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Chapter 1
Exercises
1.1
(a) Surface where electron probability = 0.
1.25
1.27
Chapter 2
Exercises
2.1
(a) Lanthanum through lutetium.
(b) Apparent radius of an atom in non-bonded contact
with another.
(c) Actual nuclear charge experienced by an electron.
2.3
2.5
1.5
5p.
1.7
Size of an orbital.
1.9
2.7
1.11
2.9
1.13
2.11
1.15
2.13
2.15
50.
1.17
2.17
2.19
2.21
1.19
1.21
E113: [Rn]7 s 2 5 f 1 4 6d 1 0 7p 1 .
E113 as +1 ion: [Rn]7s 2 5 f 1 4 6d 1 0 .
E113 as +3 ion: [Rn]5f 1 4 6d 1 0 .
2010 W. H. Freeman and Company, All Rights Reserved
2.23
4s = 2.95; 3d = 5.60.
2.27
2.29
2.31
2.33
2.35
3.11
3.13
3.15
2.41.
No specific answer.
Chapter 3
Exercises
3.1
(a) Linear combination of atomic orbitals.
(b) M.O. in which the increased electron density lies
between the two nuclei.
(c) Valence shell electron pair repulsion.
(d) Mixing atomic orbitals on a central atom.
(e) The axis containing the highest n-fold rotation
axis.
3.3
3.5
3.7
3.
2010 W. H. Freeman and Company, All Rights Reserved
3.17
3.19
3.21
3.23
3.25
3.27
3.43
3.44
3.45
3.29
3.31
3.33
Hybridization: (a) sp; (b) sp2; (c) sp3; (d) sp3d; (e)
sp3d2.
3.35
9.
3.37
3.39
3.47
3.49
3.51
3.53
3.55
Chapter 4
Exercises
4.1
(a) Metal consists of metal ions with free electrons.
(b) Smallest repeatable fragment of a crystal lattice
that.
(c) Combination of two or more solid metals.
4.3
4.5
4.7
4.9
4.11
4.13
4.19
4.21
145pm.
4.23
5.13
5.15
5.17
5.19
5.21
5.23
5.25
5.27
Chapter 5
Exercises
5.1
(a) Distortion from a spherical shape.
(b) The holes between anions in the crystal packing.
(c) The diagram used to show the three bonding
categories: metallic, covalent, and ionic.
5.3
5.5
5.7
5.9
5.29
5.31
5.37
1.15(r+ + r).
5.39
164 pm
5.41
251 pm
Chapter 6
Exercises
6.1
(a) A reaction for which G is negative.
(b) A measure of disorder.
(c) A mole of a substance is formed from its
constituent elements in their standard phases at 298 K
and 100 kPa.
6.3
6.5
Hf = 286 kJmol1;
Sf
kJmol1K1
Gf
= 237 kJmol1
Spontaneous at SATP.
6.7
1
G = 159 kJmol
6.9
6.11
N=N.
Approximate enthalpy of reaction = +112 kJmol1
6.13
6.15
6.17
U = 2649 kJmol
6.29
6.31
kJmol1.
6.19
6.21
6.23
6.33
250 kJmol1.
6.35
6.37
6.39
7.9
7.11
7.13
6.43
H = +36 kJmol1
6.45
6.46
6.47
7.15
HSO4(H2SO4)
HF is acting as a base and H2F+ is the conjugate
acid,
7.17
7.3
7.5
7.19
7.21
7.23
Chapter 7
Exercises
7.1
Polar protic: solvents with a dielectric constant
between 50 and 100.
Dipolar aprotic: solvents with dielectric constant
between 20 and 50.
Nonpolar: solvents with dielectric constant close to
zero.
2+
OH(aq)
7.25
7.27
7.29
7.31
7.33
(a) No effect.
(b) Increasing pH.
HSe(aq) + OH(aq)
(c) Decreasing pH.
Se (aq) + H2O(l)
7.61
7.63
7.65
Fe3+(AlO6)3.
[Sc(OH2)6]3+(aq) + H2O(l)
[Sc(OH2)5(OH)]2+(aq) + H3O+(aq)
(d) Increasing pH. F(aq) + H2O(l) HF(aq) +
OH(aq)
7.37
7.39
7.41
G
= 28 kJmol1. Magnesium oxide will be a
weaker base than calcium oxide (G = 59
kJmol1).
7.43
Chapter 8
Exercises
8.1
(a) A substance that will oxidize another.
(b) A two-dimensional plot of free energy against
temperature for series of reactions that involve
elements and their oxides, sulfides, or chlorides.
+3 (b) +5 (c) 3 (d) 3 (e) +5
8.3
(a)
8.5
8.7
8.9
(a) +1; (b) +2; (c) +3; (d) +4; (e) +5. An increase by
units of +1 from Group 13 to Group 17.
8.11
7.45
(a)
(b)
7.47
8.13
8.15
8.17
8.19
7.49
7.51
7.53
(a) Spontaneous.
(b) Non-spontaneous.
8.23
8.25
8.27
E = 0.267 V
8.29
E = +0.805 V
8.31
8.33
+3.
8.35
9.9
(a) Br2
(b) E = +0.52 V
(c) The Nernst expression does not have a pHdependent term.
9.11
9.13
9.15
9.17
Tin.
9.19
9.21
9.23
9.25
Thallium(I) bromide.
9.27
9.29
Yttrium.
9.35
9.37
9.39
Chapter 9
Exercises
9.1
(a) A pair of elements in a compound whose sum of
valence electrons adds up to eight.
(b) The relationship between an element and the
element to its lower right in the periodic table.
9.3
9.5
9.7
9.41
Group 15
Group 16
Group 15
CN22
OCN
Group 16
OCN
CO2
Group 17
FCN
FCO+
Chapter 10
Exercises
10.1
(a) A hydrogen atom bridging atoms in a covalent
bond in which the hydrogen is less electronegative.
(b) A hydrogen atom bridging atoms in a covalent
bond in which the hydrogen is more electronegative.
10.3
10.5
10.7
Bond energy
Electron affinity
10.9
Hydrogen
432 kJmol1
79 kJmol1
Chlorine
240 kJmol1
349 kJmol1
10.17
10.19
10.21
10.27
10.11
10.13
10.15
Chapter 11
Exercises
11.1
(a)
(b)
(c)
(d)
11.3
11.5
11.7
11.9
10
11.11
11.13
11.15
HCO3(aq)
HCO3(aq) + Na+(aq) NaHCO3(s)
2 NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
11.29
11.31
11.33
11.35
11.19
Chapter 12
11.21
Exercises
12.1
(a)
11.23
Lithium:
6 Li(s) + N2(g) 2 Li3N(s)
2 Li(s) + Cl2(g) 2 LiCl(s)
Li(s) + C4H9Cl(solv) LiC4H9(solv) + LiCl(s)
4 Li(s) + O2(g) 2 Li2O(s)
2 Li(s) + H2O(l) 2 LiOH(aq) + H2(g)
Li2O(s) + H2O(l) 2 LiOH(aq)
2 LiOH(aq) + CO2(g) Li2CO3(aq) + H2O(l)
Li2O(s) + CO2(g) Li2CO3(s)
Sodium:
2 Na(s) + Cl2(g) 2 NaCl(s)
2 Na(s) + H2O(l) 2 NaOH(aq) + H2(g)
2 Na(s) + O2(g) Na2O2(s)
Na2O2(g) + H2O(l) 2 NaOH(aq) + H2O2(aq)
2 NaOH(aq) + CO2(g) Na2CO3(aq) + H2O(l)
Na2CO3(aq) + CO2(g) + H2O(l) 2 NaHCO3(aq)
2 Na(s) + 2 NH3(l) 2 NaNH2(NH3) + H2(g)
Na2O2(s) + CO2(g) Na2CO3(s) + O2(g)
Potassium
Na(l) + KCl(l) K(g) + NaCl(l)
2 K(s) + Cl2(g) 2 KCl(s)
K(s) + O2(g) KO2(s)
2 KO2(s) + 2 H2O(l) 2 KOH(aq) + H2O2(aq) +
O2(g)
(b)
(c)
Ca(HCO3)2(aq) CaCO3(s) + H2O(l) +
CO2(g)
(d)
12.3
12.5
12.7
12.9
Steric hindrance.
12.11
Mg2+(MgCl2) + 2 e Mg(l)
2 Cl-(MgCl2) Cl2(g) + 2 e
12.15
12.17
12.19
12.21
12.23
(a)
H2O(s).
(b)
Mg(s) + Cl2(g) MgCl2(s)
Beyond the Basics
H
S
T
= +83 kJmol1
= 0.220 kJmol1K1
= 377 K
12.27
12.29
12.31
12.33
12.35
12.25
13.3
number of 1:
13.5
An arachno-cluster.
13.7
-1,042kJ. The major factors are the weak fluorinefluorine bond, and the exceedingly strong boronfluorine bond.
13.9
13.11
13.13
13.15
13.17
13.19
13.21
Chapter 13
Exercises
13.1
(a) 3 K(l) + AlCl3(s) Al(s) + 3 KCl(s)
(b) B2O3(s) + 2 NH3(g) 2 BN(s) + 3 H2O(g)
(c) 2 Al(s) + 2 OH(aq) + 6 H2O(l) 2
[Al(OH)4](aq) + 3 H2(g)
Cl3Al[O(C2H5)2].
12
13.27
13.29
13.31
13.33
13.35
13.37
13.39
14.5
14.7
14.9
14.11
13.41
13.43
13.45
14.13
= +0.354 kJmol1K1
= 181 kJmol1
Chapter 14
Exercises
14.1
(a) Li2C2(s) + 2 H2O(l) 2 LiOH(aq) + C2H2(g)
(b) SiO2(s) + 2 C(s) Si(l) + 2 CO(g)
(c) CuO(s) + CO(g) Cu(s) + CO2(g)
(d) Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)
CaCO3(s) + CO2(g) + H2O(l) Ca(HCO3)2(aq)
(e) CH4(g) + 4 S(l) CS2(g) + 2 H2S(g)
(f) SiO2(s) + 2 Na2CO3(l) Na4SiO4(s) + 2
CO2(g)
(g) PbO2(s) + 4 HCl(aq) PbCl4(aq) + 2 H2O(l)
PbCl4(aq) PbCl2(s) + Cl2(g)
14.15
14.17
14.19
14.21
14.23
14.25
Trigonal planar.
14.27
There are three Fe2+ ions and two Fe3+ ions per
formula.
14.29
14.31
14.35
14.37
CN and CO.
14.39
14.41
Carbon:
4 CO(g) + Ni(s) Ni(CO)4(g)
CO(g) + Cl2(g) COCl2(g)
CO(g) + S(s) COS(g)
H 2SO 4
HCOOH(l)
CO(g) + H2O(l)
CO2(g) + 2 Ca(s) C(s) + 2 CaO(s)
2 CO(g) + O2(g) 2 CO2(g)
catalyst
CO(g) + 2 H2(g) CH3OH(l)
2 C(s) + O2(g) 2 CO(g)
C(s) + O2(g) CO2(g)
Na2C2(s) + 2 H2O(l) 2 NaOH(aq) + C2H2(g)
2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)
Al4C3(s) + H2O(l) 3 CH4(g) + 4 Al(OH)3(s)
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l)
CH4(g) + 4 S(l) CS2(g) + 2 H2S(g)
CS2(g) + 3 Cl2(g) CCl4(g) + S2Cl2(l)
CS2(g) + S2Cl2(l) CCl4(g) + 6 S(s)
CH4(g) + NH3(g) HCN(g) + 3 H2(g)
HCN(aq) + H2O(l) H3O+(aq) + CN(aq)
Ca(OH)2(aq) + CO2(g) CaCO3(s) + H2O(l)
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + H2O(l) +
CO2(g)
CaCO3(s) + H2O(l) + CO2(g) Ca(HCO3)2(aq)
Silicon:
Si(s) + HCl(g) SiHCl3(g) + H2(g)
2 CH3Cl(g) + Si(s) (CH3)2SiCl2(l)
SiO2(s) + 2 C(s) Si(s) + 2 CO(g)
SiO2(s) + 6 HF(aq) SiF62(aq) + 2 H+(aq) + 2
H2O(l)
14
SiO2(s) + 2 Na2CO3(l)
Na4SiO4(s) + 2 CO2(g)
14.47
14.49
14.51
14.53
14.55
Y is Sn(C2H5)4, Z is SnCl(C2H5)3
3 Sn(C2H5)4(l) + SnCl4(l) 4 SnCl(C2H5)3(l)
14.57
14.59
15.9
15.11
15.13
15.15
15.17
15.19
15.21
15.23
15.25
15.27
NO bond order is 2:
Chapter 15
Exercises
15.1
(a) AsCl3(l) + 3 H2O(l) H3AsO3(aq) + 3 HCl(g)
(b) 3 Mg(s) + N2(g) Mg3N2(s)
15.5
[NF4]+F
15.61
15.63
15.65
15.67
15.69
15.45
15.71
15.73
15.47
15.75
15.77
15.79
15.31
15.33
15.35
15.37
15.39
15.41
15.49
K = 6 102
K = 7103
Equilibrium is attained much more rapidly.
15.51
(a)
(b)
(c)
15.53
H = 57 kJmol1
15.55
15.57
2 AsH3(g)
2 As(s) + 3 H2(g)
16
Chapter 16
Exercises
16.1
(a) 2 Fe(s) + 3 O2(g) 2 Fe2O3(s)
(b) BaS(s) + 4 O3(s) BaSO4(s) + 4 O2(g)
16.23
16.25
16.27
16.29
16.31
Sulfur trioxide.
16.33
16.35
16.5
16.7
16.9
16.11
16.13
16.15
16.17
16.19
16.37
16.39
16.41
16.43
16.49
16.51
(a)
(b)
16.67
16.69
16.53
16.71.
Chapter 17
Exercises
17.1
(a) UO2(s) + 4 HF(g) UF4(s) + 2 H2O(l)
16.55
mass = 94 tonne
16.57
16.59
16.61
E = 1.48 V
16.63
17.5
17.7
17.9
Because hydrogen ion does not appear in the halfequation, the reduction potential will not be pH
sensitive.
18
17.11
17.13
17.15
Zero.
17.17
17.21
H
= 7838 kJ. It would be a good propellant
because it produces a large number of small gas
molecules.
17.23
17.25
Steric hindrance.
17.27
17.29
17.31
17.35
17.37
17.39
17.41
17.43
P(CN)3
Fluorine:
Cl2(g) + 3 F2(g) 2 ClF3(g)
S(s) + 3 F2(g) SF6(g)
BrO3(aq) + F2(g) + 2 OH(aq) BrO4(aq) + 2
F(aq) + H2O(l)
2 Fe(s) + 3 F2(g) 2 FeF3(s)
H2(g) + F2(g) 2 HF(g)
2010 W. H. Freeman and Company, All Rights Reserved
17.47
Chapter 18
Exercises
18.1
(a) Xe(g) + 2 F2(g) XeF4(s)
(b) XeF4(s) + 2 PF3(g) 2 PF5(g) + Xe(g)
17.49
18.3
17.51
18.5
18.7
18.9
17.53
18.11
17.55
17.57
17.59
17.61
18.13
18.15
18.17
Rubidium or cesium.
18.19
2 Au + 7 KrF2 2 (KrF)+(AuF6) + 5 Kr
18.21
20
Chapter 19
Exercises
19.1
(a) Element belonging to the d-block.
(b) Molecules or ions covalently bonded to a central
metal ion.
(c) Energy separation between different members of
the metals d-orbital set.
19.3
19.5
19.7
19.15
19.17
(a)
[ReF6]2, the heavier metal has greater
crystal field splitting.
(b)
[Fe(CN)6]3, the higher charge has greater
crystal field splitting.
19.19
19.23
19.9
19.11
19.31
19.33
20.21
20.23
According to Fajans Rules, cations with non-noblegas configurations are likely to have a more covalent
character.
20.25
20.27
20.29
Titanium:
Chapter 20
Exercises
20.1
(a) TiCl4(l) + O2(g) TiO2(s) + 2 Cl2(g)
(b) Na2Cr2O7(s) + S(l) Cr2O3(s) + Na2SO4(s)
(c) Cu(OH)2(s) CuO(s) + H2O(l)
20.3
20.5
20.7
+ 4 OH(aq)
20.9
20.11
20.13
20.15
20.17
TiCl4(g) + O2(g)
TiO2(s) + 2 Cl2(g)
TiCl4(g) + 2 Mg(l)
Ti(s) + 2 MgCl2(l)
Vanadium:
[H2VO4](aq) + 4 H+(aq) + e VO2+(aq) + 3
H2O(l)
VO2+(aq) + 2 H+(aq) + e V3+(aq) + H2O(l)
[V(OH2)6]3+(aq) + e [V(OH2)6]2+(aq)
Chromium:
CrO42(aq) + 2 Ag+(aq) Ag2CrO4(s)
CrO42(aq) + H2O(l) HCrO4(aq) + OH(aq)
2 CrO42(aq) + 2 H+(aq) Cr2O72(aq) + H2O(l)
Cr2O72(aq) + 2 NH4+(aq) (NH4)2Cr2O7(s)
(NH4)2Cr2O7(s) Cr2O3(s) + N2(g) + 4 H2O(l)
Cr2O72(aq) + 14 H+(aq) + 6 e 2 Cr3+(aq) + 7
H2O(l)
Cr2O72(aq) + 2 K+(aq) K2Cr2O7(s)
K2Cr2O7(s) + H2SO4(aq) 2 CrO3(s) + K2SO4(aq) +
H2O(l)
K2Cr2O7(s) + 4 NaCl(s) + 6 H2SO4(l) 2 CrO2Cl2(l)
+ 2 KHSO4(s)
+ NaHSO4(s) + 3 H2O(l)
CrO2Cl2(l) + 4 OH(aq) CrO42(aq) + 2 Cl(aq) +
2 H2O(l)
Cr2O72(aq) + 14 H+(aq) + 6 e 2 Cr3+(aq) + 7
H2O(l)
2 Cr3+(aq) + Zn(s) 2 Cr2+(aq) + Zn2+(aq)
2 Cr2+(aq) + 4 CH3COO-(aq) + 2 H2O(l)
Cr2(CH3COO)4(OH2)2(s)
Manganese:
MnO4(aq) + e MnO42(aq)
MnO42(aq) + 2 H2O(l) + 2 e MnO2(s) + 4
OH(aq)
22
20.35
20.37
(a)
20.39
20.41
20.43
Vanadium.
20.45
20.47
20.49
20.51
20.55
20.57
Chapter 21
Exercises
21.1
(a)
21.26
21.28
Chapter 22
2 [Ag(CN)2](aq) + Zn(s) 2 Ag(s) +
[Zn(CN)4]2(aq)
(b)
2 Au(s) + 3 Cl2(g) 2 AuCl3(s)
21.3
21.5
21.7
21.9
21.11
21.13
Exercises
22.1
(a)
(b)
22.3
22.5
22.7
For Pd: +2 and +3. For Pt: +2, +4, and +6. Square
planar is common for the lower oxidation states,
octahedral geometry for the +6.
H2O(l) + 2 e
21.15
orbitals; diagonal
End-on overlap of a pair of
overlap of a pair of
orbitals; and the side-to-side
overlap of a pair of
orbitals.
22.9
21.17
21.18
22.11
24
22.21
22.23
Cr(CO)6
Fe(CO)5
Ni(CO)4
CO
OC
CO OC
23.17
(a)
1 MnMn bond
(b)
2 MnMn bonds
CO
OC
Mn
(c)
Hg(CH3)2 + 2 Na 2 NaCH3 + Hg
23.9
23.11
(a) hexacarbonylchromium(0)
(b) ferrocene or
bis(pentahaptocyclopentadienyl)iron(II)
(c) hexahaptobenzenetricarbonylchromium(0)
(d) pentahaptocyclopentadienyltricarbonyltungsten(I)
(e) bromopentacarbonylmanganese(I)
CO
1 FeFe bond
OC
COCO CO
CO
Fe
(a) Bi(CH3)5
(b) Si(C6H5)4 tetraphenyl silane
(c) KB(C6H5)4 postassium teraphenylborane
(d) Li4(CH3)4
(e) (C2H5)MgCl
23.7
Mn
OC
Exercises
23.1
(a) organometallic
(b) not organometallic as the bond B-O not B-C
(c) organometallic
(d) not organometallic as nitrogen is not metallic
(e) not organometallic as there is no Na-C bond
(f) organometallic
(g) organometallic
CO
23.15
23.5
CO
CO
Chapter 23
23.3
Mn
Mn
OC
CO
CO
(d)
no Mn-Mn bonds
OC
OC
Br
Mn
OC
OC
23.19
Fe
CO
Mn
Br
CO
CO
CO
(CO)3Fe
(e)
23.29
(f)
(g)
2 LiCl + (PMe3)2Pt
[PtCl2(PMe3)2] + LiCH2CH2CH2CH2Li
(a) +3
(b) +1
Ni
Ni
CO
23.25
A = tricarbonyl(5-cyclopentadienyl)(1-propenyl)tungsten(II)
B = dicarbonyl(5-cyclopentadienyl)(3-propenyl)tungsten(II)
C = tricarbonyl(5-cyclopentadienyl)(2-propenyl)tungsten(II)
hexafluorophosphate
Evolved gas = propene
23.27
Ti(S2CEt2)4.