.6
NO3− (aq ) 62.01 −205.0 −108.74 +146.4 −86.6
NH3(g) 17.03 −46.11 −16.45 192.45 35.06
NH3(aq) 17.03 −80.29 −26.50 111.3
NH +4 (aq ) 18.04 −132.51 −79.31 +113.4 79.9
NH2OH(s) 33.03 −114.2
HN3(l) 43.03 +264.0 +327.3 140.6 43.68
HN3(g) 43.03 +294.1 +328.1 238.97 98.87
N2H4(l) 32.05 +50.63 +149.43 121.21 139.3
NH4NO3(s) 80.04 −365.56 −183.87 151.08 84.1
NH4Cl(s) 53.49 −314.43 −202.87 94.6
Oxygen
O2(g) 31.999 0 0 205.138 29.355
O(g) 15.999 +249.17 +231.73 161.06 21.912
O3(g) 47.998 +142.7 +163.2 238.93 39.20
OH−(aq) 17.007 −229.99 −157.24 −10.75 −148.5
Phosphorus
P(s, wh) 30.97 0 0 41.09 23.840
P(g) 30.97 +314.64 +278.25 163.19 20.786
P2(g) 61.95 +144.3 +103.7 218.13 32.05
P4(g) 123.90 +58.91 +24.44 279.98 67.15
PH3(g) 34.00 +5.4 +13.4 210.23 37.11
PCl3(g) 137.33 −287.0 −267.8 311.78 71.84
(continued)
Atkins09819.indb 963 9/11/2013 8:55:39 AM

< /(JK −1 mol −1 ) † C< −1 −1

Phosphorus (continued)
PCl3(l) 137.33 −319.7 −272.3 217.1
PCl5(g) 208.24 −374.9 −305.0 364.6 112.8
PCl5(s) 208.24 −443.5
H3PO3(s) 82.00 −964.4
H3PO3(aq) 82.00 −964.8
H3PO4(s) 94.97 −1279.0 −1119.1 110.50 106.06
H3PO4(l) 94.97 −1266.9
H3PO4(aq) 94.97 −1277.4 −1018.7 −222
PO3−
4 (aq ) 94.97 −1277.4 −1018.7 −221.8
P4O10(s) 283.89 −2984.0 −2697.0 228.86 211.71
P4O6(s) 219.89 −1640.1
Potassium
K(s) 39.10 0 0 64.18 29.58
K(g) 39.10 +89.24 +60.59 160.336 20.786
K+(g) 39.10 +514.26
K+(aq) 39.10 −252.38 −283.27 +102.5 21.8
KOH(s) 56.11 −424.76 −379.08 78.9 64.9
KF(s) 58.10 −576.27 −537.75 66.57 49.04
KCl(s) 74.56 −436.75 −409.14 82.59 51.30
KBr(s) 119.01 −393.80 −380.66 95.90 52.30
Kl(s) 166.01 −327.90 −324.89 106.32 52.93
Silicon
Si(s) 28.09 0 0 18.83 20.00
Si(g) 28.09 +455.6 +411.3 167.97 22.25
SiO2(s, α) 60.09 −910.94 −856.64 41.84 44.43
Silver
Ag(s) 107.87 0 0 42.55 25.351
Ag(g) 107.87 +284.55 +245.65 173.00 20.79
Ag+(aq) 107.87 +105.58 +77.11 +72.68 21.8
AgBr(s) 187.78 −100.37 −96.90 107.1 52.38
AgCl(s) 143.32 −127.07 −109.79 96.2 50.79
Ag2O(s) 231.74 −31.05 −11.20 121.3 65.86
AgNO3(s) 169.88 −129.39 −33.41 140.92 93.05
Sodium
Na(s) 22.99 0 0 51.21 28.24
Na(g) 22.99 +107.32 +76.76 153.71 20.79
Na+(aq) 22.99 −240.12 −261.91 +59.0 46.4
NaOH(s) 40.00 −425.61 −379.49 64.46 59.54
NaCl(s) 58.44 −411.15 −384.14 72.13 50.50
NaBr(s) 102.90 −361.06 −348.98 86.82 51.38
NaI(s) 149.89 −287.78 −286.06 98.53 52.09
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Atkins09819.indb 964 9/11/2013 8:55:41 AM

PART 4 Data 965
M/(g mol−1) ΔfH</(kJ mol−1) ΔfG</(kJ mol−1) < /(JK −1 mol −1 ) † C< −1 −1
Sm p,m /(JK mol )
Sulfur
S(s, α) (rhombic) 32.06 0 0 31.80 22.64
S(s, β) (monoclinic) 32.06 +0.33 +0.1 32.6 23.6
S(g) 32.06 +278.81 +238.25 167.82 23.673
S2(g) 64.13 +128.37 +79.30 228.18 32.47
S2−(aq) 32.06 +33.1 +85.8 −14.6
SO2(g) 64.06 −296.83 −300.19 248.22 39.87
SO3(g) 80.06 −395.72 −371.06 256.76 50.67
H2SO4(l) 98.08 −813.99 −690.00 156.90 138.9
H2SO4(aq) 98.08 −909.27 −744.53 20.1 −293
SO2−
4 (aq) 96.06 −909.27 −744.53 +20.1 −293
HSO−4 (aq ) 97.07 −887.34 −755.91 +131.8 −84
H2S(g) 34.08 −20.63 −33.56 205.79 34.23
H2S(aq) 34.08 −39.7 −27.83 121
HS−(aq) 33.072 −17.6 +12.08 +62.08
SF6(g) 146.05 −1209 −1105.3 291.82 97.28
Tin
Sn(s, β) 118.69 0 0 51.55 26.99
Sn(g) 118.69 +302.1 +267.3 168.49 20.26
Sn2+(aq) 118.69 −8.8 −27.2 −17
SnO(s) 134.69 −285.8 −256.9 56.5 44.31
SnO2(s) 150.69 −580.7 −519.6 52.3 52.59
Xenon
Xe(g) 131.30 0 0 169.68 20.786
Zinc
Zn(s) 65.37 0 0 41.63 25.40
Zn(g) 65.37 +130.73 +95.14 160.98 20.79
Zn2+(aq) 65.37 −153.89 −147.06 −112.1 46
ZnO(s) 81.37 −348.28 −318.30 43.64 40.25
Source: NBS. † Standard entropies of ions may be either positive or negative because the values are relative to the entropy of the hydrogen ion.
Atkins09819.indb 965 9/11/2013 8:55:42 AM

Table 58.1 Expansion coefficients, α, and isothermal Table 62.1 Standard entropies (and temperatures) of
compressibilities, κT phase transitions, ΔtrsS < /(J K−1 mol−1)
α/(10−4 K−1) κT /(10−6 atm−1) Fusion (at Tf) Vaporization (at Tb)
Liquids Ar 14.17 (at 83.8 K) 74.53 (at 87.3 K)
Benzene 12.4 92.1 Br2 39.76 (at 265.9 K) 88.61 (at 332.4 K)
Carbon tetrachloride 12.4 90.5 C6H6 38.00 (at 278.6 K) 87.19 (at 353.2 K)
Ethanol 11.2 76.8 CH3COOH 40.4 (at 289.8 K) 61.9 (at 391.4 K)
Mercury 1.82 38.7 CH3OH 18.03 (at 175.2 K) 104.6 (at 337.2 K)
Water 2.1 49.6 Cl2 37.22 (at 172.1 K) 85.38 (at 239.0 K)
H2 8.38 (at 14.0 K) 44.96 (at 20.38 K)
Solids
H2O 22.00 (at 273.2 K) 109.1 (at 373.2 K)
Copper 0.501 0.735
H2S 12.67 (at 187.6 K) 87.75 (at 212.0 K)
Diamond 0.030 0.187
He 4.8 (at 1.8 K and 30 bar) 19.9 (at 4.22 K)
Iron 0.354 0.589
N2 11.39 (at 63.2 K) 75.22 (at 77.4 K)
Lead 0.861 2.21
The values refer to 20 °C.
NH3 28.93 (at 195.4 K) 97.41 (at 239.73 K)
Data: AIP(α), KL(κT). O2 8.17 (at 54.4 K) 75.63 (at 90.2 K)
Data: AIP.
Table 62.2 The standard enthalpies and entropies of vaporization of

liquids at their normal boiling point
ΔvapH</(kJ mol−1) θb/°C ΔvapS</(J K−1 mol−1)

Benzene 30.8 80.1 +87.2
Carbon disulfide 26.74 46.25 +83.7
Carbon tetrachloride 30.00 76.7 +85.8
Cyclohexane 30.1 80.7 +85.1
Decane 38.75 174 +86.7
Dimethyl ether 21.51 −23 +86
Ethanol 38.6 78.3 +110.0
Hydrogen sulfide 18.7 −60.4 +87.9
Mercury 59.3 356.6 +94.2
Methane 8.18 −161.5 +73.2
Methanol 35.21 65.0 +104.1
Water 40.7 100.0 +109.1
Data: JL.
Table 63.1 Standard Third-Law entropies at 298 K: see Tables Table 70.1 Henry’s law constants for
57.3 and 57.4 gases at 298 K, K/(kPa kg mol−1)
Water Benzene
Table 65.1 Standard Gibbs energies of formation at 298 K: CH4 7.55 × 104 44.4 × 103
see Tables 57.3 and 57.4 CO2 3.01 × 103 8.90 × 102
H2 1.28 × 105 2.79 × 104
N2 1.56 × 105 1.87 × 104
O2 7.92 × 104
Data: converted from R.J. Silbey and R.A. Alberty,
Physical chemistry. Wiley, New York (2001).
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PART 4 Data 967
Table 72.3 Mean activity coefficients in water at 298 K
b/b< HCl KCl CaCl2 H2SO4 LaCl3 In2(SO4)3

0.001 0.966 0.966 0.888 0.830 0.790
0.005 0.929 0.927 0.789 0.639 0.636 0.16
0.01 0.905 0.902 0.732 0.544 0.560 0.11
0.05 0.830 0.816 0.584 0.340 0.388 0.035
0.10 0.798 0.770 0.524 0.266 0.356 0.025
0.50 0.769 0.652 0.510 0.155 0.303 0.014
1.00 0.811 0.607 0.725 0.131 0.387
2.00 1.011 0.577 1.554 0.125 0.954
Data: RS, HCP, and S. Glasstone, Introduction to electrochemistry. Van Nostrand (1942).
Table 77.1A Standard potentials at 298 K. (a) In electrochemical order
Reduction half-reaction E</V Reduction half-reaction E</V
Strongly oxidizing Hg2+ + 2 e− → Hg +0.86
H4XeO6 + 2 H+ + 2 e− → XeO NO3− + 2H + + e − → NO2 + H2O +0.80

3+3 H2O +3.0
F2 + 2 e−→ 2F− +2.87 Ag+ + e− → Ag +0.80
Hg 22+ + 2 e − → 2 Hg +0.79
O3 + 2 H+ + 2 e− → O2 + H2O +2.07
S2O28− + 2 e − → 2 SO24− +2.05 AgF + e− → Ag + F− +0.78
Fe3+ + e− → Fe2+ +0.77
Ag2+ + e− → Ag+ +1.98
BrO− + H2O + 2 e− → Br− + 2 OH− +0.76
Co3+ + e− → Co2+ +1.81
Hg 2SO4 + 2 e− → 2 Hg + SO24− +0.62
H2O2 + 2 H+ + 2 e− → 2 H2O +1.78
Au+ + e− → Au +1.69 MnO24− + 2 H2 O + 2 e − → MnO2 + 4 OH − +0.60
Pb4+ + 2 e− → Pb2+ +1.67 MnO−4 + e − → MnO24− +0.56
2 HClO + 2 H+ + 2 e−→ Cl2 + 2 H2O +1.63 I2 + 2 e−→ 2 I− +0.54
Ce4+ + e− → Ce3+ +1.61 I3− + 2 e − → 3 I− +0.53
2 HBrO + 2 H+ + 2 e−→ Br2 + 2 H2O +1.60 Cu+ + e− → Cu +0.52

MnO4− +8 H + + 5e − → Mn2 + + 4 H2 O +1.51 NiOOH + H2O + e− → Ni(OH)2 + OH− +0.49
Mn3+ + e− → Mn2+ +1.51 Ag 2CrO4 + 2 e− → 2 Ag + CrO24− +0.45
Au3+ + 3 e− → Au +1.40 O2 + 2 H2O + 4 e− → 4 OH− +0.40

Cl2 + 2 e−→ 2 Cl− +1.36 ClO−4 + H2O + 2 e − → ClO3− + 2OH − +0.36
Cr2O27− +14 H+ + 6 e− → 2 Cr 3+ + 7 H2 O +1.33 [Fe(CN)6]3− + e− → [Fe(CN)6]4− +0.36

O3 + H2O + 2 e− → O2 + 2 OH− +1.24 Cu2+ + 2 e− → Cu +0.34
O2 + 4 H++ 4 e− → 2 H2O +1.23 Hg2Cl2 + 2 e−→ 2 Hg + 2 Cl− +0.27
ClO−4 + 2 H + + 2 e − → ClO3− + H2O +1.23 AgCl + e− → Ag + Cl− +0.22
MnO2 + 4 H+ + 2 e− → Mn2+ + 2 H2O +1.23 Bi3+ + 3 e− → Bi +0.20
Pt2+ + 2 e− → Pt +1.20 Cu2+ + e− → Cu+ +0.16
Br2 + 2 e−→ 2Br− +1.09 Sn4+ + 2 e− → Sn2+ +0.15
Pu4+ + e− → Pu3+ +0.97 NO3− + H2O + 2 e − → NO2− + 2 OH − +0.10
NO3− + 4 H + + 3 e − → NO + 2 H2O +0.96 AgBr + e− → Ag + Br− +0.0713
2 Hg 2 + + 2 e − → Hg 22+ +0.92 Ti4+ + e− → Ti3+ 0.00
ClO− + H2O + 2 e− → Cl− + 2 OH− +0.89 2 H+ + 2 e− → H2 0, by definition
(continued)
Atkins09819.indb 967 9/11/2013 8:55:51 AM


Fe3+ + 3 e− → Fe −0.04 Zn2+ + 2 e− → Zn −0.76
O2 + H2O + 2 e − → HO2 − + OH − −0.08 Cd(OH)2 + 2e − → Cd + 2 OH − −0.81
Pb2+ + 2 e− → Pb −0.13 2 H2O + 2 e−→ H2 + 2 OH− −0.83
In+ + e− → In −0.14 Cr2+ + 2e− → Cr −0.91
Sn2+ + 2 e− → Sn −0.14 Mn2+ + 2 e− → Mn −1.18
AgI + e− → Ag + I− −0.15 V2+ + 2 e− → V −1.19
Ni2+ + 2 e− → Ni −0.23 Ti2+ + 2 e− → Ti −1.63

Al3+ + 3 e− → Al −1.66
V3+ + e− → V2+ −0.26
U3+ + 3 e− → U −1.79
Co2+ + 2 e− → Co −0.28
Be2+ + 2 e− → Be −1.85
In3+ + 3 e− → In −0.34
Sc3+ + 3 e− → Sc −2.09
Tl+ + e− → Tl −0.34
Mg2+ + 2 e− → Mg −2.36
PbSO 4 + 2 e − → Pb + SO42 − −0.36
Ce3+ + 3 e− → Ce −2.48
Ti3+ + e− → Ti2+ −0.37
La3+ + 3 e− → La −2.52
Cd2+ + 2 e− → Cd −0.40
Na+ + e− → Na −2.71
In2+ + e− → In+ −0.40 Ca2+ + 2 e− → Ca −2.87
Cr3+ + e− → Cr2+ −0.41 Sr2+ + 2 e− → Sr −2.89
Fe2+ + 2 e− → Fe −0.44 Ba2+ + 2 e− → Ba −2.91
In3+ + 2 e− → In+ −0.44 Ra2+ + 2 e− → Ra −2.92
S + 2 e− → S2− −0.48 Cs+ + e− → Cs −2.92
In3+ + e− → In2+ −0.49 Rb+ + e− → Rb −2.93
O2 + e − → O2− −0.56 K+ + e− → K −2.93
U4+ + e− → U3+ −0.61 Li+ + e− → Li −3.05
Cr3+ + 3 e− → Cr −0.74 Strongly reducing
Table 77.1 Standard potentials at 298 K. (b) In alphabetical order

Ag+ + e− → Ag +0.80 Ca2+ + 2 e− → Ca −2.87
Ag2+ + e− → Ag+ +1.98 Cd(OH)2 + 2 e−→ Cd + 2 OH− −0.81
AgBr + e− → Ag + Br− +0.0713 Cd2+ + 2 e− → Cd −0.40
AgCl + e− → Ag + Cl− +0.22 Ce3+ + 3 e− → Ce −2.48
Ag 2CrO4 + 2 e − → 2Ag + CrO24− +0.45 Ce4+ + e− → Ce3+ +1.61
AgF + e− → Ag + F− +0.78 Cl2 + 2 e−→ 2 Cl− +1.36
AgI + e− → Ag + I− −0.15 ClO− + H 2O + 2 e− → Cl− + 2 OH− +0.89
Al3+ + 3 e− → Al −1.66 ClO−4 + 2 H + + 2 e − → ClO3− + H2O +1.23
Au+ + e− → Au +1.69 ClO−4 + H2O + 2 e − → ClO3− +2 OH − +0.36
Au3+ + 3 e− → Au +1.40 Co2+ + 2 e− → Co −0.28
Ba2+ + 2 e− → Ba −2.91 Co3+ + e− → Co2+ +1.81
Be2+ + 2 e− → Be −1.85 Cr2+ + 2 e− → Cr −0.91
Bi3+ + 3 e− → Bi +0.20 Cr2O27− +14 H+ + 6 e− → 2 Cr 3+ + 7H 2O +1.33
Br2 + 2 e−→ 2Br− +1.09 Cr3+ + 3 e− → Cr −0.74
BrO− + H2O + 2 e− → Br− + 2 OH− +0.76 Cr3+ + e− → Cr2+ −0.41
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PART 4 Data 969

Cs+ + e− → Cs −2.92 MnO24− + 2 H2O + 2 e − → MnO2 + 4 OH − +0.60
Cu+ + e− → Cu +0.52 Na+ + e− → Na −2.71
Cu2+ + 2 e− → Cu +0.34 Ni2+ + 2 e− → Ni −0.23
Cu2+ + e− → Cu+ +0.16 NiOOH + H2O + e− → Ni(OH)2 + OH− +0.49
F2 + 2 e−→ 2F− +2.87 NO3− + 2 H + + e − → NO2 + H2O +0.80
Fe2+ + 2 e− → Fe −0.44 NO3− + 4 H + + 3 e− → NO + 2 H2 O +0.96
Fe3+ + 3 e− → Fe −0.04
NO3− + H2O + 2 e − → NO2− + 2 OH − +0.10
Fe3+ + e− → Fe2+ +0.77
O2 + 2 H2O + 4 e− → 4 OH− +0.40
[Fe(CN)6]3− + e− → [Fe(CN)6]4− +0.36
O2 + 4 H++ 4 e− → 2 H2O +1.23
2 H+ + 2 e− → H2 0, by definition
O2 + e − → O2− −0.56
2 H2O + 2 e−→ H2 + 2 OH− −0.83
O2 + H2O + 2 e − → HO2− + OH − −0.08
2 HBrO + 2 H+ + 2 e−→ Br2 + 2 H2O +1.60
O3 + 2 H++ 2 e− → O 2+ H2O +2.07
2 HClO + 2 H+ + 2 e−→ Cl2 + 2 H2O +1.63
O3 + H2O + 2 e− → O2 + 2 OH− +1.24
H2O2 + 2 H++ 2 e− → 2 H2O +1.78
Pb2+ + 2 e− → Pb −0.13
H4XeO6 + 2 H++ 2 e− → XeO3+ 3 H2O +3.0
Hg 22+ + 2 e − → 2 Hg +0.79 Pb4+ + 2 e− → Pb2+ +1.67
PbSO 4 + 2 e − → Pb + SO24− −0.36
Hg2Cl2 + 2 e−→ 2 Hg + 2 Cl− +0.27
Hg2+ + 2 e− → Hg +0.86 Pt2+ + 2 e− → Pt +1.20
2 Hg 2 + + 2 e − → Hg 22+ +0.92 Pu4+ + e− → Pu3+ +0.97
Hg 2SO4 + 2 e− → 2 Hg + SO24− +0.62 Ra2+ + 2 e− → Ra −2.92

Rb+ + e− → Rb −2.93
I2 + 2 e−→ 2 I− +0.54
I3− + 2 e − → 3 I− +0.53 S + 2 e− → S2− −0.48
S2O28− + 2e − → 2 SO24− +2.05
In+ + e− → In −0.14
In2+ + e− → In+ −0.40 Sc3+ + 3 e− → Sc −2.09
In3+ + 2 e− → In+ −0.44 Sn2+ + 2 e− → Sn −0.14
In3+ + 3 e− → In −0.34 Sn4+ + 2 e− → Sn2+ +0.15
In3+ + e− → In2+ −0.49 Sr2+ + 2 e− → Sr −2.89
K+ + e− → K −2.93 Ti2+ + 2 e− → Ti −1.63
La3+ + 3 e− → La −2.52 Ti3+ + e− → Ti2+ −0.37
Li+ + e− → Li −3.05 Ti4+ + e− → Ti3+ 0.00
Mg2+ + 2 e− → Mg −2.36 Tl+ + e− → Tl −0.34

Mn2+ + 2 e− → Mn −1.18 U3+ + 3 e− → U −1.79
Mn3+ + e− → Mn2+ +1.51 U4+ + e− → U3+ −0.61
MnO2 + 4 H++ 2 e− → Mn2+ + 2 H2O +1.23 V2+ + 2 e− → V −1.19
MnO24− + 8 H + + 5 e − → Mn2 + + 4H2O +1.51 V3+ + e− → V2+ −0.26
MnO−4 + e − → MnO24− +0.56 Zn2+ + 2 e− → Zn −0.76
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Table 78.1 Collision cross- Table 79.1 Transport properties of gases at 1 atm
sections, σ/nm2
κ/(mW K−1 m−1) η/μP
Ar 0.36 273 K 273 K 293 K
C2H4 0.64
Air 24.1 173 182
C6H6 0.88
Ar 16.3 210 223
CH4 0.46
C2H4 16.4 97 103
Cl2 0.93
CH4 30.2 103 110
CO2 0.52
Cl2 7.9 123 132
H2 0.27
CO2 14.5 136 147
He 0.21
H2 168.2 84 88
N2 0.43
He 144.2 187 196
Ne 0.24
Kr 8.7 234 250
O2 0.40
N2 24.0 166 176
SO2 0.58
Ne 46.5 298 313
Data: KL.
O2 24.5 195 204
Xe 5.2 212 228
Data: KL.
Table 80.1 Viscosities of liquids at 298 K, η/(10−3 kg m−1 s−1)

Benzene 0.601
Carbon tetrachloride 0.880
Ethanol 1.06
Mercury 1.55
Methanol 0.553
Pentane 0.224
Sulfuric acid 27
Water† 0.891
† The viscosity of water over its entire liquid range is represented with less than 1 per
cent error by the expression log(η20/η) = A/B,
A = 1.370 23(t − 20) + 8.36 × 10 −4(t − 20)2 B = 109 + t t = θ/°C
Convert kg m−1 s −1 to centipoise (cP) by multiplying by 103 (so η ≈ 1 cP for water).
Data: AIP, KL.
Table 80.2 Ionic mobilities in water at 298 K, u/(10−8 m2 s−1 V−1)
Cations Anions
Ag+ 6.24 Br− 8.09
Ca2+ 6.17 CH3CO2− 4.24
Cu2+ 5.56 Cl− 7.91
H+ 36.23 CO2−
3 7.46
K+ 7.62 F− 5.70
Li+ 4.01 [Fe(CN)6]3− 10.5
Na+ 5.19 [Fe(CN)6]4− 11.4
NH +4 7.63 I− 7.96
[N(CH3)4 ]+ 4.65 NO3− 7.40
Rb+ 7.92 OH− 20.64
Zn2+ 5.47 SO2−
4 8.29
Data: Principally Table 80.1 and u = λ/zF.
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PART 4 Data 971
Table 81.1 Diffusion coefficients at 298 K, D/(10−9 m2 s−1)
Molecules in liquids Ions in water

I2 in hexane 4.05 H2 in CCl4(l) 9.75 K+ 1.96 Br− 2.08
in benzene 2.13 N2 in CCl4(l) 3.42 H+ 9.31 Cl− 2.03
CCl4 in heptane 3.17 O2 in CCl4(l) 3.82 Li+ 1.03 F− 1.46
Glycine in water 1.055 Ar in CCl4(l) 3.63 Na+ 1.33 I− 2.05
Dextrose in water 0.673 CH4 in CCl4(l) 2.89 OH− 5.03
Sucrose in water 0.5216 H2O in water 2.26
CH3OH in water 1.58
C2H5OH in water 1.24
Data: AIP.
Table 83.1 Kinetic data for first-order reactions
Phase θ/°C κr/s−1 t1/2

2 N2O5→ 4 NO2 + O2 g 25 3.38 × 10−5 5.70 h
HNO3(l) 25 1.47 × 10−6 131 h
Br2(l) 25 4.27 × 10−5 4.51 h
C2H6 → 2 CH3 g 700 5.36 × 10−4 21.6 min
Cyclopropane → propene g 500 6.71 × 10−4 17.2 min
CH3N2CH3→ C2H6 + N2 g 327 3.4 × 10−4 34 min
Sucrose → glucose + fructose aq(H+) 25 6.0 × 10−5 3.2 h
g: High pressure gas-phase limit.
Data: Principally K.J. Laidler, Chemical kinetics. Harper & Row, New York (1987); M.J. Pilling and P.W. Seakins, Reaction kinetics. Oxford University Press, Oxford (1995);
J. Nicholas, Chemical kinetics. Harper & Row, New York (1976). See also JL.
Table 83.2 Kinetic data for second-order reactions
Phase θ/°C kr/(dm3 mol−1 s−1)

2 NOBr → 2 NO + Br2 g 10 0.80
2 NO2 → 2 NO + O2 g 300 0.54
H2 + I2 → 2 HI g 400 2.42 × 10−2
D2 + HCl → DH + DCl g 600 0.141
2 I → I2 g 23 7 × 109
hexane 50 1.8 × 1010
CH3Cl + CH3O− methanol 20 2.29 × 10−6
CH3Br + CH3 O− methanol 20 9.23 × 10−6
H+ + OH− → H2O water 25 1.35 × 1011
ice −10 8.6 × 1012
Data: Principally K.J. Laidler, Chemical kinetics. Harper & Row, New York (1987); M.J. Pilling and P.W. Seakins, Reaction kinetics. Oxford University Press, Oxford (1995);
J. Nicholas, Chemical kinetics. Harper & Row, New York (1976).
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Table 85.1 Arrhenius parameters
First-order reactions A/s−1 Ea/(kJ mol−1)

Cyclopropane → propene 1.58 × 1015 272
CH3NC → CH3CN 3.98 × 1013 160
cis-CHD = CHD → trans-CHD = CHD 3.16 × 1012 256
Cyclobutane → 2 C2H4 3.98 × 1013 261
C2H5I → C2H4 + HI 2.51 × 1017 209
C2H6 → 2 CH3 2.51 × 107 384
2 N2O5 → 4 NO2 + O2 4.94 × 1013 103.4
N2O → N2 + O 7.94 × 1011 250
C2H5 → C2H4 + H 1.0 × 1013 167
Second-order, gas-phase A/(dm3 mol−1 s−1) Ea/(kJ mol−1)

O + N2 → NO + N 1 × 1011 315
OH + H2 → H2O + H 8 × 1010 42
Cl + H2 → HCl + H 8 × 1010 23
2 CH3 → C2H6 2 × 1010 ca.0
NO + Cl2 → NOCl + Cl 4.0 × 109 85
SO + O2 → SO2 + O 3 × 108 27
CH3 + C2H6 → CH4 + C2H5 2 × 108 44
C6H5 + H2 → C6H6 + H 1 × 108 ca.25
Second-order, solution A/(dm3 mol−1 s−1) Ea/(kJ mol−1)

C2H5ONa + CH3I in ethanol 2.42 × 1011 81.6
C2H5Br + OH− in water 4.30 × 1011 89.5
C2H5I + C2H5O− in ethanol 1.49 × 1011 86.6
C2H5Br + OH− in ethanol 4.30 × 1011 89.5
CO2 + OH− in water 1.5 × 1010 38
CH3I + S2O23− in water 2.19 × 1012 78.7
Sucrose + H2O in acidic water 1.50 × 1015 107.9
(CH3)3CCl solvolysis
in water 7.1 × 1016 100
in methanol 2.3 × 1013 107
in ethanol 3.0 × 1013 112
in acetic acid 4.3 × 1013 111
in chloroform 1.4 × 104 45
C6H5NH2 + C6H5COCH2Br in benzene 91 34
Data: Principally J. Nicholas, Chemical kinetics. Harper & Row, New York (1976) and A.A. Frost and R.G. Pearson, Kinetics
and mechanism. Wiley, New York (1961).
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PART 4 Data 973
Table 87.1 Arrhenius parameters for gas-phase reactions
A/(dm3 mol−1 s−1)

Experiment Theory Ea/(kJ mol−1) P
2 NOCl → 2 NO + Cl2 9.4 × 109 5.9 × 1010 102.0 0.16
2 NO2 → 2 NO + O2 2.0 × 109 4.0 × 1010 111.0 5.0 × 10−2
2 ClO → Cl2 + O2 6.3 × 107 2.5 × 1010 0.0 2.5 × 10−3
H2 + C2H4 → C2H6 1.24 × 106 7.4 × 1011 180 1.7 × 10−6
K + Br2 → KBr + Br 1.0 × 1012 2.1 × 1011 0.0 4.8
Data: Principally M.J. Pilling and P.W. Seakins, Reaction kinetics. Oxford University Press, Oxford (1995).
Table 88.1 Arrhenius parameters for reactions in solution. See Table 85.1.
Table 95.1 Maximum observed standard enthalpies of physisorption,

ΔadH < /(kJ mol−1) at 298 K
C2H2 −38 H2 −84

C2H4 −34 H2O −59
CH4 −21 N2 −21
Cl2 −36 NH3 −38
CO −25 O2 −21
CO2 −25
Data: D.O. Haywood and B.M.W. Trapnell, Chemisorption. Butterworth (1964).
Table 95.2 Standard enthalpies of chemisorption, ΔadH < /(kJ mol−1) at 298 K
Adsorbate Adsorbent (substrate)

Ti Ta Nb W Cr Mo Mn Fe Co Ni Rh Pt
H2 −188 −188 −167 −71 −134 −117
N2 −586 −293
O2 −720 −494 −293
CO −640 −192 −176
CO2 −682 −703 −552 −456 −339 −372 −222 −225 −146 −184
NH3 −301 −188 −155
C2H4 −577 −427 −427 −285 −243 −209
Data: D.O. Haywood and B.M.W. Trapnell, Chemisorption. Butterworth (1964).
Atkins09819.indb 973 9/11/2013 8:56:11 AM

PART 5 Character tables
The groups C1, Cs, Ci
C1, 1 E h=1 C6v, 6mm E C2 2C3 2C6 3σd 3σv h = 12

A 1 A1 1 1 1 1 1 1 z, z2, x2 + y2
A2 1 1 1 1 −1 −1 Rz
Cs= Ch, m E σh h=2 B1 1 −1 1 −1 −1 1
A′ 1 1 x, y, Rz x2, y2, z2, xy B2 1 −1 1 −1 1 −1
A″ 1 −1 z, Rx, Ry yz, zx E1 2 −2 −1 1 0 0 (x, y), (yz, zx) (Rx, Ry)

E2 2 2 −1 −1 0 0 (xy, x2− y2)
Ci = S2, 1 E i h=2 C∞v E 2Cφ† ∞σv h=∞

Ag 1 1 Rx, Ry, Rz x2, y2, z2, xy, yz, zx, A1(Σ+) 1 1 1 z, z2, x2 + y2
Au 1 −1 x, y, z A2(Σ−) 1 1 −1 Rz
E1(Π) 2 2 cos φ 0 (x, y), (yz, zx) (Rx, Ry)
The groups Cnv E2(Δ) 2 2 cos 2φ 0 (xy, x2− y2)

⋮ ⋮ ⋮ ⋮
C2v, 2mm E C2 σv σ v′ h=4 † There is only one member of this class if φ = π.
A1 1 1 1 1 z, z2, x2, y2
A2 1 1 −1 −1 xy Rz
B1 1 −1 1 −1 x, zx Ry
The groups Dn
B2 1 −1 −1 1 y, yz Rx D2, 222 E C2z C2y C2x h=4
A1 1 1 1 1 x2, y2, z2
C3v, 3m E 2C3 3σv h=6 B1 1 1 −1 −1 z, xy Rz
A1 1 1 1 z, z2, x2 + y2 B2 1 −1 1 −1 y, zx Ry
A2 1 1 −1 Rz B3 1 −1 −1 1 x, yz Rx
E 2 −1 0 (x, y), (xy, x2 − y2) (yz, zx) (Rx, Ry)
C4v, 4mm E C2 2C4 2σv 2σd h=8 D3, 32 E 2C3 3C2′ h=6
A1 1 1 1 1 1 z, z2, x2 + y2 A1 1 1 1 z2, x2 + y2
A2 1 1 1 −1 −1 Rz A2 1 1 −1 z Rz
B1 1 1 −1 1 −1 x2 − y2 E 2 −1 0 (x, y), (yz, zx), (xy, x2 − y2) (Rx, Ry)
B2 1 1 −1 −1 1 xy
E 2 −2 0 0 0 (x, y), (yz, zx) (Rx, Ry)
D4, 422 E C2 2C4 2C2′ 2C2″ h=8

C5v E 2C5 2C52 5σv h = 10, α = 72° A1 1 1 1 1 1 z2, x2 + y2
A1 1 1 1 1 z, z2, x2 + y2 A2 1 1 1 −1 −1 z Rz
A2 1 1 1 −1 Rz B1 1 1 −1 1 −1 x2 − y2
E1 2 2 cos α 2 cos 2α 0 (x, y), (yz, zx) (Rx, Ry) B2 1 1 −1 −1 1 xy
E2 2 2 cos 2α 2 cos α 0 (xy, x2− y2) E 2 −2 0 0 0 (x, y), (yz, zx) (Rx, Ry)
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Atkins09819.indb 974 9/11/2013 8:56:18 AM

Part 5 Character tables 975
The groups Dnh

D3 h, 62m E σh 2C3 2S3 3C2′ 3σv h = 12 D4 h, E 2C4 C2 2C2′ 2C2′′ i 2S4 σh 2σv 2σd h = 16
4/mmm
A1′ 1 1 1 1 1 1 z2, x2 + y2 A1 g 1 1 1 1 1 1 1 1 1 1 x2+ y2, z2
A2′ 1 1 1 1 −1 −1 Rz A2 g 1 1 1 −1 −1 1 1 1 −1 −1 Rz
A1′′ 1 −1 1 −1 1 −1 B1 g 1 −1 1 1 −1 1 −1 1 1 −1 x2 − y2
A2′′ 1 −1 1 −1 −1 1 z B2 g 1 −1 1 −1 1 1 −1 1 −1 1 xy
Eg 2 0 −2 0 0 2 0 −2 0 0 (yz, zx) (Rx, Ry)
E′ 2 2 −1 −1 0 0 (x, y), (xy, x2 − y2)
A1u 1 1 1 1 1 −1 −1 −1 −1 −1
E″ 2 −2 −1 1 0 0 (yz, zx) (Rx, Ry)
A2u 1 1 1 −1 −1 −1 −1 −1 1 1 z
B1u 1 −1 1 1 −1 −1 1 −1 −1 1
B2u 1 −1 1 −1 1 −1 1 −1 1 −1
Eu 2 0 −2 0 0 −2 0 2 0 0 (x, y)
D5 h E 2C5 2C52 5C2 σh 2S5 2S53 5σv h = 20 α = 72°

A1′ 1 1 1 1 1 1 1 1 x2+ y2, z2
A2′ 1 1 1 −1 1 1 1 −1 Rz
E1′ 2 2 cos α 2 cos 2α 0 2 2 cos α 2 cos 2α 0 (x, y)
E2′ 2 2 cos 2α 2 cos α 0 2 2 cos 2α 2 cos α 0 (x2 − y2, xy)
A1′′ 1 1 1 1 −1 −1 −1 −1
A2′′ 1 1 1 −1 −1 −1 −1 1 z
E1′′ 2 2 cos α 2 cos 2α 0 −2 −2 cos α −2 cos 2α 0 (yz, zx) (Rx, Ry)
E2′′ 2 2 cos 2α 2 cos α 0 −2 −2 cos 2α −2 cos α 0
D∞h E 2Cφ … ∞σv i 2S∞ … ∞C2′ h=∞

A1 g (Σ g+ ) 1 1 … 1 1 1 … 1 z2, x2 + y2
A1u (Σ u+ ) 1 1 … 1 −1 −1 … −1 z
A2g (Σ g− ) 1 1 … −1 1 1 … −1 Rz
A2u (Σ u− ) 1 1 … −1 −1 −1 … 1
E1 g(Πg) 2 2 cos φ … 0 2 −2 cos φ … 0 (yz, zx) (Rx, Ry)
E1u(Πu) 2 2 cos φ … 0 −2 2 cos φ … 0 (x, y)
E2 g(Δg) 2 2 cos 2φ … 0 2 2 cos 2φ … 0 (xy, x2− y2)
E2u(Δu) 2 2 cos 2φ … 0 −2 −2 cos 2φ … 0
⋮ ⋮ ⋮ … ⋮ ⋮ ⋮ … ⋮
Atkins09819.indb 975 9/11/2013 8:56:31 AM

The cubic groups

Td, 43m E 8C3 3C2 6σd 6S4 h = 24
A1 1 1 1 1 1 x2+ y2 + z2
A2 1 1 1 −1 −1
E 2 −1 2 0 0 (3z2 − r2, x2− y2)
T1 3 0 −1 −1 1 (Rx, Ry, Rz)
T2 3 0 −1 1 −1 (x, y, z), (xy, yz, zx)
Oh, m3m E 8C3 6C2 6C4 3C2 (= C 42 ) i 6S4 8S6 3σh 6σd h = 48
A1 g 1 1 1 1 1 1 1 1 1 1 x2+ y2 + z2
A2 g 1 1 −1 −1 1 1 −1 1 1 −1
Eg 2 −1 0 0 2 2 0 −1 2 0 (2z2 − x2 − y2, x2− y2)
T1 g 3 0 −1 1 −1 3 1 0 −1 −1 (Rx, Ry, Rz)
T2 g 3 0 1 −1 −1 3 −1 0 −1 1 (xy, yz, zx)
A1u 1 1 1 1 1 −1 −1 −1 −1 −1
A2u 1 1 −1 −1 1 −1 1 −1 −1 1
Eu 2 −1 0 0 2 −2 0 1 −2 0
T1u 3 0 −1 1 −1 −3 −1 0 1 1 (x, y, z)
T2u 3 0 1 −1 −1 −3 1 0 1 −1
The icosahedral group
I E 12C5 12C52 20C3 15C2 h = 60
A 1 1 1 1 1 x2+ y2 + z2
T1 3 1 (1+ 5) 1 (1− 5) 0 −1 (x, y, z) (Rx, Ry, Rz)
2 2
T2 3 1 (1− 5) 1 (1+ 5) 0 −1
2 2
G 4 −1 −1 1 0
H 5 0 0 −1 1 (2z2 − x2 − y2, x2− y2, xy, yz, zx)
Further information: P.W. Atkins, M.S. Child, and C.S.G. Phillips, Tables for group theory. Oxford University Press, Oxford (1970). In this source, which is available on the web
(see p. x for more details), other character tables such as D2, D4, D2d, D3d, and D5d can be found.
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Atkins09819.indb 976 9/11/2013 8:56:35 AM

INDEX
A ampere, 14 azimuth, 107, 112 Born–Oppenheimer approximation,

ab initio method, 251 amplitude, 19 azulene, 263 201
absolute value, 43, 128 angular (bent) molecule, 4 boron trifluoride, 279
absorbance, 381 angular momentum, 10, 103, 109 Bose–Einstein statistics, 527
absorption, 892 commutator, 115 B boson, 171
absorption spectroscopy, 377 hydrogenic atom, 156 Balmer series, 181 bouncing ball, 596
abstraction, 890 operators, 115 band, 346 bound state, 154
acceleration, 10 quantization, 108 band gap, 347, 355 boundary conditions, 75
acceleration of free fall, 12 quantum number, 113 band head, 429 boundary surface, 162
acceptor band, 356 angular node, 114 band structure, 345 Boyle temperature, 323
accidental degeneracy, 90 angular velocity, 10 bar, 5 Boyle’s law, 7
accommodation, 913 anharmonic oscillator, 409 barometric formula, 531 Boys, S.F., 245
acenaphthalene, 263 anharmonicity constant, 409 basis set, 245 Brackett series, 181
achiral molecule, 281 anion, 3 beam splitter, 379 Bragg, W. and L., 335
actinide, see actinoid anion configuration, 178 Beer–Lambert law, 381 Bragg method, 335
actinoid, 3 anode, 734 bell curve, 538 Bragg’s law, 336
activated complex, 818, 849 anthracene, 263 bent molecule, 4 Bravais lattice, 332
observation, 852 antibonding orbital, 213 benzene Brillouin’s theorem, 254
activated-complex theory, 848 antiferromagnetic phase, 359 breathing mode, 417 Brunauer, S., 925
activation-controlled limit, 844 antifreeze, 688 Hückel description, 246 buckminsterfullerene, 281
activation energy, 100, 817, 838 anti-Stokes lines, 401 symmetry elements, 275 building-up principle
negative, 826 anti-Stokes radiation, 384 VB description, 205 atoms, 176
activation parameters, 853 antisymmetric stretch, 416 benzene radical ion, 462, 489 molecules, 216
activity, 694 aperiodic crystal, 331 Bernouilli trial, 535 bulk matter, 5
conventions, 696 area under curve, 29 Berthelot equation, 325 butadiene, MO description, 233
activity coefficient, 695 aromatic stability, 246 BET isotherm, 925
determination, 743 array detector, 378 beta spin, 170
addition reaction, Arrhenius equation, 816 bimolecular reaction, 821 C
adenosine triphosphate (ATP), 721 Arrhenius parameters, 840 binomial coefficient, 535 caesium chloride structure, 347
adiabat, 578 thermodynamic, 853 binomial expansion, 535 cage effect, 843
adiabatic bomb calorimeter, 560 associated Laguerre polynomial, 155 biological standard state, 720 calorie, 12
adiabatic change asymmetric rotor, 390 black-body radiation, 34 calorimeter, 560
molecular interpretation, 578 asymmetric top, 391 block (of periodic table), 3 calorimeter constant, 561
adiabatic container, 542 asymptotic solutions, 154 block-diagonal matrix, 286 calorimetry, 560
adiabatic process, 576 atom, 2 body-centred unit cell, 332 camphor, 363
adsorbate, 912 atomic force microscopy (AFM), Bohr frequency condition, 36, canonical ensemble, 524
adsorbent, 912 318, 915 181, 377 canonical partition function, 525
adsorption, 912 atomic number, 2 Bohr radius, 155 capillary technique, 786
adsorption isotherm, 922 atomic orbital, 2, 155, 160 boiling, 660 carbon, special role, 180
adsorption rate, 919 atomic radius, 178 boiling point elevation, 688 carbon dioxide
AES (Auger electron spectroscopy), atomic weight, 5 boiling temperature, 660 isotherms, 322
916 ATP (adenosine triphosphate), 721 Boltzmann, L., 599 normal modes, 416
AFM (atomic force microscopy), attractions, 321 Boltzmann constant, 16 phase diagram, 661, 675
318, 915 attractive surface, 864 Boltzmann distribution, 16, 501 carbonyl group chromophore, 431
alanine, 282 Aufbau principle, 176 Boltzmann formula, 600 Carnot cycle, 609
alkali metal, 3 Auger effect, 916 bond, 3 carotene, 78, 384
alkaline earth metal, 3 Auger electron spectroscopy (AES), bond dissociation energy, 221 catalyst, 819, 881, 931
allene, 279 916 bond length, 201, 221 catalytic activity, 933
allowed transition, 142 Austin model 1 (AM1), 249 bond order, 220 catalytic constant, 884
alpha spin, 170 average speed, 17 bond stretching, work of, 11 catalytic efficiency, 884
AM1 (Austin model 1), 249 Avogadro’s constant, 5 bond torsion, 100 cathode, 734
amide group, 305 Avogadro’s principle, 7 bonding orbital, 211 cation, 3
ammonia AX system, 470 Born, M., 43 cation configuration, 178
inversion, 85 AX2 and AX3 spectra, 471 Born equation, 636 cavity characteristics, 438
VB description, 204 Axilrod–Teller formula, 317 Born–Haber cycle, 350 CCD (charge-coupled device), 380
amount, 5 axis of symmetry, 275, 331 Born interpretation, 43 ccp (cubic close-packed), 344
amount of substance, 5 azeotrope, 666 Born–Mayer equation, 349 cell convention, 735, 740
Atkins09819.indb 977 9/11/2013 8:56:36 AM

978 INDEX
cell potential, 736 collisional deactivation, 386, 890, 894 core hamiltonian, 240 delta scale, 465
temperature dependence, 744 collisional lifetime, 386 coronene, 108, 299 density functional theory (DFT), 256
cell reaction, 736 colour, 423 correlation analysis, 854 density of states, 34, 354, 526
Celsius scale, 6 combination band, 418 correlation energy, 253 depolarization ratio, 419
centre of inversion, 276 combination difference, 411 correlation spectroscopy (COSY), 483 depolarized line, 419
centrifugal distortion, 394 commutator, 61 correspondence principle, 77 derivative, 27
centrifugal distortion constant, 394 angular momentum, 115 cosine law, 196 derived unit, 6
centrifugal effect, hydrogenic atom, competitive inhibition, 885 cosmic ray, 21 deshielded nucleus, 465
154 complementarity, 59 COSY (correlation spectroscopy), 483 desorption rate, 919, 929
ceramic, 360 complementary observables, 61, 109 Coulomb integral, 227 destructive interference, 20
cesium, see caesium complete neglect of differential overlap Coulomb operator, 240 detector, 380
character, 286 (CNDO), 249 Coulomb potential, 13 determinant, 270
character and degeneracy, 288 complete shell, 172 Coulomb potential energy, 12 deuteration, 100
character table, 287 complex conjugate, 43, 128 Coulomb’s law, 309 deuterium lamp, 378
charge-coupled device (CCD), 380 complex number, 43, 128 covalent compound, 3 DFT (density functional theory), 256
charge–dipole interaction, 310 complex plane, 128 covalent solid, 343 diagonal matrix, 270
charge number, 13 components of vector, 195 critical constants, 326 diagonal peaks, 483
Charles’s law, 7 compressibility, 572 critical field, 360 diamagnetic, 357
chemical amount, 5 compression factor, 321 critical point, 326 diamagnetic contribution, 466
chemical bond, 3 concentration cell, 734 critical pressure, 326 diamond, 351
chemical exchange, 474 conductance, 775, 776 critical solution temperature, 667 diaphragm technique, 786
chemical kinetics, 799 conduction (electrical), 354 critical temperature, 326 diathermic container, 542
chemical potential, 658, 672, 673 conduction band, 355 critical volume, 326 dichlorobenzene, 305
chemical equilibrium, 716 conductivity, 776 cross peaks, 483 dielectric constant, 13, 310
equilibrium criterion, 673 configuration, 2 cross-relation, 908 Dieterici equation, 325
mean ionic, 700 configuration (system), 499 cross-section, 763 differential, 589
pressure dependence, 675 configuration integral, 328, 528 differential scattering, 858 differential equation, 69
solute, 695 configuration interaction (CI), 251, 252 crossed molecular beams, 860 differential overlap, 249
solvent, 683, 694 configuration state function (CSF), 252 crystal diode, 380 differential scanning calorimetry
temperature dependence, 674 conjugated polyene, 232, 264 crystal structure, 330 (DSC), 562
thermodynamic force, 782 consecutive reactions, 822 crystal structure of elements, 344 differential scattering cross-section,
chemical potential (metal), 354 consolute temperature, 667 crystal system, 331 858
chemical quench flow method, 801 constant crystallographic point group, 277 differentiation, 27
chemical shift, 465 anharmonicity, 409 CSF (configuration state function), 252 diffraction, 335
chemisorption, 914 Avogadro’s, 5 cubic close-packed (ccp), 344 diffraction (of particles), 39
chemisorption ability, 934 Boltzmann’s, 16 cubic groups, 280 diffraction grating, 378
chemistry, 1 calorimeter, 561 cubic unit cell, 331 diffusion
chiral molecule, 281 catalytic, 884 cumulative reaction probability, 866 Fick’s first law, 767
chirality, 281 centrifugal distortion, 394 current, 14, 561 reaction, 844
chlorophyll spectrum, 423 critical, 326 curvature, 27, 49 statistical view, 787
chromophore, 429 dielectric, 13, 310 CW-EPR (continuous-wave EPR), 462 surface, 917
CI (configuration interaction), 252 force, 92, 406 cyclic boundary condition, 107, 111 thermodynamic view, 782
circularly polarized wave, 21 Henry’s law, 684 cyclobutadiene, 246 diffusion coefficient, 768, 917
Clapeyron equation, 676 Madelung, 349 cyclooctatetraene, 264 KMT, 769
class, 284 Michaelis, 882 cylindrical coordinates, 106, 107 viscosity dependence, 780
classical mechanics, 9, 33 Planck’s, 35 diffusion-controlled limit, 844
Clausius–Clapeyron equation, 677 rotational, 391 diffusion equation, 784, 846
Clausius inequality, 612 Rydberg, 157, 181 D dihedral mirror plane, 275
Clebsch–Gordan series, 183 scalar coupling, 469 d orbital, 165 dihelium, 217
close-packed, 343 shielding, 173 Dalton’s law, 7 dimension of group, 285
closed shell, 172 shielding (NMR), 464, 466 Daniell cell, 735 dioxygen, 423
closed system, 541 spin–orbit coupling, 186 Davies equation, 701 dipolar field, 468
CNDO (complete neglect of constituent, 658 Davisson, C., 39 dipole, 305
differential overlap), 249 constraints, 502 Davisson–Germer experiment, 39 dipole–dipole interaction, 311, 490
co-adsorption, 931 constraints on the wavefunction, 45 de Broglie, L., 39 dipole–induced dipole interaction,
coefficient of thermal conductivity, 768 constructive interference (bonding), de Broglie relation, 39, 75, 105 314
coefficient of viscosity, 769 211 debye, 303 dipole moment, 303
coherence, 439 contact interaction, 473, 490 Debye, P., 303 addition, 304
cohesive energy density, 364 continuous distribution, 537 Debye equation, 362 direct method, 340
colatitude, 112 continuous-wave EPR (CW-EPR), 462 Debye formula, 586, 651 direct product, 293
colligative property, 687 contour diagram, 862 Debye–Hückel limiting law, 700, 854 direct product decomposition, 293
collision cross-section, 763, 837 convection, 785 Debye–Hückel theory, 700 direct sum, 286, 293
collision density, 837 convergence, 28 Debye T3 law, 586, 621 dispersion interaction, 315
collision diameter, 763 convolution theorem, 373 definite integral, 29 dissociation, 890
collision flux, 764, 913 Cooper pair, 360 degeneracy, 89, 288 dissociation and adsorption, 923
collision frequency, 763 coordination number, 344 degree of dissociation, 729 dissociation energy, 201, 221
collision-induced emission, 890 coordination number (ions), 347 degree of freedom, 658 dissociation equilibrium, 729
collision theory, 836 core, 174 delocalization energy, 246 dissociation limit, 436
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Atkins09819.indb 978 9/11/2013 8:56:36 AM

INDEX 979
distillation, 666 electrode concentration cell, 734 partition function, 601 equation of state, 320, 325
distinguishable molecules, 527 electrolyte, 734 phase transition, 616 statistical basis, 328
divergence, 28 electrolyte concentration cell, 734 reaction, 624 thermodynamic, 640
D lines, 187 electrolyte solution, 775 residual, 622 equilibrium, 15
d-metal complex, 429 electrolytic cell, 734 rotational contribution, 603 approach to, 812
d-orbital occupation, 177 electromagnetic field, 20 spin contribution, 606 chemical, 716
Dogonadze, R.R., 899 electromagnetic spectrum, 21 state function, 608 mechanical, 546
donor band, 356 electromotive force (emf), 736 statistical definition, 600 thermal, 546
dopant, 355 electron affinity, 180 surroundings, 613 thermodynamic criterion, 673
Doppler broadening, 385 electron correlation, 241, 251 thermodynamic definition, 608 equilibrium bond length, 201
Doppler effect, 385 electron density, 256 translational contribution, 602 equilibrium constant, 719
double bond, 3 electron density (X-ray), 337 vibrational contribution, 604 cell potential, 738
double bond chromophore, 431 electron diffraction, 39, 341 entropy of activation, 853 pressure dependence, 728
double integral, 30 electron microscopy, 915 enzyme, 881 rate contants, 812
double-well potential, 85 electron pairing, 203 enzyme inhibition, 885 standard potentials, 744
drift speed, 777 electron paramagnetic resonance EPR (electron paramagnetic statistical interpretation, 723
dry ice, 662 (EPR), 461, 487 resonance), 461, 487 temperature dependence, 730
DSC (differential scanning electron scattering factor, 341 EPR spectrometer, 462 equipartition theorem, 17, 518
calorimetry), 562 electron spin energy, 522 equal a priori probabilities, 498 ER (Eley–Rideal) mechanism, 933
duality, 39 electron spin resonance (ESR), 461, 487 equation error function, 98
Dubosq colorimeter, 444 electron transfer, 890, 894, 898 Arrhenius, 816 ESR (electron spin resonance),
duplet, 3 electronegativity, 225 Berthelot, 325 461, 487
dynamic equilibrium, 15 electronic configuration, 2 Born, 636 essential symmetries, 331
electronic mean energy, 521 Born–Mayer, 349 ethane
electronic partition function, 515 Clapeyron, 676 symmetry elements, 279
E electronic transitions, 422 Clausuis–Clapeyron, 677 vibrations, 417
Eadie–Hofstee plot, 906 electronvolt, 13 Davies, 701 ethanol, FID, 479
Eckart potential barrier, 83 elementary reaction, 821 Debye, 362 ethene
effect Eley–Rideal (ER) mechanism, 933 Dieterici, 325 VB description, 206
Doppler, 385 emf (electromotive force), 736 differential, 69 ethyne
Joule–Thomson, 555 emission spectroscopy, 377, 383 diffusion, 784, 846 VB description, 207
Kerr, 441 Emmett, P., 925 eigenvalue, 50, 271 Euler chain relation, 589
kinetic salt, 855 encounter pair, 843 Einstein–Smoluchowski, 788 Euler’s formula, 43, 128
Meissner, 360 endergonic reaction, 720 Eyring, 851 eutectic, 668
nuclear Overhauser, 481 endothermic process, 542 fundamental, 639 evanescent wave, 919
optical Kerr, 441 energy, 12, 542 generalized diffusion, 785 exact differential, 590
photoelectric, 37 harmonic oscillator, 93 Gibbs–Duhem, 673 excess enthalpy, 697
salting-in, 710 hydrogenic atom, 156 Gibbs–Helmholtz, 642 excess entropy, 696
Zeeman, 193 molecular vibration, 406 Hartree–Fock, 240 excess function, 696
effective mass, 93, 406 particle in a box, 76 Karplus, 472, 493 exchange–correlation energy, 257
effective nuclear charge, 173 particle on a ring, 106 Kohn–Sham, 257 exchange–correlation potential, 257
effective potential energy, 153 particle on a sphere, 115 linear differential, 69 exchange operator, 241
effective transverse relaxation time, rotational, 391 Margules, 698 excluded volume, 324
481 spherical well, 533 material balance, 846 exclusion rule, 419
efficiency three-dimensional square well, 90 McConnell, 490 exergonic reaction, 720
Carnot, 610 two-dimensional square well, 88 Michaelis–Menten, 882 exothermic process, 542
catalytic, 884 zero-point, 78 Nernst, 738 exp-6 potential energy, 318
energy transfer, 895 energy density of radiation, 143 Nernst–Einstein, 779 expansion coefficient, 571
effusion, 765 energy level, 15 osmotic virial, 690 expansion work, 544
Ehrenfest classification, 659 energy pooling, 890 partial differential, 69 expectation value, 54
eigenfunction, 50 energy quantization, 35 perfect gas, 7 extended Debye–Hückel law, 702
eigenvalue, 50, 271 energy requirement, 838 phenomenological, 767 extensive property, 5
eigenvalue equation, 50, 271 energy–time uncertainty, 143 radial wave, 152 extent of reaction, 716
eigenvector, 271 energy transfer, 890, 894 Roothaan, 242 extinction coefficient, 381
Einstein, A., 37 enhancement factor, 482 Sackur–Tetrode, 602 extrinsic semiconductor, 355
Einstein coefficients, 143 ensemble, 524 Schrödinger, 47, 92, 106, 112, Eyring equation, 851
Einstein formula, 651 enthalpy, 14, 552 140, 406
Einstein relation, 779 dependence on temperature, 553 secular, 227, 243
Einstein–Smoluchowski equation, 788 heat transaction, 553 simultaneous, 271 F
elastic collision, 757 mixing, 681, 684 of state, 320 face-centred cubic (fcc), 344
electric current, 14, 561 enthalpy of activation, 853 Stern–Volmer, 893 face-centred unit cell, 332
electric dipole, 4, 303 enthalpy of adsorption, 924 Stokes–Einstein, 779 far infrared, 21
electric dipole moment, 5, 303 enthalpy of chemisorption, 914 thermodynamic, 640 fcc (face-centred cubic), 344
electric field, 13 entropy, 14, 597 van der Waals, 323, 328, 528 femtosecond chemistry, 852
electrical heating, 561 electronic contribution, 605 van ’t Hoff (isochore), 730 Fermi contact interaction, 473, 490
electrochemical cell, 733 heating, 617 van ’t Hoff (osmotic), 689 Fermi–Dirac distribution, 354
electrochemical series, 743 measurement, 620 virial, 322 Fermi–Dirac statistics, 527
electrode, 733 mixing, 681, 684 Wierl, 341 Fermi energy, 354
Atkins09819.indb 979 9/11/2013 8:56:36 AM

980 INDEX
Fermi level, 347 frictional retarding force, 777 group defined, 283 heme, see haem
fermion, 171 frontier orbitals, 232 group theory, 283 Henry’s law, 684, 695
ferrocene, 278 FT-EPR (Fourier-transform EPR), 462 GTO (Gaussian-type orbital), 245 Henry’s law constant, 684
ferromagnetism, 359 FT-NMR (Fourier-transform NMR), Gunn diode, 378 Hermann–Mauguin system, 277
Fick’s first law, 767, 783 476 Gunn oscillator, 462 Hermite polynomial, 94
Fick’s second law, 784 full CI, 252 Hermitian operator, 51
FID (free-induction decay), 478 full rotation group, 281 orthogonal eigenfunctions, 55
field-ionization microscopy functional, 256 H hermiticity, 51
(FIM), 917 functional derivative, 257 haem, 124, 125, 300, 895 Hess’s law, 565
FIM (field-ionization microscopy), 917 fundamental charge, 2 haemerythrin, 453 heterogeneity index, 692
fine structure fundamental equation of half-life, 807, 808 heterogeneous catalyst, 881, 931
atomic spectra, 187 thermodynamics, 639 desorption, 929 heteronuclear diatomic molecule, 224
fine structure (NMR), 469 fundamental transition, 408 half-reaction, 734 hexagonally close packed (hcp), 344
first derivative, 27 furan, 297 Hall, G.G., 242 HF-SCF (Hartree–Fock self-consistent
first ionization energy, 179 halogen, 3 field), 174, 241
First Law of thermodynamics, 14, 544 hamiltonian highest occupied molecular orbital
first-order correction to energy, 133 G hydrogen molecule-ion, 209 (HOMO), 232
first-order correction to the g,u symmetry, 214 hydrogenic atom, 151 high-temperature superconductor
wavefunction, 133 g-value, 461, 488 polyatomic molecule, 238 (HTSC), 360
first-order phase transition, 659 galvanic cell, 734 spin, 458, 496 Hinshelwood, C., 876
flame calorimeter, 561 gamma-ray, 21 hamiltonian operator, 48 HMO (Hückel molecular orbital)
flash desorption, 919, 929 gas, 5 Hanes plot, 906 theory, 248
flash photolysis, 801 gas constant, 6, 320 hard-sphere potential energy, 317, 528 Hohenberg, P., 256
flow method, 800 gas discharge lamp, 378 harmonic motion, 11, 92 Hohenberg–Kohn theorem, 257
fluctuations, 526, 574 Gaussian distribution, 537 harmonic oscillator hole conduction, 355
fluorescence, 433, 890, 892 Gaussian distribution function, 538 classical, 11 HOMO (highest occupied molecular
quantum yield, 892 Gaussian function, 94 energy levels, 93 orbital), 232
quenching, 893 Gaussian-type orbital (GTO), 245 heat capacity, 574 homogeneous catalyst, 881
fluorescence resonance energy transfer general solution, 69 properties, 97 homonuclear diatomic molecule, 216
(FRET), 896 generalized diffusion equation, 785 transition rate, 142 horizontal mirror plane, 275
fluorescence spectroscopy, 383 gerade, 424 wavefunctions, 94 HTSC (high-temperature
fluorine, MO description, 220 gerade symmetry, 214 harmonic wave, 19 superconductor), 360
flux, 767 Gerlach, W., 117, 170 Harned cell, 741 Hückel approximation, 232
Fock, V., 174, 240 Germer, L., 39 harpoon mechanism, 840 Hückel method, metals, 345
Fock matrix, 248 Gibbs–Duhem equation, 673 Hartree, D.R., 174, 240 Hückel molecular orbital (HMO)
Fock operator, 240 Gibbs energy, 15, 626 Hartree–Fock equations, 240 theory, 248
forbidden transition, 142 electron transfer, 901 Hartree–Fock procedure, 174 Humphreys series, 190
force, 9 ionic solution, 699 Hartree–Fock self-consistent field Hund, F., 185
force between molecules, 318 maximum non-expansion (HF-SCF), 174, 241 Hund’s maximum multiplicity rule,
force constant, 11, 92, 406 work, 628 hcp (hexagonally close-packed), 344 177
force field, 418 mixing, 684, 697 heat, 543 Hund’s rules, 185
formula unit, 3 partial molar, 672 molecular interpretation, 550 Hush, N.S., 899
Förster theory, 895 properties, 640 heat capacity, 14 hybrid orbital, 205
forward bias, 356 variation with pressure, 641, 643 constant pressure, 553 hybridization, 205
four-circle diffractometer, 335 variation with temperature, 641 constant volume, 549, 571 hybridization and coupling constant, 472
four-level laser, 437 Gibbs energy of activation, 853 Debye formula, 651 hybridization schemes, 207
Fourier series, 371 Gibbs energy of mixing, 679 dissociation, 576 hydration half-life, 778
Fourier synthesis, 339 Gibbs energy of reaction, 716 Einstein formula, 651 hydrodynamic flow, 857
Fourier transform, 372 Gibbs–Helmholtz equation, 642 harmonic oscillator, 574 hydrodynamic radius, 778
Fourier-transform EPR (FT-EPR), 462 Gibbs phase rule, 658 low temperature, 621 hydrogen
Fourier-transform NMR (FT-NMR), glacier advance, 662 molecular basis, 572 DFT description, 258
476 glancing angle, 336 perfect gas relation, 554 ortho- and para-, 403
Fourier transform techniques, 378 globar, 378 relation between, 587 hydrogen bond, 315
fractional coverage, 914 globular protein, 703 rotational contribution, 575 hydrogen bromide PES, 222
fractional distillation, 666 glycine, 282 T 3 law, 621 hydrogen fluoride
Franck–Condon factor, 427 Gouy balance, 358 two-level system, 574 electron density, 224
Franck–Condon principle, 426, 899 gradient, 197 vibrational contribution, 575 MO description, 228, 229
free energy, 15 Graham’s law, 765 heat transaction, 548 hydrogen ion
free expansion, 546 grand canonical ensemble, 524 Heisenberg, W., 60 entropy, 623
free-induction decay (FID), 478 graphene, 351 Heisenberg uncertainty principle, 60 Gibbs energy, 635
free motion, 73 graphite, 351 helium-3, 663 hydrogen molecule
freeze–quench method, 801 gravimetry, 919 helium-4, 662 MO description, 216
freezing point depression, 688 gross selection rule, 142 helium, phase diagram, 662 VB description, 202
freezing temperature, 661 Grotrian diagram, 183 Helmholtz energy, 625 hydrogen molecule-ion, 210
frequency, 19 Grotthuss mechanism, 778 maximum work, 627 hydrogen peroxide, 278
FRET (fluorescence resonance energy ground state, hydrogenic atom, 161 properties, 644 hydrogen spectrum, 181
transfer), 896 group, 3 statistical basis, 626 hydrogenic atom, 150
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Atkins09819.indb 980 9/11/2013 8:56:36 AM

INDEX 981
hydrogenic atomic orbital, 160 inversion, 276 kinetic energy operator, 49 Wien’s, 34
hyperbolic function, 84 inversion doubling, 85, 98 kinetic isotope effect, 100 law of cosines, 196
hyperfine coupling constant, 488 inversion symmetry, 214, 424 kinetic-molecular theory (KMT), LCAO (linear combination of atomic
hyperfine structure (EPR), 488 inversion temperature, 557 16, 757 orbitals), 210
hyperpolarizability, 306 inverted region, 902 kinetic salt effect, 855 Le Chatelier’s principle, 729
ion configuration, 178 kinetic theory of gases, 757 LEED (low-energy electron
ion reactions, 854 kink, 913 diffraction), 917
I ionic atmosphere, 700 Kirchhoff ’s law, 568 Lennard-Jones potential energy, 318
IC (internal conversion), 435, 890, 892 ionic compound, 3 klystron, 462 level (of term), 186
ice, 662 ionic conductance, 776 KMT (kinetic-molecular theory), 757 lever rule, 665
ice structure, 351 ionic–covalent resonance, 204 Knudsen method, 765 Levich, V.G., 899
icosahedral group, 280 ionic mobility, 777, 778 Kohlrausch’s law, 776 Lewis structure, 3
ideal–dilute solution, 684 ionic radius, 348 Kohn, W., 238, 256, 257 LFER (linear free energy relation), 854
ideal gas, see perfect gas ionic solid, 343, 347 Kohn–Sham equation, 257 LH (Langmuir–Hinshelwood)
ideal solution, 683 ionic solution, Gibbs energy, 699 Kohn–Sham orbital, 257 mechanism, 932
ideal versus perfect, 686 ionic strength, 700 Koopmans’ theorem, 221 lifetime, 143
identity operation, 276 ionization, 890 Kronecker delta, 55, 270 lifetime broadening, 143, 386
impact parameter, 859 ionization energy, 179 ligand-field splitting parameter, 430
improper rotation, 276 hydrogenic atom, 158 ligand-to-metal charge transfer
improper rotation axis, 276 irreducible representation L (LMCT), 431
indefinite integral, 29 (irrep), 286 Lagrange method, 502 limiting law, 7, 320, 700
independent migration of ions law, 776 irrep (irreducible representation), 286 Laguerre polynomial, 155 limiting molar conductivity, 776
indistinguishable molecules, 527 irreversible change, 546 Lamb formula, 466 Linde refrigerator, 558
INDO (intermediate neglect of ISC (intersystem crossing), 435, lambda line, 662 Lindemann, F., 876
differential overlap), 249 890, 892 Langmuir–Hinshelwood (LH) Lindemann–Hinshelwood
induced dipole–induced dipole isenthalpic process, 556 mechanism, 932 mechanism, 876 , 932
interaction, 315 isobaric calorimeter, 561 Langmuir isotherm, 923, 932 line coalescence, 474
induced fit model, 882 isobaric heat capacity, 553 lanthanide, see lanthanoid linear combination, 53
induction period, 823 isochoric heat capacity, 549 lanthanide contraction, 179 linear combination of atomic orbitals
infrared active, 407 isolated system, 542 lanthanoid, 3 (LCAO), 210
symmetry analysis, 420 isomerization, 890 Laplace operator, 48 linear combination of degenerate
infrared chemiluminescence, 860 isopleth, 664 Laplacian, 112, 197 wavefunctions, 164
infrared inactive, 407 isosteric enthalpy of adsorption, 924 Laporte selection rule, 425 linear differential equation, 69
infrared spectroscopy, 407 isotherm, 322, 922 Larmor precession frequency, 459 linear free energy relation
inhibition, 885 isothermal compressibility, 572 laser action, 436 (LFER), 854
inhomogeneous broadening, 481 isothermal expansion, 547 laser characteristics, 437 linear molecule, 4
initial rates, method of, 804 entropy, 615 laser-induced fluorescence, 860 linear momentum, 9
inner transition metal, 3 isothermal Joule–Thomson coefficient, laser light scattering, 445 operator, 49
instantaneous configuration, 499 556 lattice energy, 348 linear rotor, 390, 393
insulator, 353 isotopic substitution, 399 lattice enthalpy, 350 partition function, 511
integral notation (AB|CD), 244 iteration procedure, 244, 258 lattice plane, 333 lines of force, 357
integrated absorption coefficient, 382 lattice plane separation, 334 Lineweaver–Burk plot, 883
integrated rate law, 806 lattice point, 330 linewidth, 385
integrating factor, 591 J law liquid, 5
integration, 28 Jablonski diagram, 435 Beer–Lambert, 381 mixing, 682
integration by parts, 29 jj-coupling, 185 Boyle’s, 7 liquid junction potential, 735
intensive property, 5 Joule, J., 555 Charles’s, 7 liquid–liquid system, 667
interference, 20 Joule–Thomson coefficient, 555 Coulomb’s, 309 liquid–solid system, 668
interferogram, 379 Joule–Thomson effect, 555 Dalton’s, 7 liquid–vapour system, 664
intermediate neglect of differential Debye T 3, 621 lithium configuration, 172
overlap (INDO), 249 Debye–Hückel limiting, 700, 854 LMCT (ligand-to-metal charge
internal conversion (IC), 435, 890, 892 K Fick’s first, 767, 783 transfer), 431
internal energy, 14, 543 K quantum number, 392 Fick’s second, 784 local contribution, 466
general changes, 570 Karplus equation, 472, 493 First, 14, 544 lock-and-key model, 882
heat transaction, 548 Kassel, L.S., 878 Henry’s, 684, 695 London, F., 315
properties, 639 Keesom interaction, 313 Hess’s, 565 London formula, 315
temperature dependence, 549 Kekulé structure, 205 independent migration of ions, 776 London interaction, 315
internal pressure, 327, 528, 571 Kelvin, Lord, 555 Kirchhoff ’s, 568 lone pair, 4
International system (point group), Kelvin scale, 6 Kohlrausch’s, 776 longitudinal relaxation time, 479
277 Kelvin statement, 596 limiting, 7, 320, 700 Lorentzian function, 494
intersystem crossing (ISC), 435, Kerr effect, 441 Newton’s, 10 low-energy electron diffraction
890, 892 Kerr lens, 441 Ohm’s, 561 (LEED), 917
intrinsic semiconductor, 355 Kevlar, 363 Raoult’s, 683, 695 lowest unoccupied molecular orbital
invariant integral, 291 kilogram, 5 Rayleigh–Jeans, 34 (LUMO), 232
inverse (complex number), 128 kinetic control, 827 Second, 15, 596 lumiflavin, 100
inverse Fourier transform, 372 kinetic energy, 12 Stokes’s, 777 LUMO (lowest unoccupied molecular
inverse matrix, 271 kinetic energy density, 791 Third, 622 orbital), 232
Atkins09819.indb 981 9/11/2013 8:56:37 AM

982 INDEX
lustre, 356 metal-to-ligand charge transfer molecular shape, 4 VB description, 203

Lyman series, 181 (MLCT), 431 molecular solid, 343 NMR (nuclear magnetic resonance),
metallic conductor, 353 molecular speed, 759 457
metallic solid, 343 molecularity, 821 NMR intensity, 459
M metalloid, 3 Møller, C., 253 NMR spectrometer, 459
Maclaurin series, 28 metastable excited state, 437 Møller–Plesset perturbation theory noble gas, 3
Madelung constant, 349 methane (MPPT), 253 node, 76
magic-angle spinning, 485 normal modes, 420 molten globular protein, 703 NOE (nuclear Overhauser
magnetic field strength, 357 partial charges, 306 moment of inertia, 10, 104, 388 effect), 481
magnetic quantum number, 113 symmetry elements, 276 momentum operator, 49 NOE enhancement factor, 482
magnetic resonance, 457 metre, 5 monochromatic radiation, 378 NOESY (nuclear Overhauser effect
magnetic resonance imaging (MRI), Michaelis constant, 882 monochromator, 378 spectroscopy), 483
492 Michaelis–Menten equation, 882 monoclinic unit cell, 331 non-competitive inhibition, 886
magnetic susceptibility, 357, 467 Michaelis–Menten mechanism, 882 monodisperse, 691 non-expansion work, 545
magnetically ordered lattice, 341 Michelson interferometer, 378 monopole, 305 nonlinear rotor, partition
magnetizability, 370 microcanonical ensemble, 524 Morse potential energy, 409 function, 511
magnetization, 357 microscopy, 915 most probable radius, 167 non-metal, 3
magnetization vector, 477 microwave spectroscopy, 396 most probable speed, 762 non-radiative decay, 433
magnetogyric ratio, 461 microwaves, 21 motion in three dimensions, 90 normal boiling point, 660
magnitude of vector, 195 Mie potential energy, 317 motion in two dimensions, 87 normal distribution function, 538
MALDI (matrix-assisted laser Miller indices, 333 MP2, MP3, MP4, 254 normal freezing point, 661
desorption/ionization), 452 MINDO (modified intermediate MPI (multiphoton ionization), 860 normal mode, 416
MALDI-TOF, 452 neglect of differential overlap), MPPT (Møller–Plesset perturbation symmetry analysis, 419
many-body perturbation theory, 253 249 theory), 253 normal transition temperature, 616
many-electron atom, 150, 169 minimal basis set, 245 MRI (magnetic resonance imaging), normal Zeeman effect, 194
Marcus, R.A., 878, 894, 899 mirror plane, 275 492 normalization, 44
Marcus cross-relation, 908 mixed inhibition, 886 Mulliken, R., 226 normalization constant, 44
Marcus theory, 894, 899 mixing Mulliken electronegativity, 226 nuclear g-factor, 458
Margules equations, 698 enthalpy, 681 multiphoton ionization (MPI), 860 nuclear magnetic resonance (NMR),
maser, 86 role in equilibrium, 717 multiphoton process, 426 457
mass, 5 statistical thermodynamics, 682 multiple integral, 30 nuclear magnetogyric ratio, 458
mass density, 5 mixing entropy, 681 multiplicity, 184 nuclear magneton, 458
mass number, 2 MLCT (metal-to-ligand charge multivariate calculus, 589 nuclear model, 2
material-balance equation, 846 transfer), 431 nuclear Overhauser effect (NOE), 481
matrix, 270 MNDO (modified neglect of nuclear Overhauser effect
matrix addition, 270 differential overlap), 249 N spectroscopy (NOESY), 483
matrix-assisted laser desorption/ mobility, 777 n-fold rotation, 275 nuclear spin, 457
ionization (MALDI), 452 mode locking, 440 n-to-pi* transition, 431 nuclear spin quantum number, 457
matrix diagonalization, Hückel modified intermediate neglect of n-type semiconductivity, 355 nuclear statistics, 402
method, 233 differential overlap (MINDO), naphthalene, symmetry elements, 276 nucleon, 2
matrix representation, 285 249 natural linewidth, 386 nucleon number, 2
matrix subtraction, 270 modified neglect of differential overlap NDDO (neglect of diatomic number-average molar mass, 691
maximum multiplicity, 185 (MNDO), 249 differential overlap), 249 number of moles, 5
maximum non-expansion work, 628 modulus, 43, 128 near infrared, 21
maximum velocity, 882 modulus notation, 62 nearly free-electron approximation,
maximum work, 627 molality, 680 345 O
Maxwell–Boltzmann distribution, molar absorption coefficient, 381 Néel temperature, 359 O branch, 412
17, 760 molar concentration, 6 negative activation energy, 826 observable, 48
Maxwell construction, 325 molar conductivity, 776, 778 negative temperature, 587 observed lifetime, 892
Maxwell relation, 639 molar heat capacity, 14, 553 neglect of diatomic differential overlap octahedral group, 280
McConnell equation, 490 molar mass, 5 (NDDO), 249 octahedral molecule, 4
mean activity coefficient, 699 molar mass average, 691 neighbouring group contribution, octet, 3
mean displacement, 787, 788 mole, 5 466, 467 octet expansion, 4
mean electronic energy, 521 mole fraction, 680 neodymium laser, 438 octupole, 305
mean energy, 517, 526 molecular beam, 857 neon configuration, 177 off-diagonal peaks, 483
mean free path, 764 molecular dynamics, 99 Nernst–Einstein equation, 779 ohm, 775
mean radius, 162 molecular flow, 858 Nernst equation, 738 Ohm’s law, 561
mean rotational energy, 519 molecular integral, 212, 249 Nernst filament, 378 one-dimensional random walk, 787
mean speed, 17 molecular mass, 5 Nernst heat theorem, 622 open system, 541
mean translational energy, 518 molecular modelling, 567 neutron, 2 operator, 48
mean value, 761 molecular orbital neutron diffraction, 341 angular momentum, 108
mean vibrational energy, 520 hydrogen molecule-ion, 210 Newton, I., 33 linear momentum, 49
mechanical equilibrium, 546 polyatomic molecule, 231 Newtonian flow, 768 position, 49
mechanism of reaction, 821 molecular orbital energy level Newton’s second law of motion, 10 optical activity, 281
Meissner effect, 360 diagram, 216 nitric oxide, 515 optical density, 382
melting temperature, 661 molecular orbital (MO) theory, 209 nitrogen optical Kerr effect, 441
meso-tartaric acid, 278 molecular potential energy curve, MO description, 220 orbital, 160
metal, 3 201, 212 PES, 222 orbital approximation, 169
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Atkins09819.indb 982 9/11/2013 8:56:37 AM

INDEX 983
orbital energy, 225 Helmholtz energy, 626 photon, 36 power (electric), 14

orbital notation, 214 interpretation, 508 photostationary state, 834 precession, 459
orbital overlap, 294 linear rotor, 511 physical chemistry, 1 precursor state, 928
order of group, 287 nonlinear rotor, 511 physical quantity, 6 predissociation, 436
orthogonality, 55 rate constant, 866 physisorption, 913 pre-equilibrium, 826
ortho-hydrogen, 403 rotation, 510 pi bond, 203 pre-exponential factor, 816
orthonormal, 55 spin, 522 pi-bond formation energy, 246 pressure, 5
orthorhombic lattice, 334 translation, 509 pi-electron binding energy, 234 KMT, 758
oscillating perturbation, 140 two-level system, 507 pi orbital, 218 pressure–composition diagram, 664
osmometry, 690 uniform ladder, 507 pi-to-pi* transition, 431 pressure jump, 814
osmosis, 688 vibration, 514 Planck, M., 34 primary absorption, 890
osmotic coefficient, 710 partition function density, 866 Planck distribution, 35, 143 primary kinetic isotope effect, 100
osmotic pressure, 689 pascal, 5 Planck’s constant, 35 primary quantum yield, 891
osmotic virial coefficient, 690 Pascal’s triangle, 471, 489 plane polarized wave, 21 primitive unit cell, 331, 332
osmotic virial equation, 690 Patterson synthesis, 339 plasmon, 919 principal quantum number, 2, 155
Otto cycle, 648 Pauling, L., 225 Plazcek–Teller relation, 453 principle
overall order, 803 Pauli exclusion principle, 171, 402 Plesset, M.S., 253 Aufbau, 176
overlap and symmetry, 292, 294 Pauli matrices, 298 PM3, 249 Avogadro’s, 7
overlap density, 211 Pauli principle, 171, 203, 402 PMT (photomultiplier tube), 38, 380 building-up, 176, 216
overlap integral, 212, 218, 262, 294 Pauling electronegativity, 225 point dipole, 310 correspondence, 77
overtone, 410 PDDG (pairwise distance directed point group, 276 Franck–Condon, 426, 899
oxidation, 734 Gaussian), 249 point group notation, 277 Le Chatelier’s, 729
oxidation number, 3 PDI (polydispersity index), 692 poise, 774 Pauli, 171, 203, 402
oxidation state, 3 penetration, 173 poison (catalyst), 933 Pauli exclusion, 171, 402
oxidizing agent, 734 peptide group, 268 Poisson distribution, 536 uncertainty, 60
oxocuprate superconductor, 360 perfect gas, 6, 320 polar bond, 4, 224 variation, 204, 226
oxygen molecule, 423 adiabatic expansion, 576 polar form (complex number), 128 probability amplitude, 43
MO description, 220 entropy of expansion, 615 polar molecule, 4, 303 probability density, 43
transitions, 425 mixing, 679, 681 symmetry aspects, 281 probability theory, 535
pressure and speed, 758 polarity projection operator, 294
relation between U and H, 562 symmetry aspects, 304 promotion, 205
P viscosity, 771 polarizability, 306, 399 proton, 2
p band, 346 perfect gas equation, 7 polarizability volume, 306 pseudofirst-order reaction, 804
P branch, 410, 428 perfect versus ideal, 686 polarization mechanism, 473 pulse, 90, 478
p–n junction, 356 period 2 diatomics, MO description, polarization mechanism (EPR), 491 pulse techniques, 476
p orbital, 163 219 polarized line, 419 pulsed laser, 439
p-type semiconductivity, 355 periodic crystal, 330 polyatomic molecule, MO description, pumping (laser), 437
packing fraction, 344 periodic table, 3 231 pyran, 297
paired electrons, 171 periodicity, 178 polychromatic radiation, 378 pyroelectric device, 380
pairwise distance directed Gaussian permanent dipole moment, 303 polychromator, 378
(PDDG), 249 permittivity, 13, 310 polydisperse, 691
parabolic potential energy, 92, 406 perpendicular band, 417 polydispersity index (PDI), 692 Q
para-hydrogen, 403 perpetual motion machine, 544 polyelectronic atom, 150 Q branch, 410, 412, 428
parallel band, 417 perturbation theory, 132 polyene, 232, 264 Q-switching, 439
paramagnetic, 357 PES (photoelectron spectroscopy), 221 polymorph, 662 QCM (quartz crystal microbalance),
paramagnetic contribution, 466 phase, 19, 657 polytype, 343 919
parity, 424 phase boundary, 657, 675 Pople, J., 238 QSSA (quasi-steady-state
partial charge, 4, 224, 304, 309 phase diagram, 657 population, 15, 501, 508 approximation), 823
partial derivative, 27, 589 two-component, 664 population difference, electron spin, quadrupole, 305
partial differential equation, 69 phase equilibrium, 674 462 quantization, 15
partial molar Gibbs energy, 672 phase problem, 339 population inversion, 437 angular momentum, 108
partial molar volume, 670 phase rule, 658 porphine, 300 energy, 35
partial pressure, 7 phase-sensitive detection, 462 position operator, 49 quantum number
partially miscible liquids, 667, 694 phase transition, 657 positronium, 193 angular momentum, 113
particle in a box, 74 entropy, 616 Postulate I, 42 particle in a box, 76
particle in a three-dimensional phenanthrene, 263, 300 Postulate II, 44 principal, 2, 155
well, 90 phenomenological equation, 767 Postulate II′, 43 spin, 170
particle on a plane, 87 phenylalanine, 363 Postulate III, 47, 49, 61 spin magnetic, 170
particle on a ring, 103 phosphorescence, 433, 890 Postulate IV, 50, 51 total angular momentum, 185
particle on a sphere, 111 phosphorus pentachloride, 279 Postulate V, 54 total orbital angular momentum,
particular solution, 69 photochemical process, 889 potential, 13 183
partition function, 506, 518 photochemistry, 889 potential energy, 12 total spin, 184
canonical, 525 photodiode, 380 molecular interaction, 321 vibrational, 93
electronic, 515 photoelectric effect, 37 potential energy barrier, 80 quantum oscillation, 860
entropy, 601 photoelectron, 221 potential energy curve, 201, 212 quantum yield, 891
equilibrium constant, 723 photoelectron spectroscopy (PES), 221 potential energy of ionic crystal, 349 quartz crystal microbalance (QCM),
factorization, 508 photoemission spectroscopy, 916 potential energy surface, 201, 861 919
Gibbs energy, 626 photomultiplier tube (PMT), 38, 380 power, 12 quasicrystal, 331
Atkins09819.indb 983 9/11/2013 8:56:37 AM

984 INDEX
quasi-steady-state approximation reduction, 734 Rydberg atom, 194 optical properties, 357
(QSSA), 823 reduction of representation, 286 Rydberg constant, 157, 181 semi-empirical method, 248
quenching, 893 reference state, 565 Rydberg expression, 181 separation of variables, 70, 87,
quenching method, 801 refinement (X-ray), 340 113, 151
quinoline, 278 reflection, 275 series expansion, 28
reflection (X-ray), 336 S Sham, L.J., 257
refractive index, 20 s band, 346 shape, 4
R regular solution, 697 S branch, 412 shape-selective catalyst, 931
R branch, 411, 428 relative mean speed, 762 s orbital, 161 shell, 2, 160
radial distribution function, 166 relative molecular mass, 5 Sackur–Tetrode equation, 602 SHG (second harmonic generation),
radial node, 155 relative permittivity, 310 saddle point, 863 919
radial wave equation, 152 relaxation, 813 SALC (symmetry-adapted linear shielded nucleus, 465
radiation sources, 378 relaxation time, 480 combination), 294 shielding, 173
radiative decay, 433 REMPI (resonant multiphoton salt bridge, 734 shielding constant, 173, 466
radio waves, 21 ionization), 861 salt on roads, 688 shielding constant (NMR), 464
radius ratio, 347 reorganization energy, 894, 901 salting-in effect, 710 SI (Système international), 6
rainbow angle, 860 representation, 285 SAM (scanning Auger electron side-centred unit cell, 332
rainbow scattering, 860 representative, 285 microscopy), 917 sigma bond, 202
Raman activity, symmetry repulsions, 321 Sayre probability relation, 340 sigma orbital, 210
analysis, 421 repulsive surface, 864 scalar coupling constant, 469 similarity transformation, 272
Raman spectroscopy, 377, 383 residual entropy, 622 scalar physical property, 195 simple distillation, 666
Ramsperger, H.C., 878 resistance, 775 scalar product, 195 simultaneous equations, 271
random walk, 537, 787 resonance, 3, 203, 457 scanning Auger electron microscopy single bond, 3
Rankine scale, 23 resonance condition, 461 (SAM), 917 singlet, 184
Raoult, F., 683 resonance energy transfer, 894 scanning electron microscopy (SEM), singly excited determinant, 251
Raoult’s law, 683, 695 resonance hybrid, 204 915 skimmer, 858
rate constant, 802 resonance integral, 227 scanning probe microscopy (SPM), Slater determinant, 240, 251
diffusion, 845 resonance Raman spectroscopy, 384 915 Slater-type orbital (STO), 245
electron transfer, 899 resonant mode, 438 scattered radiation, 377 sodium D lines, 187
equilibrium constant, 812 resonant multiphoton ionization, 861 scattering factor, 337 solid, 5
partition function, 866 retarding force, 777 scattering intensity, 858 solid-state NMR, 484
state-to-state, 861 retinal, 896 SCF (self-consistent field) calculation, solute activity, 695
structureless particles, 851 reverse bias, 356 174, 241 solvent activity, 694
temperature dependence, 817 reversible change, 546 Schoenflies system, 277 solvent contribution, 466, 469
transition-state theory, 851 Rice, O.K., 878 Schrödinger, E., 47 sp hybrid orbital, 207
rate-determining step (RDS), 825 Rice–Ramsperger–Kassel (RRK) Schrödinger equation sp2 hybrid orbital, 206
rate law, 802 model, 878 hydrogenic atom, 151 sp3 hybrid orbital, 205
surface process, 933 right-hand rule, 196 particle on a ring, 106 space lattice, 330
rate of adsorption, 919 ring current, 468 particle on a sphere, 112 space quantization, 116
rate of consumption, 801 rock salt structure, 347 vibration, 92, 406 spatial coherence, 439
rate of desorption, 919 root mean square displacement, 787 second derivative, 27 specific heat capacity, 14
rate of formation, 801 root mean square speed, 759 second harmonic generation (SHG), specific selection rule, 142
rate of reaction, 801 Roothaan, C.C.J., 242 919 spectral density of states, 34
Rayleigh, Lord, 34 Roothaan equations, 242 second ionization energy, 179 spectral series, 181
Rayleigh–Jeans law, 34 rotating frame, 477 second law of motion, 10 spectrometer, 378
Rayleigh line, 401 rotation, 103 Second Law of thermodynamics, 15, spectroscopic transition, 142
Rayleigh radiation, 384 rotation and translation analogies, 11 596, 597 spectroscopy, 36, 377
RDS (rate-determining step), 825 rotational constant, 391 second-order correction to the energy, speed, 9
reaction coordinate, 818, 848 rotational degeneracy, 393 134 speed of light, 20
reaction enthalpy, 564 rotational energy levels, 391 second-order phase transition, 660 sphalerite, 348
temperature dependence, 567 rotational mean energy, 519 secondary kinetic isotope effect, 100 spherical harmonics, 113, 152
reaction Gibbs energy, 716, 718 rotational partition function, 510 secular determinant, 228, 243 spherical polar coordinates, 112, 151
cell potential, 736 rotational Raman spectroscopy, 399 secular equations, 227, 243 spherical rotor, 390
reaction order, 803 rotational structure, 428 selection rule, 142 spherical top, 391
reaction product imaging, 861 rotational subgroup, 532 electronic transitions, 425 spherical well energy levels, 533
reaction quotient, 717, 718, 734 rotational temperature, 512 hydrogenic atom, 182 spin, 170
reaction rate, 801 rotational term, 391 many-electron atom, 187 spin-½ nucleus, 459
reactive cross-section, 840 RRK (Rice–Ramsperger–Kassel) molecular vibration, 407 spin correlation, 177
real gas, 322 model, 878 polyatomic vibrations, 417 spin density, 490
real solution, 694 RRKM model, 878 rotational, 396 spin hamiltonian, 458, 496
real-time analysis, 800 ruby laser, 438 rotational Raman, 400 spin–lattice relaxation time, 480
rearrangement, 890 rule symmetry aspects, 295 spin magnetic quantum number, 170
reconstruction, 918 exclusion, 419 vibrational Raman, 412 spin–orbit coupling, 186
rectangular potential energy barrier, 80 phase, 658 self-consistent field (SCF) calculation, spin–orbit coupling constant, 186
redox reaction, 734 Trouton’s, 617 174, 241 spin paramagnetism, 358
reduced mass, 151, 406 Russell–Saunders coupling, 185 SEM (scanning electron microscopy), spin partition function, 522
reducing agent, 734 ruthenocene, 278 915 spin quantum number, 170
reductant, 734 Rydberg, J., 181 semiconductor, 353, 355 spin relaxation, 479
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Atkins09819.indb 984 9/11/2013 8:56:38 AM

INDEX 985
spin–spin coupling, 472 subshell, 2, 160 Debye–Hückel, 700 transition metal, 3

spin–spin relaxation time, 480 substitution (for integration), 29 density functional, 256 transition probability, 81, 140
spinorbital, 240 substrate, 882, 912 Hückel, 248 transition rate, 140
SPM (scanning probe microscopy), sulfur dioxide spectrum, 36 kinetic molecular, 16, 757 transition state, 849
915 Sun interior, 791 Marcus, 899 transition-state theory, 848
spontaneous change, 15, 595, 625 Sun surface temperature, 34 molecular orbital (MO), 209 transition temperature, 616
Gibbs criterion, 626 superconducting quantum perturbation, 132 translation, 73
Helmholtz criterion, 626 interference device (SQUID), 358 transition-state, 848 translation and rotation analogies, 11
spontaneous emission, 144 superconductor, 353, 360 valence-bond (VB), 201 translation in two dimensions, 87
SPR (surface plasmon resonance), 919 supercritical fluid, 326 thermal conduction, 770 translational contribution, 518
square-integrable, 44 superfluid, 662 thermal conductivity, 768 translational partition function, 509
square modulus, 43, 128 superposition, 54, 59 thermal de Broglie wavelength, 509 transmission coefficient, 850
square-planar molecule, 4 supersonic jet, 858 thermal desorption spectroscopy transmission electron microscopy
square wave, 371 supersonic nozzle, 858 (TDS), 929 (TEM), 915
SQUID (superconducting quantum surface defect, 913 thermal equilibrium, 546 transmittance, 381
interference device), 358 surface growth, 913 thermal motion, 543 transport property, 767
standard boiling point, 660 surface mobility, 930 thermal neutron, 341 transpose matrix, 270
standard cell potential, 738 surface plasmon resonance (SPR), 919 thermal wavelength, 509 transverse relaxation time, 480
standard deviation, 535 surroundings, 541 thermochemistry, 560 trial wavefunction, 204
standard enthalpy symmetric rotor, 390, 392 thermodynamic control, 827 triclinic unit cell, 331
of formation, 565 symmetric stretch, 416 thermodynamic equation of state, 640 volume, 366
of fusion, 563 symmetric top, 391 thermodynamic equilibrium constant, trigonal-bipyramidal molecule, 4
of reaction, 564 symmetry-adapted linear combination 719 trigonal-planar molecule, 4
table of, 564 (SALC), 294 thermodynamic force, 783 triple bond, 3
of transition, 563 symmetry axis, 275 thermodynamic limit, 525 triple point, 6, 661
standard enthalpy change, 563 symmetry element, 275, 331 thermodynamic temperature, 6, 612 triplet, 184
standard (Third-Law) entropy, 623 symmetry number, 512, 532 thermodynamics, 14, 541 Trouton’s rule, 617
standard freezing point, 661 symmetry operation, 275, 331 thermogram, 563 tumbling, 418
standard Gibbs energy of formation, symmetry species, 287 Third Law of thermodynamics, 622 tunnelling, 80, 899
633 synchrotron radiation, 378 Third-Law entropy, 623 tunnelling (harmonic oscillator), 98
standard Gibbs energy of reaction, synchrotron storage ring, 378 Thomson, G., 39 turnover frequency, 884
633, 717, 719 system, 541 Thomson, W., 555 two-dimensional NMR, 483
standard hydrogen electrode, 740 three-body interaction, 317 two-dimensional square well, 87
standard potential, 741 three-level laser, 437 two-electron integral, 249
combining, 742 T tight-binding approximation, 345 two-fluid model, 663
standard pressure, 6 Taylor series, 28 time constant, 807 two-level system , 518
standard reaction entropy, 624 TDS (thermal desorption time-dependent perturbation theory, heat capacity, 574
standard state, 563 spectroscopy), 929 132, 139 Type I and II superconductors, 360
conventions, 696 Teller, E., 925 time-dependent Schrödinger equation,
Stark effect, 398 TEM (transmission electron 140
Stark modulation, 382 microscopy), 915 time-dependent wavefunction, 42 U
state function, 544, 608 temperature, 6, 501 time-independent perturbation theory, u,g symmetry, 214
state-to-state rate constant, 861 temperature–composition diagram, 132 ubiquitin, 563
stationary state, 139 665 time-independent Schrödinger ultrahigh vacuum, 915
steady-state approximation, 823 temperature-independent equation, 47 ultraviolet catastrophe, 34
step (surface), 913 paramagnetism (TIP), 359 time-independent wavefunction, 42 ultraviolet photoelectron spectroscopy
steric factor, 840, 878 temperature jump, 813 time-resolved spectroscopy, 383 (UPS), 222, 916
entropy of activation, 853 temperature-programmed desorption TIP (temperature-independent ultraviolet radiation, 21
steric requirement, 840 (TPD), 929 paramagnetism), 359 unbound state, 156
Stern, O., 117, 170 temporal coherence, 439 TMS (tetramethylsilane), 465 uncertainty principle, 60
Stern–Gerlach experiment, 117, 170, term symbol torque, 11 energy–time, 143
192 atomic, 183 total angular momentum, 185 uncompetitive inhibition, 885
Stern–Volmer equation, 893 molecules, 423 total angular momentum quantum undetermined multiplier, 502
Stern–Volmer plot, 893 terrace, 913 number, 185 ungerade, 424
sticking probability, 928 tetrahedral group, 280 total energy, 12 ungerade symmetry, 214
stimulated absorption, 143 tetrahedral molecule, 4 total interaction, 317 uniform electron gas, 257
stimulated emission, 144, 890 tetramethylsilane (TMS), 465 total orbital angular momentum unimolecular reaction, 821, 876
Stirling’s approximation, 537 tetraphenylmethane, 280 quantum number, 183 unit, 6
STO (Slater-type orbital), 245 theorem total rate of absorption, 143 unit cell, 331
Stokes–Einstein equation, 779 Brillouin’s, 254 total spin angular momentum unit matrix, 270
Stokes lines, 401 convolution, 373 quantum number, 184 unit vector, 195
Stokes radiation, 384 equipartition, 17, 518 TPD (temperature-programmed UPS (ultraviolet photoelectron
Stokes’s law, 777 Hohenberg–Kohn, 257 desorption), 929 spectroscopy), 222, 916
stopped-flow technique, 800 Koopmans’, 221 trajectory, 10, 12
structure factor, 337 Nernst heat, 622 transition, 139
structure refinement, 340 virial, 163 transition dipole moment, 142, 182, V
subgroup, 532 theory 295, 397, 407, 425 vacuum permittivity, 13
sublimation vapour pressure, 660 activated complex, 848 transition intensity, rotational, 397 vacuum ultraviolet, 21
Atkins09819.indb 985 9/11/2013 8:56:38 AM

986 INDEX
valence band, 355 vector representation of angular volume magnetic susceptibility, 357 Wierl equation, 341
valence-bond (VB) theory, 201 momentum, 109 VSEPR (valence-shell electron pair work, 11, 542
valence shell, 3 vector subtraction, 195 repulsion) theory, 4 constant pressure, 546
valence-shell electron pair repulsion velocity, 9 extension, 545
(VSEPR) theory, 4 velocity selector, 761, 858 varieties, 545
valence state, 226 vertical mirror plane, 275 W work function, 37
van der Waals, J.D., 323 vertical transition, 426 water wrinkle, Nature’s abhorrence
van der Waals equation, 323, 328, vibration, 92 molecular cluster, 860 of a, 785
528 vibration–rotation term, 410 normal modes, 417
van der Waals interactions, 309 vibrational mean energy, 520 phase diagram, 662
van der Waals isotherms, 325 vibrational partition function, 514 residual entropy, 622 X
van der Waals’ loops, 325 vibrational progression, 426 symmetry elements, 275 xenon discharge lamp, 378
van der Waals molecule, 860 vibrational quantum number, 93 VB description, 204 XPS (X-ray photoelectron
van der Waals parameters, 323 vibrational Raman spectra, 412, 419 water–ethanol mixture, 670 spectroscopy), 916
vanishing integral, 291 vibrational structure, 422, 426 watt, 12 X-ray, 21
van ’t Hoff equation vibrational temperature, 512 wave, 19 X-ray crystallography, 335
equilibrium, 730 vibrational term, 407 wave–particle duality, 39 X-ray fluorescence, 916
osmosis, 689 vibronic transition, 425 wavefunction, 42 X-ray photoelectron spectroscopy
vapour pressure, 326, 660 virial coefficient, 322 harmonic oscillator, 94 (XPS), 916
determination, 765 virial equation, 322 hydrogenic atom, 152, 155
regular solution, 698 virial theorem, 163 particle in a box, 76
vapour pressure lowering, 687 virtual orbital, 251 particle on a ring, 106 Y
variance, 535, 658 viscosity, 768 three-dimensional square well, 90 YAG (yttrium aluminium garnet), 438
variation principle, 204, 226 liquid, 774 two-dimensional square well, 88 yttrium aluminium garnet (YAG), 438
vector, 195 perfect gas, 771 valence-bond (VB), 202
vector addition, 195 temperature dependence, 775 wavelength, 19
vector differentiation, 197 visible light, 21 wavenumber, 20 Z
vector model, 117 volcano curve, 933 wavepacket, 59 Zeeman effect, 193
vector multiplication, 195 volt, 13 weight (configuration), 499, 600 zero-order reaction, 803
vector physical property, 195 voltaic cell, 734 weight-average molar mass, 691 zero-point energy, 78, 93
vector product, 196 volume, 5 Wien’s displacement law, 34 zinc blende (sphalerite), 348
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Peter Atkins Julio de Paula Ron Friedman Physical Chemistry Quanta (0970-1010)

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Peter Atkins Julio de Paula Ron Friedman Physical Chemistry Quanta (0970-1010)

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PART 4 Data

Table 0.2 (Continued)

Nuclide m/mu Abundance/%

Table 19.1 Effective nuclear charge, Zeff = Z − σ

Table 20.2 First and second ionization energies, I/(kJ mol−1)

Atkins09819.indb 947 9/11/2013 8:55:03 AM

Table 20.3 Electron affinities, Eea/(kJ mol−1)

Table 24.1 Bond lengths, Re/pm

(a) Bond lengths in specific molecules

(b) Mean bond lengths from covalent radii*

Atkins09819.indb 948 9/11/2013 8:55:04 AM

Table 24.2a Bond dissociation enthalpies, ΔH <(A–B)/(kJ mol−1) at 298 K*

Table 24.2b Mean bond enthalpies, ΔH <(A–B)/(kJ mol−1)*

Atkins09819.indb 949 9/11/2013 8:55:07 AM

Table 25.1 Pauling (italics) and Mulliken electronegativities

Table 34.1 Magnitudes of dipole moments (μ), polarizabilities (α), and

μ/(10−30 C m) μ/D α′/(10−30 m3) α/(10−40 J−1 C2 m2)

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Table 35.2 Lennard-Jones (12,6) potential parameters

CO2 −142 −72.2 −12.4 CO2 714.8

H2 −2.0 13.7 15.6 H2 110.0

He 11.4 12.0 11.3 10.4 He 22.64

Kr −62.9 −28.7 1.7 Kr 575.0

N2 −160.0 −10.5 6.2 21.7 N2 327.2

Ne −6.0 10.4 12.3 13.8 Ne 122.1

O2 −197.5 −22.0 −3.7 12.9 O2 405.9

Xe −153.7 −81.7 −19.6 Xe 768.0

Table 36.3 van der Waals parameters

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Table 36.5 Critical constants of gases

pc/atm Vc/(cm3 mol−1) Tc/K

Table 38.2 Ionic radii, r/pm*

Li+(4) Be2+(4) B3+(4) N3− O2−(6) F−(6)

d-block elements (high-spin ions)

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Table 38.4 Lattice enthalpies, ΔHL< /(kJ mol−1) at 298 K

Table 39.1 Magnetic susceptibilities at 298 K

χ/10−6 χm/(10−10 m3 mol−1)

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Table 43.1 Properties of diatomic molecules

␯ / cm −1 θV/K B / cm −1 θR/K Re/pm kf/(N m−1) Do/(kJ mol−1) σ

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Table 45.2 Absorption characteristics of some groups and molecules

Group ␯ max/(104 cm−1) λmax/nm ε/(dm3 mol−1 cm−1)

C = C (π* ← π) 6.10 163 1.5 × 104

Table 47.2 Nuclear spin properties

Nuclide Natural Spin, I Magnetic g-value γ /(107 T−1s−1) NMR frequency

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Table 50.1 Hyperfine coupling constants for atoms,

Data: P.W. Atkins and M.C.R. Symons, The structure of inorganic

Table 56.1 Temperature variation of molar heat capacities†

a b/(10−3 K−1) c/(105 K2)

Liquids (from melting to boiling)

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Table 56.2 Inversion temperatures, normal freezing and boiling

TI/K Tf/K Tb/K μ/(K atm−1)

Tf/K Fusion Tb/K Vaporization Tf/K Fusion Tb/K Vaporization

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Table 57.3 Thermodynamic data for organic compounds at 298 K

C(s) (graphite) 12.011 0 0 5.740 8.527 −393.51

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Table 57.3 (Continued)

Alkanals and alkanones