Self Test Answers

Shriver & Atkins: Inorganic Chemistry 5e
Answers to self-tests and exercises
CHAPTER 1 1.7 Take the summation of the rest masses of all

the nuclei of the products minus the masses of
Self-tests the nuclei of the reactants. If you get a
negative number, energy will be released.
80
35 Br
+ 1
n 81
35 Br + But what you have calculated is the mass
S1.1 0
difference, which in the case of a nuclear
S1.2 d orbitals, 5 orbitals reaction is converted to energy.
S1.3 4
1.8 0.25
S1.4 3p
1.9 13.2 eV
S1.5 The added p electron is in a different (p)
orbital, so it is less shielded. 1.10 1524nm, 1.524 X 104 cm-1
S1.6 Ni :[Ar]3d 8 4s 2 , Ni 2+ :[Ar]3d 8 1 1 1 7 1

1.11 = R = 1.0974 X10 m
S1.7 Period 4, Group 2, s block 1 2
2
S1.8 Going down a group the atomic radius 1 1 1 7 1

increases and the first ionization energy = R = 1.0288X10 m
12 4 2
generally decreases.
1 1 1
= 9.7547X106 m 1
S1.9 Group 16. The first four electrons are
removed with gradually increasing values. = R
12 32
Removing the fifth electron requires a large
increase in energy, indicating breaking into a 1 1 1
complete subshell. = R = 8.2305X106 m 1
12 22
S1.10 Adding another electron to C would result in
the stable half filled p subshell. 1.12 0 up to n-X
S1.11 Cs+ 1.13 n2
1.14
Exercises N l ml Orbital Number
designation of
orbitals
1.1 (a) 14
N+ 42 He178 O+11p + 2 1 +1, 0, 2p 3
7
1
(b)
12
6 C+11p137 N + 3 2 +2, +1, 3d 5
(c) 14 1
N+ n H+ C 3 12 , 2
7 0 1 6
4 0 0 4s 1
4 3 +3, +2, 4f 7
246 , 3
1.2 96 Cm+126 C257 1
112 Uub+ 0 n
1.3 The higher value of I2 for Cr relative to Mn is 1.15 n=5, l = 3, and ml = -3,-2,-1,0,1,2,3
a consequence of the special stability of half-
1.16 Li: = Z Zeff ; = 3-1.28 = 1.72
filled subshell configurations and the higher
Zeff of a 3d electron verses a 4s electron. Be: = Z Zeff ; = 4-1.19 = 2.09
1.4 22
10 Ne + He Mg + n
4
2
25
12
1
0 B: = Z Zeff ; = 5-2.42 = 2.58
9 9 12 4 1
1.5 4 Be+ Be C+ He +2 n
4 6 2 0 C: = Z Zeff ; = 6-3.14 = 2.86
1.6 Since helium-4 is the basic building block, N: = Z Zeff ; = 7-3.83 = 3.17
most additional fusion processes will produce
nuclei with even atomic numbers. O: = Z Zeff ; = 8-4.45 = 3.55
F: = Z Zeff ; = 9-5.10 = 3.90
1.17 The 1s electrons shield the positive charge

form the 2s electrons.
1
2 ANSWERS TO SELF-TESTS AND EXERCISES
1.18 See Figs 1.11 through 1.16 1.30

1.19 See Table 1.6 and discussion.
1.20 Table 1.6 shows SR > Ba < Ra. Ra is
anomalous because of higher Zeff due to
lanthanide contraction.
1.21 Anomalously high value for Cr is associated
with the stability of a half filled d shell.
1.22 (a) [He]2s22p2
(b) [He]2s22p5
(c) [Ar]4s2
(d) [Ar]3d10
CHAPTER 2
(e) [Xe]4f145d106s26p3
(f) [Xe]4f145d106s2 Self-tests
1.23 (a) [Ar]3d14s2
S2.1
(b) [Ar]3d2
(c) [Ar]3d5
(d) [Ar]3d4 S2.2 (a) Angular
6
(e) [Ar]3d (b) square planar
(f) [Ar] S2.3 Linear
10 1
(g) [Ar]3d 4s S2.4 S22 : 1g22u23g21u42g4 ;
(h) [Xe]4f 7 Cl2 : 1g22u23g21u42g44u1.
1.24 (a) Xe]4f145d46s2 S2.5 1g22u23g21u42g4
(b) [Kr]4d6 S2.6 [2-2+4+2] = 3
6
(c) [Xe]4f
S2.7 Bond order: CN, C=N, and CN; Bond
(d) [Xe]4f7 strength: CN > C=N > CN.
(e) [Ar] S2.8 If it contains 4 or fewer electrons.
2
(f) [Kr]4d S2.9 21 kJ mol1
1.25 (a) S S2.10 (a) +1/2
(b) Sr (b) +5
(c) V
(d) Tc Exercises
(e) In
(f) Sm 2.1 (a) angular
1.26 See Figure 1.4. (b) tetrahedral
1.27 (a) I1 increases across the row except for a dip (c) tetrahedral
at S; (b) Ae tends to increase except for Mg
(filled subshell), P (half filled subshell), and 2.2 (a) trigonal planar
at AR (filled shell). (b) trigonal pyramidal
1.28 Radii of Period 4 and 5 d-metals are similar (c) square pyramidal
because of lanthanide contraction.
1.29 2s2 and 2p0
2.3 (a) T-shaped
ANSWERS TO SELF-TESTS AND EXERCISES 3
(b) square planar (b) one

(c) linear (c) none
2.4 (a) (d) two
2.15 (a) 1g22u2
(b) 1g22u21u2
Cl Cl
(c) 1g22u21u43g1
I
(d) 1g22u23g21u42g3
Cl Cl
2.16 The configuration for the neutral C2 would be
1g21u2 1u4. The bond order would be [2-
2+4] = 2.
2.17 (a) 1g22u23g21u42g4
(b)
(b) 1
F
(c) There is no bond between the two atoms.
F 2.18 (a) 2
S 120 0 (b) 1
1800 F (c) 2
F 2.19 (a) +0.5
2.5 (a) tetrahedral (b) 0.5
(b) octahedral (c) +0.5
2.6 (a) 176 pm 2.20
(b) 217 pm
(c) 221 pm
2.7 2(SiO) = 932kJ > Si=O = 640kJ; therefore
two SiO are preferred and SiO2 should (and
does) have four single SiO bonds.
2.8 Multiple bonds are much stronger for period 2
elements than heavier elements
2.9 483 kJ difference is smaller than expected
because bond energies are not accurate.
2.10 (a) 0 2.21 (a-c)

-1
(b) 205 kJ mol
2.11 Difference in electronegativities are AB 0.5,
AD 2.5, BD 2.0, and AC 1.0. The increasing
covalent character AD < BD < AC < AB.
2.12 (a) covalent

(b) ionic (d) Possibly stable in isolation (only bonding
(c) ionic and nonbonding orbitals are filled; not stable
in solution because solvents would have
2.13 (a) sp2 higher proton affinity than He.
(b) sp3 2.22 1
(c) sp3d or spd3 2.23 HOMO exclusively F; LUMO mainly S.
2 2 2
(d) p d or sp d. 2.24 (a) electron deficient
2.14 (a) one
(b) electron precise 3.4 XA2

3.5 K3C60
CHAPTER 3
3.6 281 pm
Self-tests
3.7 429 pm
S3.1 See Fig. 3.7 and Fig. 3.32.
3.8 CuAu. Primitive 12 carat.
S3.2 See Figure 3.35.
3.9 Zintl phase region
S3.3 52%
3.10 (a) 6:6 and 8:8
S3.4 rh = ((3/2)1/2 1) r = 0.225 r
(b) CsCI
S3.5 409 pm 3.11 6
S3.6 401 pm 3.12 2B type and 4A type in a distorted
octahedral arrangement.
S3.7 FeCr3
3.13 (a) = 0.78, so fluorite
S3.8 X2A3. (b) FrI? = 0.94, so CsCl
(c) BeO? = 0.19, so ZnS
S3.9 Ti CN = 6 (thought these are as two slightly (d) InN? = 0.46, so NaCl
different distances it is often described as 4 +
2) and O CN = 3. 3.14 CsCl.
S3.10 LaInO3 3.15 Lattice enthalpies for the di- and the trivalent
ions. Also, the bond energy and third electron
S3.11 2421 kJ mol1 gain enthalpy for nitrogen will be large.
S3.12 Unlikely
3.16 4 four times the NaCl value or 3144 kJmol1.
S3.13 MgSO4 < CaSO4 < SrSO4 < BaSO4.

3.17 (a) 10906 kJmol1
S3.14 NaClO4
(b) 1888 kJ mol1
S3.15 Schottky defects. (c) 664 kJ mol1
S3.16 Phosphorus and aluminium. 3.18 (a) MgSO4

(b) NaBF4
S3.17 The dx2-y2 and dz2 have lobes pointing along
the cell edges to the nearest neighbor metals.
3.19 CsI < RbCl < LiF < CaO < NiO < AlN
S3.18 (a) n-type
(b) p-type 3.20 Ba2+; solubilities decrease with increasing
radius of the cation.
Exercises
3.21 (a) Schottky defects
3.1 a b c and = 90, = 90, = 90 (b) Frenkel defects
3.2 Points on the cell corners at (0,0,0), (1,0,0),

(0,1,0), (0,0,1), (1,1,0), (1,0,1), (0,1,1), and 3.22 Solids have a greater number of defects as
(1,1,1) and in the cell faces at (,,0), temperatures approaches their melting points.
(,1,), (0,,) (,,1), (,1,), and
(1,,). 3.23 The origin of the blue color involves electron
transfer from cationic centres.
3.3 (c) and (f) are not as they have neighbouring 3.24 Vanandium carbide and manganese oxide.
layers of the same position.
3.25 Yes. S4.9 Identify the acids and bases?

3.26 A semiconductor is a substance with an
(a) FeCl3 + Cl [FeCl4], acid is FeCl3,
electrical conductivity that decreases with
increasing temperature. It has a small, base is Cl.
measurable band gap. A semimetal is a solid (b) I + I2 I3, acid is I2, base is I.
whose band structure has a zero density of
states and no measurable band gap. S4.10 The difference in structure between
(H3Si)3N and (H3C)3N? The N atom of
3.27 Ag2S and CuBr: p-type; VO2: n-type. (H3Si)3N is trigonal planar, whereas the N
atom of (H3C)3N is trigonal pyramidal.
S4.11 Draw the structure of BF3OEt2?
CHAPTER 4
Self-tests
S4.1 (a) HNO3 + H2O H3O+ + NO3

HNO3, acid. Nitrate ion, conjugate base. H2O,
base. H3O+, conjugate acid.
(b) CO32 + H2O HCO3 + OH
Exercises
carbonate ion, base; hydrogen carbonate, or
bicarbonate, conjugate acid; H2O, acid; 4.1 Sketch an outline of the s and p blocks of
hydroxide ion, conjugate base. the periodic table, showing the elements
that form acidic, basic, and amphoteric
(c) NH3 + H2S NH4+ + HS oxides?
Ammonia, base; NH4+, conjugate acid; The elements that form basic oxides are in
hydrogen sulphide, acid; HS, conjugate base. plain type, those forming acidic oxides are in
S4.2 What is the pH of a 0.10 M HF solution? outline type, and those forming amphoteric
pH= 2.24 oxides are in boldface type.
S4.3 Calculate the pH of a 0.20 M tartaric acid

solution?
pH=1.85
S4.4 Which solvent?
dimethylsulfoxide (DMSO) and ammonia.
S4.5 Is aKBrF4 an acid or a base in BrF3?
A base.
S4.6 Arrange in order of increasing acidity?
The order of increasing acidity is [Na(H2O)6]+ 4.2 Identify the conjugate bases of the
< [Mn(H2O)6]2+ < [Ni(H2O)6]2+ < following acids?
3+
[Sc(H2O)6] .
(a) [Co(NH3)5(OH2)]3+, conjugate base is
S4.7 Predict pKa values? (a) H3PO4 pKa 3. The [Co(NH3)5(OH)]2+.
actual value, given in Table 4.1, is 2.1.
(b) HSO4? The conjugate base is SO4.

(b) H2PO4 pKa(2) 8. The actual value,
(c) CH3OH? The conjugate base is CH3O.
given in Table 4.1, is 7.4.
(d) H2PO4? The conjugate base is HPO42.
(c) HPO42 pKa(3) 13. The actual value,
given in Table 4.1, is 12.7. (e) Si(OH)4? The conjugate base is
SiO(OH)3.
S4.8 What happens to Ti(IV) in aqueous
solution as the pH is raised? (f) HS? The conjugate base is S2.
Treatment with ammonia causes the 4.3 Identify the conjugate acids of the
precipitation of TiO2. Further treatment with following bases?
NaOH causes the TiO2 to redissolve.
(a) C5H5N (pyridine)? The conjugate acid ClO4, cannot be studied in sulfuric acid.
is pyridinium ion, C5H6N+.
4.9 Is the CN group electron donating or
(b) HPO42? The conjugate acid is H2PO42. withdrawing?
(c) O2? The conjugate acid is OH. electron withdrawing
(d) CH3COOH? The conjugate acid is 4.11 Is the pKa for HAsO42 consistent with
CH3C(OH)2+. Paulings rules? No. Paulings rules are
only approximate.
(e) [Co(CO)4]? The conjugate acid is
HCo(CO)4. 4.12 What is the order of increasing acid
strength for HNO2, H2SO4, HBrO3, and
(f) CN? The conjugate acid is HCN. HClO4?
4.4 Calculate the [H3O+] and pH of a 0.10 M the order is HClO4 > HBrO3 > H2SO4 >
butanoic acid solution? pH=2.85 HNO2.
4.5 What is the Kb of ethanoic acid? 4.13 Account for the trends in the pKa values of
Kb = 5.6 10 10 the conjugate acids of SiO44, PO43, SO42,
and ClO4?
4.6 What is the Ka for C5H5NH+?
The acidity of the four conjugate acids
Ka = 5.6 106 increases in the order HSiO43 < HPO42 <
4.7
-
Predict if F will behave as an acid or a HSO4 < HClO4.
base in water? 4.14 Which of the following is the stronger acid?
- (a) [Fe(OH2)6]3+ or [Fe(OH2)6]2+? The
F will behave as a base in water.
Fe(III) complex, [Fe(OH2)6]3+, is the stronger
4.8 What are the structures and the pKa values acid.
of chloric (HClO3) and chlorous (HClO2)
(b) [Al(OH2)6]3+ or [Ga(OH2)6]3+?
acid?
O O the aluminum-containing species is more
acidic.
Cl (c) Si(OH)4 or Ge(OH)4?

H Cl H
O O Si(OH)4, is more acidic.
O
(d) HClO3 or HClO4?
HClO4 is a stronger acid.
chloric acid chlorous acid
(e) H2CrO4 or HMnO4?
Chloric acid, the predicted pKa = 2; actual
value = 1. HMnO4 is the stronger acid.
Chlorous acid, the predicted pKa = 3; actual (f) H3PO4 or H2SO4?
value = 2.
H2SO4 is a stronger acid.
4.8 Which bases are too strong or too weak to
be studied experimentally? (a) CO32 O2, 4.15 Arrange the following oxides in order of
ClO4, and NO3 in water? increasing basicity? Al2O3, B2O3, BaO,
CO2, Cl2O7, and SO3?
CO32 is of directly measurable base strength.
order of increasing basicity is Cl2O7 < SO3 <
O2, is too strong to be studied experimentally
CO2 < B2O3 < Al2O3 < BaO.
in water.
ClO42 and NO3 are too weak to be studied 4.16 Arrange the following in order of
experimentally. increasing acidity? HSO4, H3O+, H4SiO4,
CH3GeH3, NH3, and HSO3F?
(b) HSO4, NO3, and ClO4, in H2SO4?
increasing acidity is NH3 < CH3GeH3 <
HSO4, not too strong to be studied H4SiO4 < HSO4 < H3O+ < HSO3F.
experimentally.
4.17 Which aqua ion is the stronger acid, Na+ or

NO3 is of directly measurable base strength Ag+? Ag+(aq).
in liquid H2SO4.
4.18 Which of the following elements form oxide (d) AsF3(g) + SbF5(g) [AsF2][SbF6]?
polyanions or polycations? Al, As, Cu, Mo, The very strong Lewis acid SbF5 displaces the
Si, B, Ti? Lewis acid [AsF2]+ from the Lewis base F.
polycations: Al, Cu, and Ti. (e) EtOH readily dissolves in pyridine? A
polyoxoanions (oxide polyanions): Mo Lewis acidbase complex formation reaction
between EtOH (the acid) and py (the base)
polyoxoanions: As, B, and Si. produces the adduct EtOHpy.
4.19 The change in charge upon aqua ion 4.26 Select the compound with the named
polymerization? characteristic? (a) Strongest Lewis acid:
Polycation formation reduces the average BF3, BCl3, or BBr3? BBr3.
positive charge per central M atom by +1 per BeCl2 or BCl3? Boron trichloride.
M.
B(n-Bu)3 or B(t-Bu)3? B(n-Bu)3.
4.20 Write balanced equations for the formation
of P4O124 from PO43 and for the formation (b) More basic toward BMe3: NMe3 or
of [(H2O) 4Fe(OH)2Fe(OH2)4]4+ from NEt3? NMe3.
[Fe(OH2)6]3+?
2-Me-py or 4-Me-py? 4-Me-py.
4PO43 + 8H3O+ P4O124 + 12H2O
4.27 Which of the following reactions have Keq >
2[Fe(OH2)6]3+ 1? (a) R3PBBr3 + R3NBF3 R3PBF3 +
R3NBBr3? <1
[(H2O)4Fe(OH)2Fe(OH2)4+ + 2H3O+
(b) SO2 + Ph3PHOCMe3 Ph3PSO2 +
4.21 More balanced equations?
HOCMe3? > 1.
(a) H3PO4 and Na2HPO4?
(c) CH3HgI + HCl CH3HgCl + HI? <1
H3PO4 + HPO42- 2H2PO4-
(d) [AgCl2] (aq) + 2 CN (aq) [Ag (CN)2]

(b) CO2 and CaCO3? (aq) + 2Cl(aq)? >1

CO 2 + CaCO 3 + H 2O Ca2+ + 2HCO 3-
4.22 Give the equations for HF in H2SO4 and 4.28 Choose between the two basic sites in
HF in liquid NH3? Me2NPF2?
H2SO4 + HF H3SO4+ + F- The phosphorus atom in Me2NPF2 is the

softer of the two basic sites, so it will bond
NH3 + HF NH2- + H2F+ more strongly with the softer Lewis acid BH3
4.23 Why is H2Se a stronger acid than H2S? As The hard nitrogen atom will bond more
you go down a family in the periodic chart, strongly to the hard Lewis acid BF3.
the acidy of the homologous hydrogen
4.29 Why is trimethylamine out of line?
compounds increases.
Trimethyl amine is sterically large enough to
4.24 Identifying elements that form Lewis fall out of line with the given enthalpies of
acids? All of the p-block elements except reaction.
nitrogen, oxygen, fluorine, and the lighter
4.30 Discuss relative basicities? (a) Acetone and
noble gases form Lewis acids in one of their
DMSO?
oxidation states.
DMSO is the stronger base regardless of how
4.25 Identifying acids and bases: (a) SO3 + H2O
hard or how soft the Lewis acid is. The
HSO4 + H+? The acids in this reaction ambiguity for DMSO is that both the oxygen
are the Lewis acids SO3 and H+ and the base atom and sulfur atom are potential basic sites.
is the Lewis base OH.
(b) Me2S and DMSO? Depending on the
(b) Me[B12] + Hg2+ [B12] +
EA and CA values for the Lewis acid, either
MeHg+? The Lewis acid Hg2+ displaces the
base could be stronger.
Lewis acid [B12] from the Lewis base CH3.
4.31 Write a balanced equation for the
(c) KCl + SnCl2 K+ + [SnCl3]? The dissolution of SiO2 by HF?
Lewis acid SnCl2 displaces the Lewis acid K+
from the Lewis base Cl.
SiO2 + 6HF 2H2O + H2SiF6 (c) C6H5COOH?

or C6H5COOH + HF C6H5COO- + H2F+
SiO2 + 4HF 2H2O + SiF4 4.37 The dissolution of silicates by HF? both
Both a Brnsted acidbase reaction and a 4.38 Are the f-block elements hard? yes.
Lewis acidbase reaction. 4.39 Calculate the enthalpy change for I2 with
4.32 Write a balanced equation to explain the phenol?
foul odor of damp Al2S3? The foul odor fH = -20.0kJ/mol

suggests H2S formation.
Al2 S 3 + 3H 2 O Al2 O 3 + 3H 2 S
4.33 Describe solvent properties? (a) Favor CHAPTER 5
displacement of Cl by I from an acid
center? If you choose a solvent that
Self-tests
decreases the activity of chloride relative to
iodide, you can shift the following
S5.1 Half-reactions and balanced reaction for
equilibrium to the right:
oxidation of zinc metal by permanganate
acid-Cl- + I- acid-I- + Cl- ions?
2[MnO4 (aq) + 8H+ (aq) + 5e Mn2+(aq)
(b) Favor basicity of R3As over + 4H2O(l)] reduction
R3N? Alcohols such as methanol or ethanol
would be suitable. 5 [ Zn(s) Zn2+(aq) + 2e ] oxidation
+ 3+
(c) Favor acidity of Ag over Al ? An
example of a suitable solvent is diethyl ether. 2MnO4 (aq) + 5Zn(s) + 16H+(aq)
Another suitable solvent is H2O. 5Zn2+(aq) + 2Mn2+(aq) + 8H2O(l)
(d) Promote the reaction 2FeCl3 + ZnCl2 S5.2 Does Cu metal dissolve in dilute HCl? No.
Zn2+ + 2[FeCl4]? A suitable solvent is
acetonitrile, MeCN. S5.3 Can Cr2O72 be used to oxidize Fe2+, and
would Cl oxidation be a problem? Yes.
4.34 Propose a mechanism for the acylation of
Cl- oxidation is not a problem.
benzene? An alumina surface, such as the
partially dehydroxylated one shown below, S5.4 Fuel cell emf with oxygen and hydrogen
would provide Lewis acidic sites that could gases at 5.0 bar?
abstract Cl:
E = 1.25 V.
S5.5 The fate of SO2 emitted into clouds? The
aqueous solution of SO42 and H+ ions
precipitates as acid rain.
S5.6 Can Fe2+ disproportionate under standard
conditions? No.
S5.7 bpy binding to Fe(III) or Fe(II)? Fe(II)
4.35 Why does Hg(II) occur only as preferentially.
HgS? Mercury(II) is a soft Lewis acid, and
so is found in nature only combined with soft S5.8 Potential of AgCl/Ag,Cl couple?
Lewis bases, the most common of which is Eox= 1.38 V
S2.
S5.9 Latimer diagram for Pu? (a) Pu(IV)
4.36 Write Brnsted acidbase reactions in disproportionates to Pu(III) and Pu(V) in
liquid HF? aqueous solution; (b) Pu(V) does not
(a) CH3CH2OH? The balanced equation disproportionate into Pu(VI) and Pu(IV).
is:
CH 3CH 2OH + HF CH 3CH 2OH 2+ + F- S5.10 Frost diagram for thallium in aqueous
acid?
(b) NH3? The equation is
NH + + F-
NH 3 + HF 4
5.3 Write balanced equations, if a reaction

occurs, for the following species in aerated
aqueous acid? (a) Cr2+?
4Cr2+(aq) + O2(g) + 4H+(aq) 4Cr3+(aq)
+ 2H2O(l) E = 1.65 V
(b) Fe2+?
4Fe2+(aq) + O2(g) + 4H+(aq) 4Fe3+(aq)
+ 2H2O(l) E = 0.46 V
(c) Cl? no reaction.
(d) HOCl? No reaction.
S5.11 The oxidation number of manganese? (e) Zn(s)?
Mn2+(aq) 2Zn(s) + O2(g) + 4H+(aq) 2Zn2+(aq)

S5.12 Compare the strength of NO3 as an +2H2O(l) E = 1.99 V
oxidizing agent in acidic and basic
A competing reaction is:
solution?
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g) (E =
Nitrate is a stronger oxidizing agent in acidic
0.763 V).
solution than in basic solution.
S5.13 The possibility of finding Fe(OH)3 in a 5.4 Balanced equations for redox reactions?
waterlogged soil? Fe(OH)3 is not stable. (a) Fe2+?
S5.14 The minimum temperature for reduction (i) Fe2+ will not oxidize water.
of MgO by carbon? 1800C or above.
(ii) Fe2+ will not reduce water.
(iii) Fe2+ will reduce O2 and in doing so will
Exercises be oxidized to Fe3+.
5.1 Oxidation numbers? (iv) disproportionation will not occur.
2 NO(g) + O2(g) 2 NO2(g) (b) Ru2+? Ru2+ will not oxidize or reduce
+1 -2 0 +4 -2 water. Ru2+ will reduce O2 and in doing so
will be oxidized to Ru3+. Ru2+ will
2Mn3+(aq) + 2H2O MnO2 + Mn2+ + 4H+(aq) disproportionate in aqueous acid to Ru3+ and
+3 +1 -2 +4 -2 +2 +1 metallic ruthenium.
LiCoO2(s) + C(s) LiC(s) + CoO2(s) (c) HClO2? HClO2 will oxidize water, will
+1 +3 -2 0 +1-1 +4 -2 not reduce water. HClO2 will reduce O2 and
in doing so will be oxidized to ClO3. HClO2
Ca(s) + H2(g) CaH2(s) will disproportionate in aqueous acid to ClO3
0 0 +2 -1 and HClO.
5.2 Suggest chemical reagents for redox (d) Br2? Br2 will not oxidize or reduce water.
transformations? (a) Oxidation of HCl to Br2 will not reduce O2. Br2 will not
Cl2? S2O82, H2O2, or PbO2 to oxidize Cl disproportionate in aqueous acid to Br and
to Cl2. HBrO.
(b) Reducing Cr3+(aq) to Cr2+(aq)? metallic 5.5 Standard potentials vary with
manganese, metallic zinc, or NH3OH+. temperature in opposite directions? The
(c) Reducing Ag+(aq) to Ag(s)? The reduced amino and cyano complexes must have
form of any couple with a reduction potential different equilibrium shifts with respect to
less than 0.799 V. changes in temperature that results in the
opposite directions of change for the cell
(d) Reducing I2 to I? The reduced form of potential.
any couple with a reduction potential less than
0.535 V. 5.6 Balance redox reaction in acid solution:
MnO4 + H2SO3 Mn2+ + HSO4? pH
dependence?
2MnO4 (aq) + 5H2SO3(aq) + H+(aq) 5.13 Calculate the equilibrium constant for
2Mn2+(aq) +5HSO3 (aq) + 3H2O(l) Au+(aq) + 2CN(aq) [Au(CN)2](aq)?
The potential decreases as the pH increases. K = 5.7 1038
5.14 Find the approximate potential of an
aerated lake at pH = 6, and predict the
5.7 Write the Nernst equation for (a) The
predominant species? (a) Fe? 0.5 0.6 V
reduction of O2?
(b) Mn? E = 0.55 V
Q = 1/(p(O2)[H+]4)
(c) S? At pH 0, 0.387 V. At pH 14, SO42
and
would again predominate. HSO4 is the
E = E [(0.059V)/4][log(1/(p(O2)[H+]4)] predominant sulfur species at pH 6.
(b) The reduction of Fe2O3(s)? 5.15 Frost diagram and standard potential for
+ 6
Q = 1/[H ] and E = E (RT/nF)(13.8 pH) the HSO4/S8(s) couple? 0.387 V
5.8 Using Frost diagrams? (a) What happens 5.16 Equilibrium constant for the reaction
when Cl2 is dissolved in aqueous basic Pd2+(aq) + 4 Cl(aq) [PdCl4]2(aq) in 1 M
solution? Cl2 is thermodynamically HCl(aq)? K = 4.37 1010
susceptible to disproportionation to Cl and 5.17 Reduction potential for MnO4 to MnO2(s)
ClO4 when it is dissolved in aqueous base. at pH = 9.00? E = 0.98 V
The oxidation of ClO is slow, so a solution of 5.18 Tendency of mercury species to act as an
Cl and ClO is formed when Cl2 is dissolved oxidizing agent, a reducing agent, or to
in aqueous base. undergo disproportionation? Hg2+ and
(b) What happens when Cl2 is dissolved in Hg22+ are both oxidizing agents. None of
aqueous acid solution? Cl2 will not these species are likely to be good reducing
agents. Hg22+ is not likely to undergo
disproportionate. Cl2 is thermodynamically
disproportionation.
capable of oxidizing water.
5.19 Thermodynamic tendency of HO2 to
(c) Should HClO3 disproportionate in undergo disproportionation? E = +1.275 V.
aqueous acid solution? Kinetic. (is positive), HO2 will undergo
5.9 Write equations for the following disproportionation.
reactions: (a) N2O is bubbled into aqueous 5.20 Dissolved carbon dioxide corrosive towards
NaOH solution? iron? Carbon dioxide and water generate
carbonic acid which encourages the corrosion
5N2O(aq) + 2OH(aq) 2NO3(aq) + process by lowering solution pH.
4N2 (g) + H2O(l)
5.21 What is the maximum E for an anaerobic
(b) Zinc metal is added to aqueous acidic environment rich in Fe2+ and H2S? 0.1 V.
sodium triiodide?
5.22 How will edta4 complexation affect M2+
2+
Zn(s) + I3 (aq) Zn (aq) + 3I (aq)
M0 reductions? The reduction of a M(edta)2
complex will be more difficult than the
(c) I2 is added to excess aqueous acidic reduction of the analogous M2+ aqua ion.
HClO3?
5.23 Which of the boundaries depend on the
3I2(s) + 5ClO3 (aq) + 3H2O(l) 6IO3 choice of [Fe2+]? Any boundary between a
(aq) + 5Cl (aq) + 6H+(aq) soluble species and an insoluble species will
5.10 Electrode potential for Ni2+/Ni couple at pH change as the concentration of the soluble
species changes. The boundaries between the
= 14? E = 0.21 V
two soluble species, and between the two
5.11 Will acid or base most favour the following insoluble species, will not depend on the
half-reactions? (a) Mn2+ MnO4? Base choice of [Fe2+].
(b) ClO4 ClO3? Acid 5.24 Under what conditions will Al reduce
(c) H2O2 O2? Base MgO? Above about 1400C.
(d) I2 2I? Acid or base, no difference.

5.12 Determine the standard potential for the
reduction of ClO4 to Cl2? 1.392 V
CHAPTER 6 SF6 has Oh symmetry. Analysis of the

stretching vibrations leads to:
Self-tests str = A1g (Raman, polarized) + Eg
(Raman) + T1u (IR).
S6.1 Sketch the S4 axis of an NH4+ ion. How
many of these axes are there in the ion? SF5Cl has C4v symmetry. Analysis of the
Three S4 axes.
stretching vibrations leads to:
S6.2 (a) BF3 point group? D3h. str = 3A1 (IR and Raman, polarized)
2
(b) SO4 point group? Td. + 2B1 (Raman) + E (IR, Raman).
S6.3 Symmetry species of all five d orbitals of S6.14 Symmetries of all the vibration modes of
the central Xe atom in XeF4 (D4h, Fig. 6.3)? [PdCl4]2-? A1g + B1g + B2g + A2u + B2u + 2Eu
dx2-y2 is B1g;
dxy is B2g; S6.15 SALCs for sigma bonding in O? A1g + Eg
dxz and dyz are Eg; +T1u.
dz2 is A1g.
S6.4 What is the maximum possible degeneracy
Exercises
for an Oh molecule? 3.
S6.5 A conformation of the ferrocene molecule 6.1 Symmetry elements? (a) a C3 axis and a v
that lies 4 kJ mol1 above the lowest energy plane in the NH3 molecule?
configuration is a pentagonal antiprism. Is
it polar? No.
S6.6 Is the skew form of H2O2 chiral? Yes. N N
H H
S6.7 Can the bending mode of N2O be Raman H H
H H
active? Yes.
S6.8 Confirm that the symmetric mode is Ag?
D2h character table, which is the Ag symmetry C3 v
type.
S6.9 Show that the four CO displacements in (b) a C4 axis and a h plane in the square-
the square-planar (D4h) [Pt(CO)4]2+ cation planar [PtCl4]2 ion?
transform as A1g + B1g + Eu. How many
bands would you expect in the IR and
Raman spectra for the [Pt(CO)4]2+ cation?
The reducible representation: Cl Cl Cl Cl
D4h E 2C4 C2 Pt Pt
2C2 2C2 i 2S4 Cl Cl Cl Cl
h 2 v 2 d
3N 4 0 0 2
0 0 0 4 2 0 C4 h
Reduces to A1g + B1g + Eu
A1g + B1g are Raman active. Eu is IR active. 6.2 S4 or i? (a) CO2? i
(b) C2H2? i.
S6.10 Orbital symmetry for a tetrahedral array
of H atoms in methane? A1 (c) BF3? neither.
S6.11 Orbital symmetry for a square-planar (d) SO42? three different S4.
array of H atoms? B2g. 6.3 Assigning point groups: (a) NH2Cl? Cs
S6.12 Which Pt atomic orbitals can combine with (b) CO32? D3h
which of these SALCs? The atomic orbitals
much have matching symmetries to (c) SiF4? Td
generate SALCs. 5s and 4dz2 have A1g
(d) HCN? Cv.
symmetry; the dx2-y2 has B1g symmetry; and
5px and 5py have Eu symmetry. (e) SiFClBrI? C1.
S6.13 Predict how the IR and Raman spectra of (f) BrF4? D4h.
SF5Cl differ from that of SF6?
6.4 How many planes of symmetry does a 6.12 [AuCl4] ion? of all 3N displacements
benzene molecule possess? What chloro- and irreducible representations?
substituted benzene has exactly four planes A1g + A2g + B1g + B2g + Eg + 2A2u + B2u + 3Eu
of symmetry? 7,and C6H3Cl3.
6.5 The symmetry elements of orbitals? (a) An 6.13 IR and Raman to distinguish between: (a)
s orbital? Infinite number of Cn axes, plus planar and pyramidal forms of PF3, (b)
an infinite number of mirror planes of planar and 90o-twisted forms of B2F4 (D2h
symmetry, plus center of inversion, i. and D2d respectively)?
(b) A p orbital? An infinite number of mirror (a) Planar PF3, D3h, vibrations are: A1
planes that pass through both lobes and (Raman, polarized) + 2E (IR and Raman) +
include the long axis of the orbital. In A2 (IR).
addition, the long axis is a Cn axis, where n Pyramidal PF3, C3v, vibrations are: 2A1 (IR
can be any number from 1 to . and Raman, polarized) + 2E (IR and Raman)
(c) A dxy orbital? Center of symmetry, three (b) For the planar form of B2F4 (D2h):
mutually perpendicular C2 axes, three The vibrations are:
mutually perpendicular mirror planes of 3Ag (Raman, polarized) + 2B2g (Raman) +
symmetry, two planes that are rotated by 45 B3g (Raman) + Au(inactive) + 2B1u (IR) +
about the z axis from the xz plane and the yz B2u (IR) + 2B3u (IR).
plane.
(d) A dz2 orbital? In addition to the For the 90o-twisted form of B2F4 (D2d)
The vibrations are: 3A1 (Raman, polarized) +
symmetry elements possessed by a p orbital:
B1 (Raman) + 2B2 (IR and Raman ) + 3E (IR
(i) a center of symmetry, (ii) a mirror plane
and Raman).
that is perpendicular to the C axis, (iii) an
infinite number of C2 axes that pass through
6.14 (a) Take the 4 hydrogen 1s orbitals of CH4
the center of the orbital and are perpendicular and determine how they transform under
to the C axis, and (iv) an S axis. Td. (b) Confirm that it is possible to reduce
6.6 SO32 ion? (a) Point group? C3v this representation to A1 + T2. (c) Which
atomic orbitals on C can form MOs with
(b) Degenerate MOs? 2 H1s SALCs?
(c) Which s and p orbitals have the Using symmetry Td, 3N reduces to: A1 + T2.
maximum degeneracy? 3px and 3py orbitals The MOs would be constructed from SALCs
are doubly degenerate. with H1s and 2s and 2p atomic orbitals on C.
6.7 PF5? (a) Point group? D3h.

6.15 Use the projection operator method to
(b) Degenerate MOs? 2. construct the SALCs of A1 + T2 symmetry
(c) Which p orbitals have the maximum that derive from the four H1s orbitals in
degeneracy? 3px and 3py atomic orbitals are methane..
doubly degenerate s = (1/2)(1 + 2 + 3 + 3) (= A1)
6.8 AsCl5 Raman spectrum consistent with a px = (1/2)(1 2 + 3 3) (= T2)
trigonal bipyamidal geometry? No. py = (1/2)(1 2 3 + 3) (= T2)
6.9 Vibrational modes of SO3? (a) In the plane pz = (1/2)(1 + 2 3 3) (= T2)
of the nuclei? 5 SALCs for -bonds
(b) Perpendicular to the molecular plane? (a) BF3?
1 (1/3)(1 + 2 + 3) (= A1)
(1/6)(21 2 3) and (1/2)(2 3) (=
6.10 Vibrations that are IR and Raman active?
E)
(a) SF6? None.
(b) PF5?
(b) BF3? The E modes are active in both IR (axial F atoms are 4 + 5)
and Raman. (1/2)(4 + 5) (= A1)
6.11 Vibrations of a C6v molecule that are (1/2)(4 5) (= A2)
neither IR nor Raman active? Any A2, B1, (1/3)(1 + 2 + 3) (= A1)
or B2 vibrations of a C6v molecule will not be (1/6)(21 2 3) and (1/2)(2 3) (=
observed in either the IR spectrum or the E)
Raman spectrum.
CHAPTER 7 Exercises
7.1 Name and draw the structures of the
Self-tests complexes? (a) [Ni(CO)4]? Nickel
tetracarbonyl or tetracarbonyl nickel(0).
S7.1 Give formulas corresponding to the
following names? (a) Cis- CO
diaquadichloroplatinum(II)? cis-
[PtCl2(OH2)2],
Ni
trans-diaquadichloroplatinum(II), trans- CO
OC
[PtCl2(OH2)2]. CO
(b) Diamminetetra(isothiocyanato) (b) [Ni(CN)4]2? Tetracyanonickelate (II).
chromate(III)?
[Cr(NCS)4(NH3)2] . ,can exist as, cis- 2-
[Cr(NCS)4(NH3)2] or trans-
[Cr(NCS)4(NH3)2] . NC CN
Ni
(c) Tris(ethylenediamine)rhodium (III)? NC CN
[Rh(en)3]3+.
(d) Bromopentacarbonylmanganese
(I)? [MnBr (CO)5]. (c) [CoCl4]2? Tetrachlorocobaltate (II)
(e) Chlorotris(triphenylphosphine)rhodium
(I)? [RhCl(PPh3)3]. 2-
Cl
S7.2 What type of isomers are possible for
[Cr(NO2)26H2O]? The hydrate isomers
and linkage isomers of the NO2 group. Also, Co
Cl
[Cr(ONO)(H2O)5]NO2 H2O. Cl
Cl
S7.3 Identifying isomers? Note that the two
phosphine ligands in the trans isomer are (d) [Mn(NH3)6]2+?
related, therefore, they exhibit the same Hexaamminemanganesium (II)
2+
chemical shift.
NH3
S7.4 Sketches of the mer and fac isomers of H3N NH3
[Co(gly)3]? Mn
H3N NH3
NH3
7.2 Write the formulas for the following

complexes?
(a) [CoCl(NH3)5]Cl2
(b) [Fe(OH2)6](NO3)3
(c) cis-[FeCl2(en)2]
S7.5 Which of the following are chiral? (a) cis-
(d) [Cr(NH3)5OHCr(NH3)5]Cl5
[CrCl2 (ox)2]3? Chiral .
7.3 Name the following complexes?
(b) trans-[CrCl2(ox)2]3 ? Not chiral.
(a) cis-[CrCl2(NH3)4]+? cis-
(c) cis-[RhH(CO)(PR3)2]? Not chiral.
tetra(ammine)di(chloro)chromium(III)
S7.6 Calculate all of the stepwise formation -
constants? Kf1 = 1 X 105. Kf2 will be 30% (b) trans-[Cr(NCS)4(NH3)2] ? trans-
less or 30000, Kf3 = 9000, Kf4 = 2700, Kf5 = di(ammine)tetrakis(isothiocyanato)chromate
810, and finally Kf6 = 243. (III)
(c) [Co(C2O4)(en)2]+?
bis(ethylenediamine)oxalatocobalt(III).
7.4 Four-coordinate complexes? (a) Sketch the

two observed structures?
L L L
M M
L L L L
L
tetrahedral square planar

(b) Isomers expected for MA2B2?
tetrahedral complex, no isomers, for a square-
planar complex, two isomers, cis and trans.
7.5 For five-coordinate complexes, sketch the
two observed structures?
A A
E B B
M E M
E B B
A
Trigonal Bipyramidal Square based pyramid

A = axial ligands A = axial
E = equatorial ligands B = basal
[Mg(edta)(OH2)]2
7.6 Six-coordinate complexes? (a) Sketch the 7.11 What types of isomers are [RuBr(NH3)5]Cl
two observed structures? and [RuCl(NH3)5]Br? Ionization isomers.
7.12 Which complexes have isomers?
[CoBrClI(OH2)]
7.13 Which complexes have isomers?
(a) [Pt(ox)(NH3)2] no isomers
(b) [PdBrCl(PEt3)2] has two isomers.

(b) Which one of these is rare? Trigonal
prism. (c) [IrHCO(PR3)2] has two isomers.
7.7 Explain the difference between
monodentate, bidentate, and (d) [Pd(gly)2] has two isomers.
quadridentate? A monodentate ligand can
bond to a metal atom only at a single atom, a 7.14 How many isomers are possible for the
bidentate ligand can bond through two atoms, following complexes?
a quadridentate ligand can bond through four (a) [FeCl(OH2)5]2+? None.
atoms.
(b) [IrCl3(PEt3)2]? 2
7.8 What type of isomers do you get with
ambidentate ligands? linkage isomers.
(c) [Ru(biby)3]2+? 2
7.9 Which ligand could act like a chelating (d) [CoCl2(en)(NH3)2]+? 4
ligand? (a) Triphenylphosphite, no/
(b) Bis(dimethyl)phosphino ethane (dmpe) (e) [W(CO)4(py)2] 2
yes.
(c) Bipyridine (bipy), yes.
(d) Pyrazine, no.
7.10 Draw structures of complexes that contain
the ligands (a) en, (b) ox, (c) phen, and (d)
edta? .
7.15 Draw all possible isomers for [MA2BCDE]? identical reflections to those of rutile TiO2 but
Including optical isomers, 15 isomers are shifted to slightly higher diffraction angles.
possible! .
S8.2 TiO2 in sunscreens?
A A A
B A B A B A
Titania articles absorb this ultraviolet
M M M radiation
C D E C D E
E D C S8.3 Molecular shape and vibrational modes for
XeF2? Trigonal bipyramidal, 4 total
vibrational modes.
A A A
B E B E B C
S8.4 (a) 77Se-NMR spectrum consists of a triplet
M M M of triplets? The triplet of triplets.
D C C D D E
A A A (b) Proton resonance of the hydrido ligand
consist of eight equal intensity lines? yes.
S8.5 EPR signal of new material arises from W
A A A
E A D A C A sites?
M M M
B
C
D E
B
C D
E
B 14% of naturally occurring tungsten is 183W,
which has I = . Thus, the signal is split into
2 lines.
7.16 Which of the following complexes are S8.6 Isomer shift for iron in Sr2FeO4? The
chiral? (a) [Cr(ox)3]3? Chiral Smaller and less positive.
(b) cis-[PtCl2(en)]? Chiral (The en is not S8.7 Why does the mass spectrum of ClBr3 have
planar). five peaks separated by 2 u? Halogen
isomers.
(c) cis-[RhCl2(NH3)4]+? not chiral.
(d) [Ru(bipy)3]2+? chiral
Exercises
(e) fac-[Co(NO2)3(dien)]? Not chiral.
8.1 How would you determine crystalline
(f) mer-[Co(NO2)3(dien)]? Chiral (dien is components in mineral sample? Powder X-
not planar). ray diffraction.
7.17 Which isomer, or , is the complex 8.2 Why are there no diffraction maxima in
Mn(acac)3, shown in the exercise? The borosilicate glass? Glass has no long-range
isomer. periodicity or order.
7.18 Draw both isomers, or , of the complex 8.3 What is the minimum size of a cubic
[Ru(en)3]+2 ? crystal that can be studied? 0.5 m by 0.5
m by 0.5 m.
N N
N N N N 8.4 Wavelength of neutron at 2.20 km/s? 1.80

Ru Ru 1012 m or 180 pm.
N N N N
8.5 Order of stretching frequencies? The
N N
smaller effective mass of the oscillator for
isomer isomer CN causes the molecule to have the higher
stretching frequency. The bond order for NO
7.19 Suggest a reason why Kf5 is so different? is 2.5, and N is heavier than C, hence CO has
Because of a change in coordination. a higher stretching frequency than NO.
7.20 Compare these values with those of 8.6 Wavenumber for OO in O2+? In the region
ammonia given in exercise 7.19 and suggest of 1800 cm 1.
why they are different? The chelate effect. 8.7 UV photoelectron spectrum of NH3? The
band at 11 eV is due to the lone pair and the
pyramidal angle. The ionised molecule has
CHAPTER 8 greater planarity, thus the long progression.
8.8 Raman bands assignments? N(SiH3)3 is
Self-tests planar. N(CH3) 3 is pyramidal.
S8.1 Main features of the CrO2 powder XRD

pattern? XRD pattern for CrO2 will show
8.9 Single 13C peak in NMR? Chemically S9.1 Found in aluminosilicate minerals or
distinct carbonyls are exchanging position sulfides?
sufficiently quickly. Cd and Pb will be found as sulfides.
Rb and Sr can be found in aluminosilicate
8.10 Form of 19F-NMR and 77Se-NMR spectra minerals.
of 77SeF4? 19F NMR spectrum reveals two Cr and Pd can be found in both oxides and
1:3:3:1 quartets. The 77Se-NMR spectrum is a sulfides.
triplet of triplets.
8.11 NMR spectral features for XeF5? All 5 of S9.2 Sulfur forms catenated polysulfides
the F atoms are chemically equivalent. whereas polyoxygen anions are unknown?
Approximately 25% is present as 129Xe, I = Owing to a strong tendency to form strong
1/2, and in this case the 19F resonance is a double bonds, it is more likely that
doublet. The final result is a composite: two polyoxygen anions will form pi bonds that
lines of 12.5% intensity from the 19F coupled limit extended bonding owing to restrictions
to the 129Xe, and one remaining line of 75%. on pi orbital overlap through multiple
bridging centres.
8.12 g-values? 1.94, 1.74, and 1.56.
8.13 Slower process, NMR or EPR? NMR. S9.3 Shape of XeO4 and identify the Z + 8
compound with the same structure?
8.14 Differences in EPR spectrum for d-metal A tetrahedral geometry. The same structure is
with one electron in solution versus frozen? SmO4.
In aqueous solution at room temperature,
molecular tumbling removes the effect of the S9.4 Comment on fH values? It is evident from
g-value anisotropy. In frozen solution, g- the values that as we move down the group,
value anisotropy can be observed. steric crowding of the fluorines is minimized.
8.15 Isomer shift for iron in BaFe(VI)O4? A S9.5 Further data useful when drawing
positive shift for Fe(VI) well below +0.2 mm comparisons with the value for V2O5? We
s-1. would have to know the products formed
8.16 Charge on Fe atoms in Fe4[Fe(CN)6]3? EPR upon decomposition.
and Mssbauer.
8.17 No quadrupole splitting in Mssbauer Exercises
spectrum of SbF5? The geometry must be
close to cubic in the solid state. 9.1 Maximum stable oxidation state? (a) Ba;
+2, (b) As; +5, (c) P; +5, (d) Cl; +7.
8.18 No peak in the mass spectrum of Ag at 108
u? Two isotopes, 107Ag (51.82%) and 109Ag
9.2 Form saline hydrides, oxides and
(48.18%). Compounds that contain silver will peroxides, and all the carbides react with
have two mass peaks. water to liberate a hydrocarbon?
8.19 Peaks in mass spectrum of the alkaline earth metals or Group 2 elements.
Mo(C6H6)(CO)3? 258, 230, 200, 186, and
174. 9.3 Elements vary from metals through
metalloids to non-metals; form halides in
8.20 Cyclic voltammogram of Fe(III) complex? oxidation states +5 and +3 and toxic
The complex undergoes a reversible one- gaseous hydrides? Elements in Group 15.
electron reduction with a reduction potential
of 0.21 V. Above 0.720 V the complex is 9.4 BornHaber cycle for the formation of the
oxidized. hypothetical compound NaCl2? Which
thermochemical step is responsible for the
8.21 Zeolite of composition CaAl2Si6O16.nH2O,
fact that NaCl2 does not exist?
determine n.? n=7.2 As an integer, n = 7.
The second ionization energy of
8.22 Ratio of cobalt to acetylacetonate in the sodium is 4562 kJ mol-1 and is responsible for
product? The ratio is 3:1. the fact that the compound does not exist.
CHAPTER 9 9.5 Inert pair effect beyond Group 15? The

relative stability of an oxidation state in which
the oxidation number is 2 less than the group
Self-tests number is an example of the inert pair effect.
9.6 Ionic radii, ionization energy, and metallic 10.3 Assign oxidation numbers to elements?
character? Metallic character, ionic radii
(a) H2S? H = +1, S = 2.
decrease across a period and down a group.
Ionization energy increases across a period (b) KH? H = 1, K = +1.
and decreases down a group.
(c) [ReH9]2? H = 1, Re = +7.
9.7 Names of ores? (a) Mg; MgCO3 magnesite, (d) H2SO4? H = +1, O = 2, S = +6.
(b) Al; Al2O3 bauxite, and (c) Pb; PbS galena.
(e) H2PO(OH)? H bonded to an oxygen
9.8 Identify the Z + 8 element for P. atom = +1. H bonded to the phosphorus atom?
Similarities? V (vanadium). If they are assigned an oxidation number of
+1, and O = 2, then P = +1.
10.4 Preparation of hydrogen gas?
9.9 Calculate fH for SeF6?
fH = 1397 kJ mol-1. (i) CH4(g) + H2O CO(g) + 3H2(g) (1000C)
(ii) C(s) + H2O CO(g) + H2(g) (1000C)
CHAPTER 10 (iii) CO(g) + H2O CO2(g) + H2 (g)

10.5 Properties of hydrides of the elements? (a)
Self-tests Position in the periodic table? See Figure
10.2.
S10.1 Which of the following CH4, SiH4,, or GeH4 (b) Trends in fG? See Table 10.1.
-
would best H+ or H donor?
(c) Different molecular
CH4, the strongest Bronsted acid. GeH4 hydrides? Molecular hydrides are found in
would be the best hydride donor. groups 13/III through 17/VII.
S10.2 Reactions of hydrogen compounds?
10.6 What are the physical properties of water
(a) Ca(s) + H2(g) CaH2(s). without hydrogen bonding? It most likely
(b) NH3(g) + BF3(g) H3NBF3(g). would be a gas at room temperature; ice
would be denser than water.
(c) LiOH(s) + H2(g) NR.
10.7 Which molecule has the stronger hydrogen
S10.3 A procedure for making Et3MeSn? bonds? SHO has a weaker hydrogen bond
2Et3SnH + 2Na 2Na+Et3Sn + H2 than OHS.
Na+Et3Sn + CH3Br Et3MeSn + NaBr 10.8 Name and classify the following?
(a) BaH2? barium hydride.
Exercises (b) SiH4? silane.
10.1 Where does Hydrogen fit in the periodic (c) NH3? ammonia,
chart? (a) Hydrogen in group 1? Hydrogen
has one valence electron like the group 1 (d) AsH3? Arsine.
metals and is stable as H+, especially in (e) PdH0.9? palladium hydride.
aqueous media.
(f) HI? hydrogen iodide.
(b) Hydrogen in group 17? Hydrogen can
fill its 1s orbital and make a hydride H. The 10.9 Chemical characteristics of hydrides?
halogens are diatomic gases just like (a) Hydridic character? Barium hydride
hydrogen, but chemically it fits well in both
group 1 and group 17. (b) Brnsted acidity? Hydrogen iodide.
(c) Hydrogen in group 14? There is no (c) Variable composition? PdH0.9 .
reason for hydrogen to be placed in this
(d) Lewis basicity? Ammonia.
group.
10.10 Phases of hydrides of the elements? BaH2
10.2 Low reactivity of hydrogen? Hydrogen
and PdH0.9 are solids, none is a liquid, and
exists as a diatomic molecule (H2). It has a
SiH4, NH3, AsH3, and HI are gases.
high bond enthalpy. It also only has two
electrons shared between two protons. 10.11 Structures of H2Se, P2H4, and H3O+? The
Lewis structures of these three species are:
10.21.1 Dihydrogen as an oxidizing agent? Its

reaction with an active s-block metal such as
sodium.
H3O+ should be trigonal pyramidal.

CHAPTER 11
10.12 The reaction that will give the highest
proportion of HD? Reaction (b) will
produce 100% HD and no H2 or D2. Self-tests
10.13 Most likely to undergo radical S11.1 Change in cell parameter for CsCl? At 445
reactions? (CH3)3SnH, the tin compound is C the CsCl structure changes to rock-salt and
the most likely to undergo radical reactions assumes the face centered cubic.
with alkyl halides.
S11.2 Lattice enthalpies of formation? LiF is 625
10.14 Arrange H2O, H2S, and H2Se in order? kJ mol1 and for NaF is 535 kJ mol1.
(a) Increasing acidity? H2O < H2S < H2Se. S11.3 Trend is stability of Group 1 ozonides?
(b) Increasing basicity toward a hard Group 1 ozonides are less stable compared to
acid? H2Se < H2S < H2O. the superoxides.
10.15 The synthesis of binary hydrogen S11.4 Sketch the thermodynamic cycle of Group
compounds? (i) direct combination of the 1 carbonate.
elements, (ii) protonation of a Brnsted base,
and (iii) metathesis using a compound such as M2CO3(s) M2O(s) +
LiH, NaBH4, or LiAlH4. CO2(g)
10.16 Compare BH4, AlH4, and GaH4? Since
AlH4 is more hydride-like, it is the
strongest reducing agent.
10.17 Compare period 2 and period 3 hydrogen
compounds? Period 2 compounds:
- except for B2H6, are all exoergic
2M+(g) + CO32(g) 2M+(g) +
- tend to be weaker Brnsted acids and O2(g) + CO2(g)
stronger Brnsted bases
- bond angles in period 2 hydrogen S11.5 Explain the differences in temperature of
compounds reflect a greater degree of sp3 decomposition of LiNO3 and KNO3? KNO3
hybridization decomposes in two steps at two different
temperatures.
- Several period 2 compounds exhibit strong
hydrogen bonding. KNO3(s) KNO2(s) + 1/2O2(g)
- boiling points of HF, H2O, and NH3 are all
higher than their respective period 3 2KNO2(s) K2O(s) + 2NO2(g) + 1/2O2(g)
homologues.
LiNO3 decomposes in one step.
10.18 Suggest a method for the preparation of
BiH3?
LiNO3(s) 1/2 Li2O(s) + NO2(g) + 1/4O2(g)
The redistribution of methylbismuthine,
BiH2Me. S11.6 Predicted 7Li NMR of Li3N? Two peaks in
the NMR spectrum at low temperature. Only
3BiH2Me 2BiH3 + BiMe3
one resonance in the NMR at high
10.19 Describe the compound formed between temperature.
water and Kr? A clathrate hydrate.
Exercises
10.20 Potential energy surfaces for hydrogen
bonds? (See Figure 10.9) The surface for 11.1 (a) Why are group 1 metals good reducing
the H2O, Cl system has a double minimum, agents? They have one valence electron in
while the surface for the bifluoride ion has a the ns1 subshell, and relatively low first
single minimum. ionization energies.
(b) Why are group 1 metals poor CHAPTER 12

complexing agents? They are large,
electropositive metals and have little tendency
to act as Lewis acids. Self-tests
11.2 Trends of the fluorides and chlorides of the S12.1 Predict whether (a) BeCl2 and (b) BaCl2
group 1 metals? are predominantly ionic or covalent?
Fluoride is a hard Lewis base and will form
strong complexes with hard Lewis acids. The BeCl2 is covalent; BaCl2 is ionic.
trends reverse for the chloride ion.
S12.2 Calculate the lattice enthalpies for CaO
11.3 Synthesis of group 1 alkyls? Most alkyl and CaO2 and check that the above trend is
lithiums are made using elemental lithium confirmed?
with the corresponding alkyl chlorides.
Calcium oxide and calcium peroxide are 3465
11.4 Which is more likely to lead to the desired kJ mol1 and 3040 kJ mol1.
result? (a) Cs+ or Mg2+, form an acetate
complex? Mg2+. S12.3 Use ionic radii to predict a structure type
(b) Be or Sr, dissolve in liquid of BeSe?
ammonia? Strontium. According to Table 3.6 should be close to
+ + ZnS-like structure.
(c) Li or K , form a complex with
C2.2.2? Potassium ion.
S12.4 Calculate the lattice enthalpy of MgF2 and
comment on how it will affect the solubility
11.5 Identify the compounds? compared to MgCl2?
MgF2 is 2991 kJ mol1, will reduce solubility
NaOH H2O + Sodium metal + O2 Na2O2 + compared to MgCl2.
heat Na2O
Exercises
+ NH3
12.1 Why are compounds of beryllium covalent
whereas those of the other group 2
NaNH2 elements are predominantly ionic?
11.6 Trends in solubility? Higher for LiF and Be has large polarizing power and a high
CsI, lower for CsF and LiI. charge density due.
11.7 Thermal stability of hydrides versus 12.2 Why are the properties of beryllium more
carbonates? Hydrides decompose to similar to aluminium and zinc than to
elements. Carbonates decompose to oxides. magnesium?
Because of a diagonal relationship between
11.8 The structures of CsCl and NaCl? Be and Al.
6-coordinate Na+, 8-coordinate Cs+.
12.3 Identify the compounds A, B, C, and D of
11.9 The effect of the alkyl group on the the group 2 element M?
structure of lithium alkyls? Whether a
molecule is monomeric or polymeric is based on M + H2O M(OH)2; A = M(OH)2
the streric size of the alkyl group less bulky M(OH)2 + CO2 MCO3; B = MCO3
alkyl groups lead to polymerization. 2MCO3 + 5C 2MC2 + 3CO2; C = MC2
MC2 + 2H2O M(OH)2 + C2H2
11.10 Predict the products of the following M(OH)2 + 2HCl MCl2 + 2H2O; D = MCl2.
reactions?
(a) CH3Br + Li Li(CH3) + LiBr 12.4 Why does beryllium fluoride form a glass
when cooled from a melt?
(b) MgCl2 + LiC2H5 Mg(C2H5)Br + LiBr BeF2 adopts SiO2 like arrangement.
(c) C2H5Li + C6H6 LiC6H5 + C2H6 12.5 Why is magnesium hydroxide a much more
effective antacid than calcium or barium
hydroxide? Mg(OH)2 is sparingly soluble
and mildly basic.
11
12.6 Explain why Group 1 hydroxides are much S13.1 B nuclei have I = 3/2. Predict the number
more corrosive to metals than Group 2 of lines and their relative intensities in the
1
hydroxides? H-NMR spectrum of BH4? 4. Relative
intensity ratio is 1:3:3:1.
Group 1 hydroxides are more soluble than
group 2 hydroxides, and therefore have higher S13.2 Write an equation for the reaction of
OH concentrations. LiBH4 with propene in ether solvent and a
1:1 stoichiometry and another equation for
12.7 Which of the salts MgSeO or BaSeO would
4 4 its reaction with ammonium chloride in
be expected to be more soluble in water? THF with the same stoichiometry?
MgSeO4 Simple alkenes are inert towards LiBH4.
THF
12.8 Which Group 2 salts are used as drying LiBH4 + NH4Cl BH3NH3 + LiCl + H2
agents and why?
S13.3 Write and justify balanced equations for
Anhydrous Mg, and Ca sulphates are
plausible reactions between (a) BCl3 and
preferred as drying agents, because of the
ethanol, (b) BCl3 and pyridine in
higher affinity of Mg and Ca sulphates for
hydrocarbon solution, (c) BBr3 and
water.
F3BN(CH3)3?
12.9 How do group 2 salts give rise to scaling (a) BCl3 and ethanol?
from hard water?
BCl3(g) + 3 EtOH(l) B(OEt)3(l) + 3 HCl(g)
Salts of divalent ions have low solubility.
(b) BCl3 and pyridine in hydrocarbon
solution?
12.10 Predict structures for BeTe and BaTe.
BeTe, close to ZnS-like structure. BaTe, close BCl3(g) + py(l) Cl3B py(s)
to CsCl-like structure. (c) BBr3 and F3BN(CH3)3?
BBr3(l) + F3BN(CH3)3(s) BF3(g) +
12.11 Use the data in Table 1.7 and the Ketelaar
Br3BN(CH3)3(s)
triangle in Fig. 2.38 to predict the nature of
the bonding in BeBr , MgBr , and BaBr .
S13.4 Suggest a reaction or series of reactions for
2 2 2
BeBr2 should be covalent. MgBr2 should be the preparation of N, N, N-trimethyl-

ionic. BaBr2 should be ionic B,B,B-trimethylborazine starting with
methylamine and boron trichloride?
12.12 The two Grignard compounds C H MgBr
Cl3BNCH3 + 3CH3MgBr
2 5
and 2,4,6-(CH ) C H MgBr dissolve in THF.

(CH3)3B3N3(CH3)3 + 3Mg(Br, Cl)2
3 3 6 2
What differences would be expected in the

structures of the species formed in these
S13.5 How many framework electron pairs are
solutions?
present in B H and to what structural
4 10
C2H5MgBr will be tetrahedral with two category does it belong? Sketch its
molecules of solvent coordinated to the structure?
magnesium. The bulky organic group in
7, arachno species.
2,4,6-(CH3)3C6 H2MgBr leads to a
The structure of B4H10:
coordination number of two.
12.13 Predict the products of the following

reactions?
(a) MgCl2 + 2LiC2H5 2LiCl +
Mg(C2H5)2
(b) Mg + (C2H5)2Hg Mg(C2H5)2 + Hg
(c) Mg + C2H5HgCl C2H5MgCl + Hg
S13.6 Propose a plausible product for the
reaction between Li[B H ] and Al (CH ) ?
CHAPTER 13
10 13 2 3 6

[B10H11 (AlCH3)]
Self-tests
S13.7 Propose a synthesis for the polymer (c) C = B2O3

precursor 1,7-B C H (Si(CH ) Cl) from 1,2-
10 2 10 3 2 2 13.6 Does B2H6 survive in air? If not, write the
B C H and other reagents of your choice?
10 2 12 equation for the reaction?
1,2 - B10C2H12

1,7-B10C2H12 (90%) + 1,12- No, it explodes in air.
B10C2H12 (10%) B2H6 + 3 O2 B2O3 + 3 H2O2
1,7-B10C2H10Li2 + 2Si(CH3)2Cl2 1,7 - 13.7 Predict how many different boron

B10C2H10(Si(CH3)2 + 2LiCl environments would be present in the
S13.8 Propose, with reasons, the chemical proton-decoupled 11B-NMR of a) B5H11, b)
equation (or indicate no reaction) for B4H10? a) 3 b) 2.
reactions between (a) (CH3)2SAlCl3 and 13.8 Predict the products from the
GaBr3? hydroboration of (a) (CH3)2C=CH2, (b)
(Me)2SalCl3 + GaBr3 Me2SGaBr3 + AlCl3. CH CH?
(b) TlCl and formaldehyde (HCHO) in (a) BH3 + (CH3)2C=CH2

acidic aqueous solution? No reaction. B[CH2-CH(CH3)2]3
(b) BH3 + CH CH
Exercises B(CH=CH2)3
13.1 Give a balanced chemical equation and 13.9 Diborane has been used as a rocket
conditions for the recovery of boron? propellant. Calculate the energy released
B2O3 + 3Mg 2B + 3MgO H < 0 from 1.00 kg of diborane given the
following values of fH/kJ mol-1: B2H6 =
13.2 Describe the bonding in (a) BF3? Covalent. 31, H2O = -242, B2O3 = -1264. The
(b) AlCl3? In the solid state, a layered combustion reaction is B2H6 (g) + 3 O2(g)
structure. At melting point, dimers. (c) B2H6? 3 H2O (g) + B2O3 (s). What would be the
Electron-deficient dimer. problem with diborane as a fuel?
-73,172 kJ.
13.3 Arrange the following in order of
increasing Lewis acidity: BF3, BCl3, AlCl3. Diborane is extremely toxic, and the boron
In the light of this order, write balanced containing product of combustion is a solid,
chemical reactions (or no reaction) for (a) B2O3.
BF3N(CH3)3 + BCl3 , (b) BH3CO +
BBr3? 13.10 Using BCl3 as a starting material and other
BCl3 > BF3 > AlCl3 reagents of your choice, devise a synthesis
(a) BF3N(CH3)3 + BCl3 for the Lewis acid chelating agent, F2B
BCl3N(CH3)3 + BF3 (BCl3 > BF3) C2H4BF2?
(b) BH3CO + BBr3 NR 2BCl3 + 2Hg B2Cl4 + 2HgCl2
13.4 Thallium tribromide (1.11 g) reacts B2Cl4 + 4AgF B2F4 + 4AgCl
quantitatively with 0.257 g of NaBr to form B2F4 + C2H4 F2CH2CH2BF2
a product A. Deduce the formula of A.
Identify the cation and anion? 13.11 Given NaBH4, a hydrocarbon of your
TlBr3 + NaBr NaTlBr4 choice, and appropriate ancillary reagents
and solvents, give formulas and conditions
13.5 Identify compounds A, B, and C? for the synthesis of (a) B(C2H5)3, (b)
Et3NBH3?
LiAlH4
BF3 A Heat, Ether
(a) BCl3 + 3C2H5MgCl
B(C2H5)3 + 3MgCl2
(b) [HN(C2H5)3]Cl + NaBH4

CaF2 H2O H2 + H3BN(C2H5)3 + NaCl
13.12 Draw the B12 unit that is a common motif

of boron structures; take a viewpoint along
a C2 axis?
C B
heat
(a) A = B2H6
(b) B = B(OH)3
(2) B10H12(SEt2)2 + C2H2

B10C2H12 + 2SEt2 + H2
(3) 2 B10C2H12 + 2EtO + 4EtOH
2 B9C2H12 + 2B(OEt)3 + 2H2
(4) Na[B9C2H12] + NaH
Na2[B9C2H11] + H2
THF
(5) 2Na2[B9C2H11] + FeCl2
2NaCl + Na2[Fe(B9C2H11)2]
H 2-
B
H
H H
B
B B
H H
B B
H
C B
13.13 Which boron hydride would you expect to H
be more thermally stable, B6H10 or B6H12? C B
H H B H
Give a generalization by which the thermal
Fe
stability of a borane can be judged? H B H H
B C
B6H10 H
B C H
13.14 How many skeletal electrons are present in B B H
H
B5H9? 14 B B
H B H
13.15 (a) Give a balanced chemical equation H
(including the state of each reactant and B
product) for the air oxidation of H
pentaborane(9). (b) Describe the probable
disadvantages, other than cost, for the use 13.18 (a) What are the similarities and
of pentaborane as a fuel for an internal differences in structure of layered BN and
combustion engine? graphite (Section 13.9)? (b) Contrast their
Heat reactivity with Na and Br2. (c) Suggest a
(a) 2B5H9 (l) + 12O2 (g) rationalization for the differences in
5B2O3 (s) + 9H2O (l) structure and reactivity.
(a) Their structures? Both of these
(b) The boron containing product of substances have layered structures.
combustion is a solid, B2O3. (b) Their reactivity with Na and
13.16 (a) From its formula, classify B10H14 as Br2? Graphite reacts, boron nitride is
closo, nido, or arachno. (b) Use Wades
unreactive.
rules to determine the number of
framework electron pairs for (c) Explain the differences? The large
decaborane(14). (c) Verify by detailed HOMOLUMO gap in BN means it is more
accounting of valence electrons that the difficult to remove an electron from it than
number of cluster valence electrons of from the HOMO of graphite.
B10H14 is the same as that determined in
(b)? 13.19 Devise a synthesis for the borazines (a)
(a) nido . Ph3N3B3Cl3 and (b) Me3N3B3H3, starting
(b) 12. with BCl3 and other reagents of your
(c) The total number of valence elections is choice. Draw the structures of the
(10x3)+(14x1)=44; the number of cluster products?
valence is the remainder of 44-20=24. (a) Ph3N3B3Cl3?
13.17 Starting with B10H14 and other reagents of 3 PhNH3+Cl + 3 BCl3 Ph3N3B3Cl3 + 9 HCl
your choice, give the equations for the (b) Me3N3B3H3?
synthesis of [Fe(nido-B9C2H11)2]2-, and
sketch the structure of this species? 3 MeNH3+Cl + 3 BCl3 Me3N3B3Cl3 + 9 HCl
(1) B10H14 + 2SEt2 Me3N3B3Cl3 + 3 LiH Me3N3B3H3 + 3 LiCl
B10H12(SEt2)2 + H2
The structures:
Exercises
14.1 Silicon forms the chlorofluorides SiCl3F,
SiCl2F2, and SiClF3. Sketch the structures
of these molecules?
13.20 Give the structural type and describe the

structures of B4H10, B5H9, and 1,2-
B10C2H12?
B4H10, is an arachno borane. 14.2 Explain why CH4 burns in air whereas CF4
B5H9, is a nido borane. does not. The enthalpy of combustion of
1,2-B10C2H12 is a closo carborane CH4 is 888 kJ mol1 and the CH and CF
bond enthalpies are 413 and 489 kJ
13.21 Arrange the following boron hydrides in mol1 respectively?
order of increasing Brnsted acidity, and The bond enthalpy of a CF bond is higher
draw a structure for the probable structure than the bond enthalpy of a CH bond.
of the deprotonated form of one of them:
B2H6, B10H14, B5H9? In a series of boranes, 14.3 SiF4 reacts with (CH3)4NF to form
the acidity increases as the size of the borane [(CH3)4N][SiF5]. (a) Use the VSEPR rules
increases. to determine the shape of the cation and
anion in the product; (b) Account for the
fact that the 19F NMR spectrum shows two
fluorine environments?
CHAPTER 14 (a) The cation is [(CH3)4N]+
+
Self-tests CH3
S14.1 Describe how the electronic structure of
graphite is altered when it reacts with (a) N
potassium, (b) bromine? H3C CH3
(a) With potassium? Potassium results in a C
material with a higher conductivity. H3
(b) With bromine? Bromine can remove
electrons from the -symmetry HOMOs of The anion is SiF5
graphite. This also results in a material with a F
-
higher conductivity.
S14.2 Use the bond enthalpy data in Table 14.2
F
and above to calculate the standard
enthalpy of formation of CH4 and SiH4?
Si F
CH4: fH= 61kJ mol1
SiH4: fH= +39 kJ mol1 F
S14.3 Propose a synthesis of D13CO2 starting
from 13CO? F
13 13
CO(g) + 2MnO2(s) CO2(g) + Mn2O3(s) (b) There are two different fluorine
environments.
2Li(s) + D2 2LiD(s)
13
CO2(g) + LiD(et) Li+D13CO2(et) 14.4 Draw the structure and determine the
charge on the cyclic anion [Si4O12] ?
8- 14.11 Give balanced chemical equations and

O
conditions for the recovery of silicon and
germanium from their ores?
O
Si
O
SiO2(s) + C(s) Si(s) + CO2(g) H < 0
Si
GeO2(s) + 2H2(g) Ge(s) + 2H2O(g)
O O
Si H < 0
O O
Si
14.12 (a) Describe the trend in band gap energy,
Eg, for the elements carbon (diamond) to
O tin (grey). (b) Does the electrical
Charge = 8. conductivity of silicon increase or decrease
119
when its temperature is changed from 20C
14.5 Predict the appearance of the Sn-NMR to 40C?
spectrum of Sn(CH3)4? Doublet
(a) There is a decrease in band gap energy
14.6 Predict the appearance of the 1H-NMR from carbon (diamond) to grey tin. (b)
spectrum of Sn(CH3)4? Doublet Increase.
14.7 Use the data in Table 14.2 and the 14.13 Preferably without consulting reference
additional bond enthalpy data given here material, draw a periodic table and
to calculate the enthalpy of hydrolysis of indicate the elements that form saline,
CCl4 and CBr4. Bond enthalpies/(kJ mol1): metallic, and metalloid carbides?
OH = 463, HCl = 431, HBr = 366? Ionic(silane) Metallic Metalloid
hHCCl4 = 110 kJmol1 carbides carbides carbides
hHCBr4 = 86 kJmol1 Group I Li, Na, K,
elements Rb, Cs
14.8 Identify the compounds A to F:? Group II Be, Mg, Ca,
(A) SiCl4 (B) SiRCl3 (C) RSi(OH)3. (D) elements Sr, Ba
RSiOSiR +H2O (E) SiR4 (F)? SiO2 Group 13 Al B
elements
YYYYY14.9 (a) Summarize the trends in Group 14 Si
relative stabilities of the oxidation states of elements
the elements of Group 14, and indicate the 3d-Block Sc, Ti, V,
elements that display the inert pair effect. elements Cr, Mn, Fe,
(b) With this information in mind, write Co, Ni
balanced chemical reactions or NR (for no 4d-Block Zr, Nb, Mo,
reaction) for the following combinations, elements Tc, Ru
and explain how the answer fits the trends.
5d-Block La, Hf, Ta,
(i) Sn2+(aq) + PbO2(s) (excess) (air elements W, Re, Os
excluded) (ii) Sn2+(aq) + O2(air) ? 6d-Block Ac
(a) +4 is the most stable oxidation state for elements
the lighter elements, but +2 is the most stable Lanthanides Ce, Pr, Nd,
oxidation state of Pb. Pb therefore displays Pm, Sm,
the inert-pair effect. Eu, Gd, Tb,
(b) (i) Sn2+ + PbO2 + 4 H+ Sn4+ + Pb2+ + Dy, Ho, Er,
2H2O, (ii) 2Sn2+ + O2 + 4H+ 2Sn4+ + Tm, Yb, Lu
2H2O.
14.14 Describe the preparation, structure and
14.10 Use data from Resource section 3 to classification of (a) KC8, (b) CaC2, (c) K3C60?
determine the standard potential for each (a) KC8? Formed by heating graphite with
of the reactions in Exercise 14.5 (b). In potassium vapor or by treating graphite with a
each case, comment on the agreement or solution of potassium in liquid ammonia.
disagreement with the qualitative There is a layered structure of alternating sp2
assessment you gave for the reactions? carbon atoms and potassium ions, a saline
(i) V = +1.31 V. (ii) V= 1.08 V. Both carbide.
reactions agree with the predictions made in
Excercise 14.5. (b) CaC2? Ca(l) + 2C(s) CaC2(s) or
CaO(s) + 3C(s) CaC2(s) + CO(g)
Calcium carbide contains discrete C22 ions. NH3 + ClO + H+ [H3NCl-O] + H+

H2NCl + H2O
(c) K3C60? A solution of C60 can be treated
with elemental potassium. It is ionic. H2NCl + NH3 H2NNH2 + HCl
Both can be thought of as redox reactions.
14.15 Write balanced chemical equations for the
reactions of K2CO3 with HCl(aq) and of S15.5 When titrated against base a sample of
Na4SiO4 with aqueous acid? polyphosphate gave end points at 30.4 and
K2CO3(aq) + 2HCl(aq) 2KCl(aq) + CO2(g) + 45.6 cm3. What is the chain length?
H2O(l) There are (30.4 cm3)/(7.6 cm3) = 4 strongly
Na4SiO4(aq) + 4HCl(aq) 4NaCl(aq) + SiO2(s) + acidic OH groups per molecule. A molecule
2H2O(l) with 2 terminal OH groups and four further
OH groups is a tetrapolyphosphate.
14.16 Describe in general terms the nature of the
[SiO3]n2 ion in jadeite and the silica- Exercises
alumina framework in kaolinite? 15.1 List the elements in Groups 15 and indicate
The structures of jadeite and kaolinite consist the ones that are (a) diatomic gases, (b)
of extended one- and two-dimensional nonmetals, (c) metalloids, (d) true metals.
structures, respectively. The [SiO32]n ions in Indicate those elements that display the
jadeite are a linear polymer of SiO4 inert-pair effect?
tetrahedra. The two-dimensional
aluminosilicate layers in kaolinite represent Type of Diatomic Inert pair
another way of connecting SiO4 tetrahedra. element gas? effect?
N Non- yes No
metal
14.17 (a) How many bridging O atoms are in the P Non- no No
framework of a single sodalite cage? (b) metal
Describe the (supercage) polyhedron at the As nonmetal no No
centre of the Zeolite A structure in Fig.
Sb metalloid no No
14.3?
Bi metalloid no Yes
(a) 48.
O nonmetal yes No
(b) Eight sodalite cages are linked together to S nonmetal no No
form the large cage of zeolite A. Se nonmetal no No
Te nonmetal no No
CHAPTER 15
15.2 (a) Give complete and balanced chemical
equations for each step in the synthesis of
Self-tests H PO from hydroxyapatite to yield (a)
3 4
high-purity phosphoric acid and (b)

S15.1 Consider the Lewis structure of a segment fertilizer-grade phosphoric acid. (c)
of the structure of bismuth shown in Fig. Account for the large difference in costs
15.2. Is this puckered structure consistent between these two methods?
with the VSEPR model? Yes.
(a) high-purity phosphoric acid?
S15.2 Refined hydrocarbons and liquid hydrogen
are also used as rocket fuel. What are the 2Ca3(PO4)2 + 10C + 6SiO2
advantages of dimethylhydrazine over P4 + 10CO + 6CaSiO3
these fuels?
P4 (pure) + 5O2 P4O10
Dimehylhydrazine ignites spontaneously, and
produces less CO2. P4O10 + 6H2O 4H3PO4 (pure)
S15.3 From trends in the periodic table, decide (b) Fertilizer grade H3PO4?
whether phosphorus or sulphur is likely to
Ca5(PO4)3OH + 5H2SO4
be the stronger oxidizing agent? Sulphur.
3H3PO4 (impure) + 5CaSO4 + H2O
S15.4 Summarize the reactions that are used for
the synthesis of hydrazine and (c) Account for the difference in cost?
hydroxylamine. Are these reactions best
described as electron-transfer processes or
nucleophilic displacements?
Fertilizer-grade phosphoric acid involves a P4O10 + 6H2O 4H3PO4

single synthetic step for a product that
(c) Reaction of the product from part (b)
requires little or no purification.
with CaCl2?
15.3 Ammonia can be prepared by (a) the
2H3PO4(l) + 3CaCl2(aq)
hydrolysis of Li N or (b) the high-
3
temperature, high-pressure reduction of N 2 Ca3(PO4)2(s) + 6HCl(aq)

by H . Give balanced chemical equations
2
for each method starting with N , Li, and

2
15.9 Starting with NH3(g) and other reagents of
H , as appropriate. (c) Account for the
2
your choice, give the chemical equations
lower cost of the second method? and conditions for the synthesis of (a)
HNO , (b) NO2 , (c) NH OH, (d) N3?
3 2
(a) Hydrolysis of Li3N?

(a) HNO3?
6Li + N2 2Li3N
4NH3(aq) + 7O2(g) 6H2O(g) + 4NO2(g)
2Li3N + 3H2O 2NH3 + 3Li2O
High temperature
(b) Reduction of N2 by H2?
(b) NO2?
N2 + 3H2 2NH3
2NO2(aq) + 2OH(aq)
(c) Account for the difference in cost? The
second process is considerably cheaper than NO2(aq) + NO3(aq) + H2O(l)
the first, because lithium is very expensive. (c) NH2OH? cold aqueous acidic solution
15.4 Show with an equation why aqueous NO2(aq) + 2HSO3(aq) + H2O(l)
solutions of NH NO are acidic?
4 3
NH3OH+(aq) + 2SO42(aq)
NH4NO3(s) + H2O NH4+ + NO3-(aq) (d) N3? at elevated temperatures:
15.5 Carbon monoxide is a good ligand and is 3NaNH2(l) + NaNO3
toxic. Why is the isoelectronic N molecule
2
not toxic? NaN3 + 3NaOH + NH3(g)

N2 itself, with a triple bond between the two 2NaNH2(l) + N2O NaN3 + NaOH +
atoms, is strikingly unreactive. NH3
15.6 Compare and contrast the formulas and 15.10 Write the balanced chemical equation
stabilities of the oxidation states of the corresponding to the standard enthalpy of
common nitrogen chlorides with the formation of P O (s). Specify the structure,
4 10
phosphorus chlorides? physical state (s, l, or g), and allotrope of

the reactants. Do either of the reactants
The only isolable nitrogen chloride is NCl3,
differ from the usual practice of taking as
and it is thermodynamically unstable. Both
reference state the most stable form of an
PCl3 and PCl5 are stable.
element?
15.7 Use the VSEPR model to predict the
P4(s) + 5O2(g) P4O10(s)
probable shapes of (a) PCl4+, (b) PCl4, (c)
AsCl ? 5 15.11 Without reference to the text, sketch the
+ general form of the Frost diagrams for
(a) PCl4 ? tetrahedron.
phosphorus (oxidation states 0 to +5) and
(b) PCl4? A see-saw. bismuth (0 to +5) in acidic solution and
discuss the relative stabilities of the +3 and
(c) AsCl5? A trigonal bipyramid. +5 oxidation states of both elements?
15.8 Give balanced chemical equations for each (i) Bi(III) is much more stable than Bi(V), and
of the following reactions: (a) oxidation of (ii) P(III) and P(V) are both about equally
P with excess oxygen, (b) reaction of the
4
stable.
product from part (a) with excess water, (c)
reaction of the product from part (b) with
a solution of CaCl and name the product?
2
(a) Oxidation of P4 with excess O2?

P4 + 5O2 P4O10
(b) Reaction of the product from part (a)
with excess H2O?
and H2PO22 useful as oxidizing or

reducing agents?
E = 0.839 V.
HPO32 and H2PO2 ions will be much better
reducing agents than oxidizing agents.
15.16 Identify the compounds A, B, C, and D?
D
LiAlH4
15.12 Are reactions of NO2 as an oxidizing agent Cl2

Cl2/hv
generally faster or slower when pH is AS A B
lowered? Give a mechanistic explanation
for the pH dependence of NO2 oxidations?
3RMgBr
The rates of reactions in which nitrite ion is
reduced are increased as the pH is lowered.
15.13 When equal volumes of nitric oxide (NO) C
and air are mixed at atmospheric pressure
a rapid reaction occurs, to form NO and 2
(a) A = AsCl3
N O . However, nitric oxide from an
2 4
(b) B = AsCl5
automobile exhaust, which is present in the (c) C = AsR3
parts per million concentration range, (d) D = AsH3
reacts slowly with air. Give an explanation
for this observation in terms of the rate law 15.17 Sketch the two possible geometric isomers
and the probable mechanism? of the octahedral [AsF Cl ] and explain
4 2
The rate law must be more than first order in how they could be distinguished by 19F
NO concentration. NMR?
15.14 Give balanced chemical equations for the The cis isomer gives two 19F signals and the
reactions of the following reagents with trans isomer gives one signal.
PCl and indicate the structures of the
5
products: (a) water (1:1), (b) water in

excess, (c) AlCl , (d) NH Cl?
3 4
(a) H2O? tetrahedral POCl3.

PCl5 + H2O POCl3 + 2HCl
(b) H2O in excess?
2PCl5(g) + 8H2O(l) 2H3PO4(aq) +
10HCl(aq)
(c) AlCl3? tetrahedral.
PCl5 + AlCl3 [PCl4]+[AlCl4]
(d) NH4Cl? Cyclic molecules or linear
chain polymers
15.18 Identify the nitrogen compounds A, B, C,
nPCl5 + nNH4Cl D, and E?
[(N = P(Cl)2)n] + 4nHCl (a) A = NO2
(b) B = HNO3; C = NO
15.15 Use standard potentials (Resource section (c) D = N2O4
3) to calculate the standard potential of the
reaction of H3PO2 with Cu2+. Are HPO22 (d) E= NO2
(e) F = NH4+
15.19 Use the Latimer diagrams in Resource 16.3 Which hydrogen bond would be stronger:
section 3 to determine which species of N SH . . . O or OH . . . S?
and P disproportionate in acid conditions?
OH hydrogen bonds are stronger.
The species of N and P that disproportionate
16.4 Which of the solvents ethylenediamine
are N2O4, NO, N2O, NH3OH+, H4P2O6, and P.
(which is basic and reducing) or SO (which
2
is acidic and oxidizing) might not react

with (a) Na S , (b) K Te ?
2 4 2 3
CHAPTER 16
ethylenediamine is a better solvent than sulfur
dioxide.
Self-tests
16.5 Rank the following species from the
S16.1 Determine whether the decomposition of strongest reducing agent to the strongest
H O is spontaneous in the presence of
2 2
oxidizing agent: SO42,SO32,O3SO2SO32?
either Br or Cl ? 2 2
S2O82 > SO42 > SO32
The decomposition of H2O2 is 16.6 Predict which oxidation states of Mn will
thermodynamically favored in presence of Br be reduced by sulfite ions in basic
In Presence of Cl conditions?
The decomposition of H2O2 is Mn (+VII, +VI, +V, +IV, +III) will be

thermodynamically favored in presence of Cl reduced by sulfite ions in basic solution.
. 16.7 (a) Give the formula for Te(VI) in acidic
S16.2 Probable structures of SO2F- and aqueous solution and contrast it with the
(CH3) 3NSO2, and predict reactions with formula for S(VI). (b) Offer a plausible
OH-. explanation for this difference?
Both are trigonal pyramidal. OH- displaces (a) Formulas? H5TeO6 and HSO4
F or (CH3) 3N.
(b) An explanation? Tellurium is a larger
Exercises element than sulfur and can increase its
coordination number.
16.1 State whether the following oxides are
acidic, basic, neutral, or amphoteric: CO , 2
16.8 Use the standard potential data in
P O , SO , MgO, K O, Al O , CO?
2 5 3 2 2 3
Resource section 3 to predict which
oxoanions of sulfur will disproportionate in
CO2, SO3, P2O5, and Al2O3 are amphoteric. acidic conditions?
CO is neutral; MgO and K2O are acidic.
S2O62and S2O32.
16.2 (a) Use standard potentials (Resource 16.9 Use the standard potential data in
section 3) to calculate the standard Resource section 3 to predict whether
potential of the disproportionation of H O 2 2
SeO32 is more stable in acidic or basic
in acid solution. (b) Is Cr a likely catalyst 2+
solution?
for the disproportionation of H O ? (c) 2 2
Given the Latimer diagram The SeO32 is marginally more stable in acid
solutions.
-0.13 1.51
O2 HO2- H2O2 16.10 Predict whether any of the following will be
reduced by thiosulfate ions,S2O32, in acidic
in acidic solution, calculate rG for the conditions: VO2+, Fe3+, Cu+, Co3+?
disproportionation of hydrogen superoxide
(HO ) into O and H O , and compare the
2
2 2 2
Fe3+ and Co3+ will be reduced.
result with its value for the
disproportionation of H O ? 2 2
16.11 SF reacts with BF to form [SF ][BF ]. Use
4 3 3 4
(a) The disproportionation of H2O2 and VSEPR theory to predict the shapes of the
HO2? 1.068 V. cation and anion?
(b) Catalysis by Cr2+? Cr2+ is not capable SF4+ trigonal pyramidal, BF4 tetrahedral.
of decomposing H2O2.
(c) The disproportionation of HO2? rG = 16.12 Tetramethylammonium fluoride (0.70 g)
157 kJ. For the disproportionation of H2O2 reacts with SF (0.81 g) to form an ionic
4
(part (a)), rG = 103 kJ. product. (a) Write a balanced equation for
the reaction and (b) sketch the structure of gree

the anion. (c) How many lines would be n
observed in the F-NMR spectrum of the
19
B liqu lower soft dark
anion? r2 id er red-
bro
(a) SF4 + (CH3)4NF [(CH3)4N]+[SF5]; (b)
wn
square pyramidal structure; (c) two F
I2 soli lowest soft dark
environments.
d est viol
16.13 Identify the sulfur-containing compounds
et
A, B, C, D, E, and F?
H gas Col
A = S2Cl2, B = S4N4, C = S2N2, D = K2S2O3, e orle
ss
E = S2O62, F = SO2.
N gas colo
e rless
CHAPTER 17 A gas colo
r rless
K gas colo
Self-tests r rless
X gas colo
S17.1 One source of iodine is sodium iodate,
e rless
NaIO . Which of the reducing agents
3
SO (aq) or Sn (aq) would seem practical

2
2+
from the standpoints of thermodynamic

17.2 Describe how the halogens are recovered
feasibility and plausible judgements about
from their naturally occurring halides and
cost? Standard potentials are given in
rationalize the approach in terms of
Resource section 3?
standard potentials. Give balanced
Both. SO2 is cheaper. chemical equations and conditions where
appropriate?
S17.2 Predict the 19F-NMR pattern for IF7?
For F:
2 resonances.
F2 + H2SO4 CaSO4 + 2 HF
S17.3 From the perspective of structure and
bonding, indicate several polyhalides that 2 HF + 2 KF 2 K+HF2
are analogous to [pyIpy]+, and describe
their bonding? 2 K+HF2 + electricity F2 + H2 + 2 KF
Examples include I3, IBr2, ICl2, and IF2. For Cl:

The three centers contribute four electrons to 2 Cl + 2 H2O + electricity Cl2 + H2 +
three molecular orbitals, one bonding, one 2 OH
nonbonding, and one antibonding.
For Br and I:
Exercises
2 X + Cl2 X2 + 2 Cl (X = Br,
17.1 Preferably without consulting reference I)
material, write out the halogens and noble
gases as they appear in the periodic table, 17.3 Sketch a choralkali cell. Show the half-cell
and indicate the trends in (a) physical state reactions and indicate the direction of
(s, l, or g) at room temperature and diffusion of the ions. Give the chemical
pressure, (b) electronegativity, (c) hardness equation for the unwanted reaction that
of the halide ion, (d) color? would occur if OH migrated through the

membrane and into the anode

Phy Electron Har Col compartment?
sica egativit dnes or
l y s of A drawing of the cell is shown in Figure 17.3.
stat hali anode: 2 Cl(aq) Cl2(g) + 2 e
e de
ion cathode: 2 H2O(l) + 2 e 2 OH(aq) + H2(g)
F gas highest hard light - unwanted reaction:
2 (4.0) est yell
ow 2 OH(aq) + Cl2(aq) ClO(aq) +
C gas lower soft yell Cl(aq) + H2O(l)
l2 er ow-
17.4 Sketch the form of the vacant s* orbital of shapes of IF and the cation and anion in X,
3
a dihalogen molecule and describe its role (c) predict how many 19F-NMR signals
in the Lewis acidity of the dihalogens? would be observed in IF and X? 3
a). X = IF4N(CH3)4
b) Different possible arrangements of
IF3:
Since the 2u* antibonding orbital is the

LUMO for a X2 molecule, it is the orbital that
accepts the pair of electrons from a Lewis
base.
17.5 Which dihalogens are thermodynamically
capable of oxidizing H O to O ? The shape of anion IF4 is Square planar.
The shape of cation (CH3)4N+ is
2 2
Cl2 and F2. Tetrahedral.

17.6 Nitrogen trifluoride, NF , boils at 129C
3
and is devoid of Lewis basicity. By c).IF3, two. IF4, one.

contrast, the lower molar mass compound
NH boils at 33C and is well known as a
3
Lewis base. (a) Describe the origins of this 17.9 Use the VSEPR model to predict the shapes
very large difference in volatility. (b) of SbCl , FClO , and [ClF ]+?
5 3 6
Describe the probable origins of the SbCl5 is trigonal bipyramidal, FClO3 is

difference in basicity? pyramidal, and ClF6 is octahedral.
(a) Difference in volatility? Ammonia 17.10 Indicate the product of the reaction
exhibits hydrogen bonding. between ClF and SbF ? 5 5
(b) Explain the difference in basicity? The +

[ClF4] [SbF6] .
strong electron-withdrawing effect in NF3

reduces the basicity. 17.11 Sketch all the isomers of the complexes
MCl F and MCl F . Indicate how many
4 2 3 3
fluorine environments would be indicated

17.7 Based on the analogy between halogens in the 19F-NMR spectrum of each isomer?
and pseudohalogens write: (a) the balanced MCl4F2, the cis isomer, 1; the trans isomer, 2.
equation for the probable reaction of MCl3F3, the fac isomer, 1 the mer isomer, 2.
cyanogen, (CN) , with aqueous sodium
2
hydroxide, (b) the equation for the

probable reaction of excess thiocyanate
with the oxidizing agent MnO (s) in acidic
2
aqueous solution, (c) a plausible structure

for trimethylsilyl cyanide?
(a) The reaction of NCCN with NaOH?
NCCN(aq) + 2 OH(aq) CN(aq) +
NCO(aq) + H2O(l)
(b) The reaction of SCN with MnO2 in
aqueous acid?
2SCN(aq) + MnO2(s) + 4 H+(aq)
(SCN)2(aq) + Mn2+(aq) + 2 H2O(l)
(c) The structure of trimethylsilyl
cyanide? Trimethylsilyl cyanide contains
an SiCN single bond.
17.8 Given that 1.84 g of IF reacts with 0.93 g of

3
[(CH ) N]F to form a product X, (a) identify

3 4
X, (b) use the VSEPR model to predict the

17.12 (a) Use the VSEPR model to predict the 17.19 Explain why CsI (s) is stable with respect to
3
probable shapes of [IF ] and IF . (b) Give a 6

+
7 the elements but NaI (s) is not?
3
plausible chemical equation for the

Large cations stabilize large, unstable anions.
preparation of [IF ][SbF ]? 6 6
17.20 Write plausible Lewis structures for (a)

(a) The structures of [IF6]+ and IF7? IF6+,
ClO and (b) I O and predict their shapes
octahedral; IF7, pentagonal bipyramid. 2 2 6
and the associated point group?

(b) The preparation of [IF6] [SbF6]?
(a).
IF7 + SbF5 [IF6][SbF6]
17.13 Predict the shape of the doubly chlorine

bridged I Cl molecule by using the VSEPR
2 6
(b) I2O5?
model and assign the point group?
A planar dimer (I2Cl6).
17.14 Predict the structure and identify the point

group of ClO F? trigonal pyramidal, Cs2
symmetry.
17.15 Predict whether each of the following
17.21 (a) Give the formulas and the probable
solutes is likely to make liquid BrF a 3
relative acidities of perbromic acid and
stronger Lewis acid or a stronger Lewis
periodic acid. (b) Which is the more stable?
base: (a) SbF , (b) SF , (c) CsF?
5 6
(a) The formulas are HBrO4 and H5IO6. The

(a) SbF5? increases the acidity of BrF3.
difference lies in iodines ability to expand its
(b) SF6? No effect on the acidity or basicity coordination shell.
of BrF3. (b) Relative stabilities? Periodic acid is
(c) CsF? Increases the basicity of BrF3. thermodynamically more stable.
17.16 Predict the appearance of the F-NMR 19 17.22 (a) Describe the expected trend in the
spectrum of IF ? Two resonances. 5
+ standard potential of an oxoanion in a
solution with decreasing pH. (b)
. Demonstrate this phenomenon by
17.17 Predict whether each of the following calculating the reduction potential of ClO4
compounds is likely to be dangerously at pH = 7 and comparing it with the
explosive in contact with BrF and explain 3
tabulated value at pH = 0?
your answer: (a) SbF , (b) CH OH, (c) F , 5 3 2
(d) S Cl ?
2 2
(a) The expected trend? E decreases as the
pH increases.
(a) SbF5? Since SbF5 cannot be oxidized, it
will not form an explosive mixture with BrF3. (b) E at pH 0 and pH 7 for ClO4?
(b) CH3OH? Methanol, being an organic E = 1.201 V (see Appendix 2).
compound, is readily oxidized by strong
At pH 7, V = 0.788 V
oxidants.
17.23 With regard to the general influence of pH
(c) F2? No. on the standard potentials of oxoanions,
(d) S2Cl2? S2Cl2 will be oxidized to higher explain why the disproportionation of an
valent sulfur fluorides. oxoanion is often promoted by low pH?
Low pH results in a kinetic promotion:
protonation of an oxo group aids oxygen
17.18 The formation of Br from a 3

halogen bond scission.
tetraalkylammonium bromide and Br is 2
only slightly exoergic. Write an equation 17.24 Which oxidizing agent reacts more readily
(or NR for no reaction) for the interaction in dilute aqueous solution, perchloric acid
of [NR ][Br ] with I in CH Cl solution and
4 3 2 2 2
or periodic acid? Give a mechanistic
give your reasoning? explanation for the difference?
Br3 + I2 2 IBr + Br Periodic acid.

17.25 (a) For which of the following anions is 18.2 Which of the noble gases would you choose
disproportionation thermodynamically as (a) The lowest-temperature
favourable in acidic solution: OCl , ClO2 , 2 refrigerant? Helium.
ClO2 , and ClO4 ? (If you do not know the
(b) An electric discharge light source
properties of these ions, determine them
from a table of standard potentials.) (b) requiring a safe gas with the lowest
For which of the favourable cases is the ionization energy? Xenon.
reaction very slow at room temperature? (c) The least expensive inert
The rates of disproportionation are probably atmosphere? Argon.
HClO > HClO2 > ClO3. 18.3 By means of balanced chemical equations
17.26 Which of the following compounds present and a statement of conditions, describe a
an explosion hazard? (a) NH ClO , (b) 4 4
suitable synthesis of (a) XeF2? Xe and F2
Mg(ClO ) , (c) NaClO , (d) [Fe(H O) ][ClO ] .
4 2 4 2 6 4 2
at 400C, or photolyze Xe and F2 in glass:
Explain your reasoning? Xe(g) + F2(g) XeF2(s)
(a) NH4ClO4? Ammonium perchlorate is a (b) XeF6? High temperature, but have a large
dangerous compound, since the N atom of the excess of F2:
NH4+ ion is in its lowest oxidation state and
can be oxidized. Xe(g) + 3 F2(g) XeF6(s)
(b) Mg(ClO4)2? Not an explosion hazard. (c) XeO3?
(c) NaClO4? Not an explosion hazard. XeF6(s) + 3 H2O(l) XeO3(s) + 6 HF(g)
(d) [Fe(H2O)6] [ClO4]2? An explosion 18.4 Draw the Lewis structures of (a) XeOF4?
hazard, since Fe(II) can be oxidized to Fe(III). (b) XeO2F2? (c) XeO64?
17.27 Use standard potentials to predict which of

the following will be oxidized by ClO ions
in acidic conditions: (a) Cr3+, (b) V3+, (c)
Fe2+, (d) Co2+?
(a) Cr3+? No. (b) V3+? Yes. (c) Fe2+? Yes. (d)
Co2+? No.
18.5 Give the formula and describe the

CHAPTER 18 structure of a noble gas species that is
isostructural with (a) ICl4? XeF4
Self-tests (b) IBr2? Linear geometry. Isostructural
with XeF2.
S18.1 Write a balanced equation for the
decomposition of xenate ions in basic (c) BrO3? Trigonal pyramidal geometry.
solution for the production of perxenate Isostructural with XeO3.
ions, xenon, and oxygen (d) ClF? Isostructural with the cation XeF+.
4
2 HXeO4 (aq) + 2 OH (aq) XeO6 (aq) + Xe(g) 18.6 (a) Give a Lewis structure for XeF7?
+ O2(g) + 2 H2O(l)
Exercises
18.1 Explain why helium is present in low
concentration in the atmosphere even
though it is the second most abundant
element in the universe?
(b) Speculate on its possible structures by
Helium present in todays atmosphere is the using the VSEPR model and analogy with
product of ongoing radioactive decay. other xenon fluoride anions? Pentagonal
bipyramid.
18.7 Use molecular orbital theory to calculate the group oxidation number is not achieved
the bond order of the diatomic species E2+ by N?
with E=He and Ne? He22+ = 0.5, Ne22+ = 0.5.
18.8 Identify the xenon compounds A, B, C, D,

and E?
A = XeF2(g)

B = [XeF]+[MeBF3]
C = XeF6
D = XeO3 19.2 Explain why the enthalpy of sublimation of
E = XeF4 (g). Re(s) is significantly greater than that of
Mn(s)?
18.9 Predict the appearance of the 129Xe-NMR As atoms become heavier, more energy is
spectrum of XeOF3+. needed to vaporize them.
1:3:3:1 quartet
19.3 State the trend in the stability of the group
18.10 Predict the appearance of the 19F-NMR oxidation state on descending a group of
spectrum of XeOF4. metallic elements in the d block. Illustrate
Strong central line, two other lines the trend using standard potentials in
symmetrically distributed around the central acidic solution for Groups 5 and 6.
line. The group oxidation number increases in
stability as you descend a group.
CHAPTER 19 19.4 For each part, give balanced chemical
equations or NR (for no reaction) and
Self-tests rationalize your answer in terms of trends
in oxidation states.
S19.1 Refer to the appropriate Latimer diagram
in Resource section 3 and identify the (a) Cr2+ (aq) + Fe3+ (aq) ?
oxidation state and formula of the species
Cr2+(aq) + Fe3+(aq) Cr3+(aq) + Fe2+(aq)
that is thermodynamically favoured when
an acidic aqueous solution of V2+ is exposed (b) CrO42 (aq) + MoO2 (s) ?
to oxygen?
2 CrO42 + 3 MoO2(s) + 10 H+
+
+4; VO2
2 Cr3+ + 3 H2MoO4 + 2 H2O
S19.2 Suggest a use for molybdenum(IV) sulfide
that makes use of its solid-state structure. (c) MnO4 (aq) + Cr3+ (aq) ?
Rationalize your suggestion? MoS2 used as 6 MnO4 + 10Cr3+ + 11H2O
a lubricant. The slipperiness of MoS2 is
because of the ease with which one layer can 6Mn2+ + 5Cr2O72 + 22 H+
glide over another. 19.5 (a) Which ion, Ni (aq) or Mn (aq), is more
2+ 2+
S19.3 Describe the probable structure of the likely to form a sulfide in the presence of
compound formed when Re3Cl9 is dissolved H S? (b) Rationalize your answer with the
2
in a solvent containing PPh3? trends in hard and soft character across

Period 4. (c) Give a balanced chemical
Discrete molecular species such as Re3Cl123 equation for the reaction.
or Re3Cl9(PPh3)3 are formed.
More likely for Ni2+ to form a sulphide.
Hardness decreases from left to right in the d
Exercises block.
19.1 Without reference to a periodic table, Ni2+(aq) + H2S(aq) NiS(s) + 2 H+(aq)
sketch the first series of the d block,
including the symbols of the elements. 19.6 Preferably without reference to the text (a)
Indicate those elements for which the write out the d block of the periodic table,
group oxidation number is common by C, (b) indicate the metals that form
those for which the group oxidation difluorides with the rutile or fluorite
number can be reached but is a powerful structures, and (c) indicate the region of
oxidizing agent by O, and those for which the periodic table in which metal-metal
bonded halide compounds are formed,
giving one example?
Metalmetal bonded halide compounds are 19.9 Speculate on the structures of the following
found within bold border. Example: Sc5Cl6. species and present bonding models to
justify your answers:
(a) [Re(O)2 (py)4]+, (b) [V (O)2 (ox)2]3, (c)
[Mo(O)2(CN)4]4, (d) [VOCl4]2? The first
three are dioxo complexes and will have cis-
dioxometal structural units. (d) VOCl42, has a
square-pyramidal structure with an apical oxo
ligand.
19.7 Write a balanced chemical equation for the
reaction that occurs when cis- 19.10 Which of the following are likely to have
[RuLCl(OH2)]+ (see Fig. 19.9) in acidic structures that are typical of (a)
solution at +0.2 V is made strongly basic at predominantly ionic, (b) significantly
the same potential. Write a balanced covalent, (c) metal-metal bonded
equation for each of the successive compounds: NiI , NbCl , FeF , PtS, and
2 4 2
reactions when this same complex at pH = WCl ? Rationalize the differences and
2
6 and +0.2 V is exposed to progressively speculate on the structures? (a) NiI2? ionic
more oxidizing environments up to +1.0 V. compound with significant degree of covalent
Give other examples and a reason for the character
redox state of the metal center affecting the
extent of protonation of coordinated (b) NbCl4? significantly covalent.
oxygen. (c) FeF2? ionic.
II +
cis-[Ru LCl(OH2)] + Ox + OH cis- (d) PtS ? significant amount of covalent
[RuIIILCl(OH)]+ + Red + H2O character.
cis-[RuIILCl(OH2)]+ + H2O cis- (e) WCl2 ? metalmetal bonding.
[RuIIILCl(OH)]+ + H3O+ + e
19.11 Indicate the probable occupancy of s, p,
cis-[RuIIILCl(OH2)]+ + H2O cis- and d bonding and antibonding orbitals,
[RuIVLCl(OH)]+ + H3O+ + e and the bond order for the following
tetragonal prismatic complexes?
As oxidation state of the metal increases,
ability to accept electron density from an OH (a) [Mo2(O2CCH3)4]? 242 configuration,
or O2 ligand increases. molybdenum-molybdenum quadruple bond.
19.8 Give plausible balanced chemical reactions (b) [Cr2(O2CC2H5)4]? 242,chromium
(or NR for no reaction) for the following chromium quadruple bond.
combinations, and state the basis for your
answer: (a) MoO42 (aq) plus Fe2+ (aq) in (c) [Cu2(O2CCH3)4]? 242*2*4*2
acidic solution? No reaction. configuration, no metalmetal bond in this
molecule.
(b) The preparation of [Mo6O19]2(aq) from
K2MoO4(s)? 6 MoO42(aq) + 10 H+(aq) 19.12 Explain the differences in the following
[Mo6O19]2(aq) + 5 H2O(l) redox couples, measured at 25oC?
Higher oxidation states become more stable
(c) ReCl5 (s) plus KMnO4(aq)? on descending a group.
5 ReCl5(s) + 2 MnO4(aq) + 12 H2O(l)
19.13 Addition of sodium ethanoate to aqueous
5 ReO4(aq) + 2 Mn2+(aq) + 25 Cl(aq) + solutions of Cr(II) gives a red diamagnetic
24 H+(aq) product. Draw the structure of the
product, noting any features of interest?
(d) MoCl2(s) plus warm HBr(aq)?
6 MoCl2(s) + 2 Br(aq) [Mo6Cl12]2(aq)
+ Br2(aq)
(e) TiO(s) with HCl(aq) under an inert
atmosphere? 2TiO (s) + 6H+ (aq)
3+
2Ti + H2(g) + 2H2O(l) E = +0.37 V.
(f) Cd(s) added to Hg2+(aq)?
Hg2+ (aq) + Cd(s) Hg(l) + Cd2+ (aq)
differences in the 68 eV region can be

attributed to the lack of d electrons for Mg(II).
S20.5 What terms arise from a p1d1
O O configuration? 1F and 3F terms are possible.
O S20.6 Identifying ground terms (Hint: Because d9
Cr O is one electron short of a closed shell with L
O = 0 and S = 0, treat it on the same footing
Cr as a d1 configuration.) (a) 2p2? 3P (called a
O
O triplet P term).
O (b) 3d9? 2D (called a doublet D term).
S20.7 What terms in a d2 complex of Oh
symmetry correlate with the 3F and 1
D
terms of the free atom? An F terms are
3
T1g, 3T2g, and 3A2g. Similarly, D terms are
19.14 Consider the two ruthenium complexes in 1
T2g and 1Eg.
Table 19.8. Using the bonding scheme
depicted in Figure 19.19, confirm the S20.8 Use the same Tanabe-Sugano diagram to
bonding orders and electron configurations predict the energy of the first two spin-
given in the table. allowed quartet bands in the spectrum of
[Cr(OH2)6]3+ for which o = 17 600 cm-1
[Ru2Cl2(ClCO2)4]- :
and B = 700 cm-1.
2.5 +, mixed valence at the Ru center, in line 17500 cm1 and 22400 cm1.
with the energy level scheme [0.5 (8-3)].
S20.9 The spectrum of [Cr(NCS)6]3- has a very
[Ru2 (CH3COCH3)2(ClCO2)4]: 2+, the bond weak band near 16 000 cm-1, a band at 17
order of 2.0 should also be expected [0.5x(8- 700 cm-1 with max= 5160 dm3 mol-1 cm-1, a
4)]. band at 23 800 cm-1 with max= 5130 dm3
mol-1 cm-1, and a very strong band at 32
400 cm-1. Assign these transitions using the
d3 Tanabe-Sugano diagram and selection
CHAPTER 20 rule considerations. (Hint: NCS- has low-
lying * orbitals.)
Self-tests
(i) The very low intensity of the band at 16,000
S20.1 What is the LFSE for both high- and low- cm1 is a clue that it is a spin-forbidden
spin d7 configurations? A high-spin d7 transition, probably 2Eg 4A2g.
configuration is t25geg2. High spin, 0.8 o.
(ii) Spin-allowed but Laporte-forbidden bands
S20.2 The magnetic moment of the complex typically have ~ 100 M1 cm1, so it is
[Mn(NCS)6]4 is 6.06B. What is its electron likely that the bands at 17,700 cm1 and
3 2
configuration? t2g eg 23,800 cm1 are of this type.
(iii) The band at 32,400 cm1 is probably a charge
S20.3 Account for the variation in lattice transfer band, since its intensity is too
enthalpy of the solid fluorides in which high to be a ligand field (dd) band.
each metal ion is surrounded by an
octahedral array of F ions: MnF (2780 kJ Exercises
mol1), FeF2 (2926 kJ mol1), CoF2 (2976 kJ
20.1 Determine the configuration (in the form
mol1), NiF2 (3060 kJ mol1), and ZnF2
(2985 kJ mol1). t2g x egy or ext2y, as appropriate), the
If it were not for ligand field stabilization number of unpaired electrons, and the
energy (LFSE), MF2 lattice enthalpies would ligand-field stabilization energy in terms of
increase from Mn(II) to Zn(II). O or T and P for each of the following
complexes using the spectrochemical series
S20.4 Suggest an interpretation of the to decide, where relevant, which are likely
photoelectron spectra of [Fe(C5H5)2] and to be high-spin and which low-spin.
[Mg(C5H5)2] shown in Fig. 20.18? (a) [Co(NH3)6]3+? d6, low spin, no unpaired
In the spectrum of [Mo(CO)6], the ionization electrons, LFSE = 2.40.
energy around 8 eV was attributed to the t2g (b) [Fe(OH2)6]2+? d6, high spin, four
electrons that are largely metal-based. The unpaired electrons, LFSE = 0.40.
(c) [Fe(CN)6]3? d5, low spin, one unpaired (c) [Fe(CN)6]3

electron. LFSE is 2.00.
(d) The ruthenium complex.
(d) [Cr(NH3)6]3+? d3, three unpaired (e) The Co2+ complex.
electrons, low spin, LFSE = 1.20.
20.6 Interpret the variation, including the overall
(e) [W(CO)6]? d6, low spin, no unpaired trend across the 3d series, of the following
electrons, LFSE = 2.40. values of oxide lattice enthalpies (in kJ
(f) Tetrahedral [FeCl4]2? d6, high spin, mol1). All the compounds have the rock-
four unpaired electrons, LFSE = 0.6 T. salt structure: CaO (3460), TiO (3878), VO
(3913), MnO (3810), FeO (3921), CoO
(g) Tetrahedral [Ni(CO)4]? d10, 0 unpaired (3988), NiO (4071)? There are two factors
electrons, LFSE = 0. that lead to the values: (i) decreasing ionic
radius from left to right across the d block,
20.2 Both H- and P(C6H5)3 are ligands of similar
and (ii) LFSE.
field strength, high in the spectrochemical
series. Recalling that phosphines act as .20.7 A neutral macrocyclic ligand with four
acceptors, is -acceptor character required donor atoms produces a red diamagnetic
for strong-field behaviour? What orbital low-spin d8 complex of Ni(II) if the anion is
factors account for the strength of each the weakly coordinating perchlorate ion.
ligand? When perchlorate is replaced by two
No. thiocyanate ions, SCN, the complex turns
violet and is high-spin with two unpaired
Thus there are two ways for a complex to
electrons. Interpret the change in terms of
develop a large value of 0, by possessing
structure? Shift from square planar to
ligands that are -acids or by possessing tetragonal complex.
ligands that are strong -bases (or both).
20.8 Bearing in mind the Jahn-Teller theorem,
20.3 Estimate the spin-only contribution to the Predict the structure of
magnetic moment for each complex in [Cr(OH2)6]2+? Elongated octahedron.
Exercise 20.1. Spin-only contributions are:
complex N SO = [(N)(N + 2)]1/2 20.9 The spectrum of d1 Ti3+(aq) is attributed to
[Co(NH3)6] 3+
0 0 a single electronic transition eg t2g. The
[Fe(OH2)6]2+ 4 4.9 band shown in Fig. 20.3 is not symmetrical
[Fe(CN)6]3 1 1.7 and suggests that more than one state is
[Cr(NH3)6]3+ 3 3.9 involved. Suggest how to explain this
[W(CO)6] 0 0 observation using the Jahn-Teller
[FeCl4]2 4 4.9 theorem? The electronic excited state of
[Ni(CO)4] 0 0 Ti(OH2)63+ has the configuration t2g0eg1, and
so the excited state possesses eg degeneracy.
Therefore, the single electronic transition is
20.4 Solutions of the complexes [Co(NH3)6]2+, really the superposition of two transitions, one
[Co(OH2)6]2+ (both Oh), and [CoCl4]2- are from an Oh ground-state ion to an Oh excited-
colored. One is pink, another is yellow, and state ion, and a lower energy transition from
the third is blue. Considering the an Oh ground-state ion to a lower energy
spectrochemical series and the relative distorted excited-state ion.
magnitudes of T and O, assign each color
to one of the complexes. [CoCl4]2 is blue, 20.10 Write the RussellSaunders term symbols
[Co(NH3)6]2+ is yellow, [Co(OH2)6]2+ is pink. for states with the angular momentum
quantum numbers (L,S):
20.5 For each of the following pairs of
complexes, identify the one that has the (a) L = 0, S = 5/2? 6S
larger LFSE: (b) L = 3, S = 3/2? 4F
(a) [Cr(OH2)6]2+ or [Mn(OH2)6]2+ (c) L = 2, S = 1/2? 2D
(b) [Mn(OH2)6]2+ or [Fe(OH2)6]3+
(d) L = 1, S = 1? 3P
(c) [Fe(OH2)6]3+ or [Fe(CN)6]3-
(d) [Fe(CN)6]3 or [Ru(CN)6] 20.11 Identify the ground term from each set of
(e) tetrahedral [FeCl4]2or tetrahedral terms: (a) 3F, 3P, 1P, 1G? 3F.
[CoCl4]2 (b) 5D, 3H, 3P, 1G, 1I? 5D
(a) The chromium complex. (c) 6S, 4G, 4P, 2I? 6S
3+
(b) The Fe complex.
20.12 Give the Russell-Saunders terms of the max52 dm3 mol-1 cm-1, and a strong band at
configurations and identify the ground higher energy with max= 2 x 104 dm3 mol1
term? (a) 4 s1? 2S. cm1. What do you suggest for the origins
of these transitions? First, the intense band
(b) 3p2? 1
D, 3P, 1S. The ground term is 3P.
at relatively high energy is undoubtedly a
20.13 The gas-phase ion V3+ has a 3F ground term. spin-allowed charge-transfer transition. The
The 1D and 3P terms lie, respectively, 10 two bands with max = 60 and 80 M1 cm1 are
642 and 12 920 cm1 above it. The energies probably spin-allowed ligand field transitions.
of the terms are given in terms of Racah The very weak peak is most likely a spin-
parameters as E(3F) = A - 8B, E(3P) = A + forbidden ligand field transition.
7B, E(1D) = A - 3B + 2C. Calculate the
20.20 Ordinary bottle glass appears nearly
values of B and C for V3+. B = (12920 cm
1 colorless when viewed through the wall of
)/(15) = 861.33 cm1 and C = 3167.7 cm1.
the bottle but green when viewed from the
20.14 Write the d-orbital configurations and use end so that the light has a long path
the TanabeSugano diagrams (Resource through the glass. The color is associated
section 6) to identify the ground term of (a) with the presence of Fe3+ in the silicate
Low-spin [Rh(NH3)6]3+? 1A1g. matrix. Suggest which transitions are
responsible for the color? The faint green
(b) [Ti(H2O)6]3+? 2T2g. color, which is only observed when looking
(c) High-spin [Fe(H2O)6]3+? 6A1g. through a long pathlength of bottle glass, is
caused by spin-forbidden ligand field
20.15 Using the Tanabe-Sugano diagrams in transitions.
Resource section 6, estimate O and B for
(a) [Ni(H2O)6]2+ (absorptions at 8500, 15400 20.21 Solutions of [Cr(OH2)6]3+ ions are pale blue
and 26000 cm-1) ? 0 = 8500 cm1 and B green but the chromate ion, CrO42, is an
770 cm1. intense yellow. Characterize the origins of
the transitions and explain the relative
(b) [Ni(NH3)6]2+ (absorptions at 10750, intensities. The blue-green color of the Cr3+
17500 and 28200 cm-1)? 0 = 10,750 cm1 ions in [Cr(H2O)6]3+ is caused by spin-
and B 720 cm1. allowed but Laporte-forbidden ligand field
20.16 The spectrum of [Co(NH3)6]3+ has a very transitions. The relatively low molar
weak band in the red and two moderate absorption coefficient is the reason that the
intensity bands in the visible to near-UV. intensity of the color is weak. The oxidation
How should these transitions be assigned? state of chromium in dichromate dianion is
The first two transitions listed above Cr(VI); the intense yellow color is due to
correspond to two low-spin bands. The very LMCT transitions.
weak band in the red corresponds to a spin- 20.22 Classify the symmetry type of the d orbital
forbidden transition. in a tetragonal C4v symmetry complex, such
20.17 Explain why [FeF6]3- is colorless whereas as [CoCl(NH3)5] , where the Cl lies on the
[CoF6]3 is colored but exhibits only a z-axis. (a) Which orbitals will be displaced
single band in the visible. No spin-allowed from their position in the octahedral
transitions are possible for the Fe3+; the molecular orbital diagram by
complex is expected to be colorless. The d6 interactions with the lone pairs of the Cl
Co3+ ion in [CoF6]3 is also high spin, but in ligand? (b) Which orbital will move
this case a single spin-allowed transition because the Cl ligand is not as strong a
makes the complex colored and gives it a one- base as NH3? (c) Sketch the qualitative
band spectrum. molecular orbital diagram for the C4v
complex. The Cl atom lone pairs of electrons
20.18 The Racah parameter B is 460 cm1 in can form molecular orbitals with dxz and dyz.
[Co(CN)6]3- and 615 cm-1 in [Co(NH3)6]3+. These metal atomic orbitals are -antibonding
Consider the nature of bonding with the MOs, and so they will be raised in energy.
two ligands and explain the difference in
nephelauxetic effect? Ammonia and cyanide
ion are both -bases, but cyanide is also a -
acid.
20.19 An approximately octahedral complex of
Co(III) with ammine and chloro ligands
gives two bands with max between 60 and
80 dm3 mol1 cm1, one weak peak with
20.23 Consider the molecular orbital diagram for Exercises

a tetrahedral complex (based on Fig. 20.7)
and the relevant d-orbital configuration 21.1 The rate constants for the formation of
and show that the purple color of MnO4- [CoX(NH3)5]2+ from [Co(NH3)5OH2]3+ for X
ions cannot arise from a ligand-field = Cl2, Br2, N3, and SCN differ by no more
transition. Given that the wavenumbers of than a factor of two. What is the
the two transitions in MnO4- are 18 500 and mechanism of the substitution? Dissociative.
32 200 cm1, explain how to estimate T 21.2 If a substitution process is associative, why
from an assignment of the two charge- may it be difficult to characterize an aqua
transfer transitions, even though T cannot ion as labile or inert? The rate of an
be observed directly. The oxidation state of associative process depends on the identity of
manganese in permanganate anion is the entering ligand and, therefore, it is not an
Mn(VII), which is d0. Therefore, no ligand inherent property of [M(OH2)6]n+.
field transitions are possible.
21.3 The reactions of Ni(CO)4 in which
The difference in energy between the two phosphines or phosphites replace CO to
transitions, E(t2) E(e) = 13700 cm1, is just give Ni(CO)3L all occur at the same rate
equal to T. regardless of which phosphine or phosphite
20.24 The lowest energy band in the spectrum of is being used. Is the reaction d or a? d.
[Fe(OH2)6]3+ (in 1M HClO4) occurs at 21.4 Write the rate law for formation of
lower energy than the equivalent transition [MnX(OH2)5]1 from the aqua ion and X.
in the spectrum of [Mn(OH2)6]2+. Explain How would you undertake to determine if
why this is. the reaction is d or a?
The extra charge of the iron complexes keeps rate = (kKE[Mn(OH2)62+][X])/(1 + KE[X])
the eg and t2g levels close
21.5 Octahedral complexes of metal centers with
high oxidation numbers or of d metals of
CHAPTER 21
the second and third series are less labile
than those of low oxidation number and d
Self-tests metals of the first series of the block.
Account for this observation on the basis of
a dissociative rate-determining step.
S21.1 Calculate the second-order rate constant Metal centers with high oxidation numbers
for the reaction of trans-[PtCl(CH3) have stronger bonds to ligands than metal
(PEt3)2] with NO2 in MeOH, for which npt centers with low oxidation numbers.
= 3.22 ? k2(NO2) = 100.71 = 5.1 M1s1 Furthermore, period 5 and 6 d-block metals
S21.2 Given the reactants PPh , NH , and [PtCl ] ,
3 3 4
2- have stronger metal ligand bonds.
Propose efficient routes to both cis- and 21.6 A Pt(II) complex of
trans- [PtCl2(NH3)(PPh3)]? tetramethyldiethylenetriamine is attacked
by Cl- 105 times less rapidly than the
diethylenetriamine analogue. Explain this
observation in terms of an associative rate-
determining step. The greater steric
hindrance.
21.7 The rate of loss of chlorobenzene, PhCl,
from [W(CO)4L(PhCl)] increases with
increase in the cone angle of L. What does
this observation suggest about the
mechanism? The mechanism is
dissociative.
21.8 The pressure dependence of the
replacement of chlorobenzene (PhCl) by
S21.3 Use the data in Table 21.8 to estimate an piperidine in the complex
appropriate value for KE and calculate kr2 [W(CO)4(PPh3)(PhCl)] has been studied.
for the reactions of V(II) with Cl- if the The volume of activation is found to be
observed second-order rate constant is 111.3 cm3 mol1. What does this value
1.2x102 dm3 mol1 s1. KE = 1 M1, k = 1.2 suggest about the mechanism? Mechanism
102 s1. must be dissociative.
(ii) The anomalously high rate of substitution

21.9 Does the fact that [Ni(CN)5]3 can be by OH signals an alternate path, that of base
isolated help to explain why substitution hydrolysis.
reactions of [Ni(CN)4]2 are very rapid?
(iii) The implication is that a complex without
For a detectable amount of [Ni(CN)5]3 to
build up in solution, the forward rate constant protic ligands will not undergo anomalously
kf must be numerically close to or greater than fast OH ion substitution.
the reverse rate constant kr. 21.14 Predict the products of the following
21.10 Reactions of [Pt(Ph) 2(SMe2) 2] with the reactions: (a) [Pt(PR3)4]2+ + 2Cl? cis-
bidentate ligand 1,10-phenanthroline [PtCl2(PR3)2].
(phen) give [Pt(Ph) 2phen]. There is a (b) [PtCl4]2 + 2PR3? trans-[PtCl2(PR3)2].
kinetic pathway with activation
parameters H = 1101 kJ mol1 and S (c) cis-[Pt(NH3)2(py)2]2+ + 2Cl? trans-
= 142 J K 1 mol 1. Propose a mechanism. [PtCl2(NH3)(py)].
A possible mechanism is loss of one 21.15 Put in order of increasing rate of
dimethyl sulfide ligand, followed by the substitution by H2O the complexes:
coordination of 1,10-phenanthroline. [Co(NH3)6]3+, [Rh(NH3)6]3+, [Ir(NH3)6]3+,
[Mn(OH2)6]2+, [Ni(OH2)6]2+?
21.11 A two-step synthesis for cis- and trans-
[PtCl2(NO2) (NH3)] start with [PtCl4]2? The order of increasing rate is [Ir(NH3)6]3+ <
[Rh(NH3)6]3+ < [Co(NH3)6]3+ < [Ni(OH2)6]2+
< [Mn(OH2)6]2+.
21.16 State the effect on the rate of dissociatively
activated reactions of Rh(III) complexes of
each of (a) an increase in the positive
charge on the complex? decreased rate.
(b) changing the leaving group from NO3
to Cl? Decreased rate.
(c) changing the entering group from Cl to
I? This change will have little or no effect
on the rate.
(d) changing the cis ligands from NH3 to
H2O? Decreased rate.
21.12 How does each of the following affect the
rate of square-planar substitution 21.17 Write out the inner- and outer-sphere
reactions? (a) Changing a trans ligand pathways for reduction of
from H to Cl? Rate decreases. azidopentaamminecobalt(III) ion with
V2+(aq). What experimental data might be
(b) Changing the leaving group from Cl to used to distinguish between the two
I? The rate decreases. pathways?
(c) Adding a bulky substituent to a cis The inner-sphere pathway:
ligand? The rate decreases.
[Co(N3)(NH3)5]2+ + [V(OH2)6]2+
(d) Increasing the positive charge on the [[Co(N3)(NH3)5]2+, [V(OH2)6]2+}
complex? Rate increase.
{[Co(N3)(NH3)5]2+, [V(OH2)6]2+}
21.13 The rate of attack on Co(III) by an entering {[Co(N3)(NH3)5]2+, [V(OH2)5]2+, H2O}
group Y is nearly independent of Y with
the spectacular exception of the rapid {[Co(N3)(NH3)5]2+, [V(OH2)5]2+, H2O}
reaction with OH. Explain the anomaly. [(NH3)5CoN=N=NV(OH2)5]4+
What is the implication of your explanation [(NH3)5CoN=N=NV(OH2)5]4+ [(NH3)5Co
for the behaviour of a complex lacking N=N=NV(OH2)5]4+
Brnsted acidity on the ligands? (i) The
general trend: octahedral Co(III) complexes [(NH3)5CoN=N=NV(OH2)5]4+ [Co(OH2)6]2+ +
undergo dissociatively activated ligand [V(N3)(OH2)5]2+
substitution. The outer sphere pathway:
[Co(N3)(NH3)5]2+ + [V(OH2)6]2+
{[Co(N3)(NH3)5]2+ [V(OH2)6]2+}
{[Co(N3)(NH3)5]2+,[V(OH2)6]2+} {[Co(N3)(NH3)5]+ , Using these values gives K12 = 1.81 1028.

[V(OH2)6]3+} Substitution of these values in the Marcus-
{[Co(N3)(NH3)5] +,[V(OH2)6]3+} {[Co(OH2)6]2+ , Cross relationship gives k12 = 8.51 1015
[V(OH2)6]3+ dm3mol1s1.21.21 The
photochemical substitution of
21.18 The compound [Fe(SCN)(OH2)5]2+ can be [W(CO)5(py)] (py = pyridine) with
detected in the reaction of triphenylphosphine gives
[Co(NCS)(NH3)5]2+ with Fe2+(aq) to give W(CO)5(P(C6H5)3). In the presence of
Fe3+(aq) and Co2+(aq). What does this excess phosphine, the quantum yield is
observation suggest about the approximately 0.4. A flash photolysis study
mechanism? Appears to be an inner-sphere reveals a spectrum that can be assigned to
electron transfer reaction. the intermediate W(CO)5. What product
21.19 Calculate the rate constants for electron and quantum yield do you predict for
transfer in the oxidation of [V(OH2)6]2+ (E substitution of [W(CO)5(py)] in the
(V3+/V2+) = 0.255 V) and the oxidants (a) presence of excess triethylamine? Is this
[Ru(NH3)6]3+ (EO(Ru3+/Ru2+) = + 0.07 V), reaction expected to be initiated from the
(b) [Co(NH3)6]3+ (EO(Co3+/Co2+) = +0.10 V). ligand field or MLCT excited state of the
Comment on the relative sizes of the rate complex? The product will be
constants. [W(CO)5(NEt3)], and the quantum yield will
be 0.4.
(a) [Ru(NH3)6]3+ k = 4.53 103 dm3mol1s1
21.22 From the spectrum of [CrCl(NH3)s]2+ shown
3+ 2 3 1 1
(b) [Co(NH3)6] k = 1.41 10 dm mol s in Fig. 20.32, propose a wavelength for
photoinitiation of reduction of Cr(III) to
Relative sizes? The reduction of the Ru
Cr(II) accompanied by oxidation of a
complex is more thermodynamically favoured
ligand. ~250 nm.
and faster.
21.20 Calculate the rate constants for electron CHAPTER 22
transfer in the oxidation of [Cr(OH2)6]2+
(EO(Cr3+/Cr2+) = 0.41 V) and each of the
oxidants [Ru(NH3)6]3+ (EO(Ru3+/Ru2+) =
Self-tests
+0.07 V), [Fe(OH2)6]3+ (EO(Fe3+/Fe2+) =
+0.77 V) and [Ru(bpy)3]3+ (EO(Ru3+/Ru2+) = S22.1 Is Mo(CO)7 likely to be stable? No.
+1.26 V). Comment on the relative sizes of S22.2 What is the electron count for and
the rate constants oxidation number of platinum in the anion
(a) k11 (Cr3+/Cr2+) = 1 105 dm3mol1s1; k22 of Zeises salt, [PtCl3(C2H4)]? Treat
CH =CH as a neutral two-electron donor.
(Ru3+/Ru2+ for the hexamine complex) = 6.6
2 2
o Electron count, 16; oxidation number, +4.

103 dm3mol1s1; f12 = 1; K12 = e [nF /RT]
where o = 0.07 V (0.41V) = 0.48 V; n = 1; S22.3 What is the formal name of
F = 96485 C; R = 8.31 Jmol1K1 and T = 298 [Ir(Br)2(CH3)(CO)(PPh3)2]?
Dibromocarbonylmethylbis(triphenylphos-
K. Using these values gives K12 = 1.32 108.
phine)iridium(III).
Substitution of these values in the Marcus-
Cross relationship gives k12 = 2.95 103 S22.4 Which of the two iron compounds Fe(CO)5
dm3mol1s1. and [Fe(CO)4(PEt3)] will have the higher
(b) k11 (Cr3+/Cr2+) = 1 105 dm3mol1s1; k22 CO stretching frequency? Which will have
(Fe3+/Fe2+ for the aqua complex) = 1.1 the longer MC bond? Fe(CO)5
o
dm3mol1s1; f12 = 1; K12 = e[nF /RT] where o
S22.5 Show that both are 18-electron species.
= 0.77 V (0.41V) = 1.18 V; n = 1; F =
96485 C; R = 8.31 Jmol1K1 and T = 298 K. (a) [(6-C7H8)Mo(CO)3] (49)?
Using these values we get K12 = 9.26 1019.
Substitution of these values in the Marcus- 6-C7H8 = 6 electrons, Mo atom = 6.
carbonyl = 2 electrons, total = 18.
Cross relationship gives k12 = 3.19 107
dm3mol1s1. (b) [(7-C7H7)Mo(CO)3]+(51)? 7-C7H7+ = 6
(c) k11 (Cr3+/Cr2+) = 1 105 dm3mol1s1; electrons, Mo atom = 6, 3 COs = 6, total = 18.
k22 (Ru3+/Ru2+ for the bipy complex) = 4 108
o S22.6 Propose a synthesis for
dm3mol1s1; f12 = 1; K12 = e[nF /RT] where o Mn(CO)4(PPh3)(COCH3) starting with
= 1.26 V (0.41V) = 1.67 V; n = 1; F = [Mn2(CO)10], PPh3, Na and CH3I.
96485 C; R = 8.31 Jmol1K1 and T = 298 K.
Mn2(CO)10 + 2 Na 2Na[Mn(CO)5] Exercises

Na[Mn(CO)5] + CH3I Mn(CH3)(CO)5 + NaI 22.1 Name the species, draw the structures of,
Mn(CH3)(CO)5 + PPh3 Mn(CO)4(PPh3)(COCH3) and give valence electron counts to the
metal atoms? Do any of the complexes
deviate from the 18-electron rule? If so,
S22.7 The IR spectrum of [Ni2(5-Cp)2(CO)2] has how is this reflected in their structure or
a pair of CO stretching bands at 1857 cm1 chemical properties?
(strong) and 1897 cm1 (weak). Does this
complex contain bridging or terminal CO (a) Fe(CO)5? Pentacarbonyliron(0), 18e;
ligands, or both? (Substitution of 5-C5H5 (b) Mn2(CO)10?
ligands for CO ligands leads to small shifts decacarbonyldimanganese(0), 18e;
in the CO stretching frequencies for a
terminal CO ligand.) Bridging (c) V(CO)6? hexcarbonylvanadium(0), 17e
S22.8 By using the same molecular orbital (d) [Fe(CO)4]2? tetracarbonylferrate(2),

diagram, comment on whether the removal 18e;
of an electron from [Fe(5-Cp)2] to (e) La(5-Cp*)3?
produce [Fe(5-Cp)2]+ should produce a tris(pentamethylcyclopentadienyl)lanthanum(I
substantial change in MC bond length II), 18e;
relative to neutral ferrocene. It will not.
(f) Fe(3-allyl)(CO)3Cl?
allyltricarbonylchloroiron(II), 18e;
S 22.9 The compound [Fe4(Cp)4(CO)4] is a dark-
green solid. Its IR spectrum shows a single (g) Fe(CO)4(PEt3)?
CO stretch at 1640 cm1. The 1H NMR tetracarbonyltriethylphosphineiron(0);
spectrum is a single line even at low (h) Rh(CO)2(Me)(PPh3)?
temperatures. From this spectroscopic dicarbonylmethyltriphenylphosphinerhodium(
information and the CVE, propose a I),16e-
structure for [Fe4(Cp)4(CO)4]. TA
tetrahedron with 4 terminal Cp rings and four (i) Pd(Cl)(Me)(PPh3)2?
capping COs. chloromethylbis(triphenylphosphine)
palladium(II), 16e;
S22.10 If Mo(CO)3L3 is desired, which of the
ligands P(CH3)3 or P(t-Bu)3 would be (j) Co(5-C5H5)(4-C4Ph4)?
preferred? Give reasons for your choice. cyclopentadienyltetraphenylcylcobutadinecob
PMe3 would be preferred. alt(I), 18e;
S22.11 Assess the relative substitutional (k) [Fe(5-C5H5)(CO2)]?
reactivities of indenyl and fluorenyl (86) dicarbonylcyclopentadienylferrate(0), 18e;
compounds? Fluorenyl compounds are more
reactive than indenyl. (l) Cr(6-C6H6)(6-C7H8)?
benzenecycloheptatrienechromium(0), 18e;
S22.12 Show that the reaction is an example of (m) Ta(5-C5H5)2Cl3?
reductive elimination? trichlorobiscyclopentadineyltanatalum(V),
18e;
Cl
Ph3P
Pd
Cl Cl
Pd
PPh3
+ PhCl
(n) Ni(5-C5H5)NO?
Ph PPh3 Ph3P Cl cyclopentadineylnitrosylnickel(0),18e.
Cl
22.2 Sketch an 2 the interactions of 1,4-
The decrease in both coordination number and
butadiene with a metal atom and (b) do the
oxidation number by 2.
same for an 4 interaction.
S22.13 Explain why [Pt(PEt3)2(Et)(Cl)] readily
decomposes, whereas [Pt(PEt3)2 (Me)(Cl)]
does not? The ethyl group in
[Pt(PEt3)2(Et)(Cl)] is prone to -hydride
elimination.
22.3 What hapticities are possible for the

interaction of each of the following ligands
with a single d-block metal atom such as spectrum? Check your answer and give the
cobalt? (a) C2H4? 2 number of expected bands for each by
(b) Cyclopentadienyl? Can be 5, 3, or 1. consulting Table 22.7.
Cs symmetry complex, 3
(c) C6H6? 6, 4, and 2.
22.8 Provide plausible reasons for the
(d) Cyclooctadiene? 2 and 4 . differences in IR wavenumbers between each of the
following pairs:
(e) Cyclooctatetraene?8, 6, 4, 2. (a) Mo(PF3)3(CO)3 2040, 1991 cm1 versus
Mo(PMe3)3(CO)3 1945, 1851 cm1? CO
22.4 Draw plausible structures and give the bands of the trimethylphosphine complex are
electron count of (a) Ni(3-C3H5)2 (b) 100 cm1 or more lower in frequency. PMe3 is
Co(4-C4H4)(5-C5H5) (c) Co(3- primarily a -donor ligand. PF3 is primarily
C3H5)(CO)3. If the electron count deviates
a -acid ligand.
from 18, is the deviation explicable in
terms of periodic terms. (b) MnCp(CO)3 2023, 1939 cm1 vs.
MnCp*(CO)3 2017, 1928 cm1? CO bands
(a) Ni(3-C3H5)2 16, very common for group of the Cp* complex are lower in frequency
9 and group 10 elements. than the corresponding bands of the Cp
complex. Cp* is a stronger donor ligand than
(b) Co(4-C4H4)(5-C5H5)? 18. Cp.
(c) Co(3-C3H5)(CO)3? 18. 22.9 The compound Ni3(C5H5)3(CO)2 has a
single CO stretching absorption at 1761
cm1. The IR data indicate that all C5H5
ligands are pentahapto and probably in
identical environments. (a) On the basis of
these data, propose a structure.
22.5 State the two common methods for the

preparation of simple metal carbonyls and
illustrate your answer with chemical
equations. Is the selection of method based
on thermodynamic or kinetic
considerations?
(1) Mo(s) + 6 CO(g) Mo(CO)6(s) (high
temperature and pressure required) (b) Does the electron count for each metal
in your structure agree with the 18-
(2) 2 CoCO3(s) + 2 H2(g) + 8 CO(g)
electron rule? If not, is nickel in a
Co2(CO)8(s) + 2 CO2 + 2 H2O
region of the periodic table where
The reason that the second method is deviations from the 18-electron rule
preferred is kinetic. are common? No. Deviations from the
22.6 Suggest a sequence of reactions for the rule are common for cyclopentadienyl
preparation of Fe(CO)3(dppe), given iron complexes to the right of the d block.
metal, CO, dppe (Ph2PCH2CH2PPh2), and 22.10 Decide which of the two complexes W(CO)6
other reagents of your choice. or IrCl(CO)(PPh3)2 should undergo the
Fe(s) + 5 CO(g) Fe(CO)5(l) (high temperature faster exchange with 13CO. Justify your
and pressure required) answer. The Ir complex. It has an A
Fe(CO)5(l) + diphos(s) Fe(CO)3(diphos)(s) + 2 mechanism.
CO(g) 22.11 Which metal carbonyl in each of (a)
22.7 Suppose that you are given a series of [Fe(CO)4]2 or [Co(CO)4] (b) [Mn(CO)5]
metal tricarbonyl compounds having the or [Re(CO)5]should be the most basic
respective symmetries C2v, D3h, and Cs. toward a proton? What are the trends on
Without consulting reference material, which your answer is based ?
which of these should display the greatest (a) [Fe(CO)4]2 The trend involved is the
number of CO stretching bands in the IR greater affinity for a cation that a species with
a higher negative charge has.
(b) The rhenium complex. The trend involved

is the greater MH bond enthalpy for a period 22.17 Suggest syntheses of (a) [Mo(7-
6 metal ion relative to a period 4 metal ion in C7H7)(CO)3]BF4 from Mo(CO)6 and (b)
the same group. [IrCl2(COMe)(CO)(PPh3)2] from
[IrCl(CO)(PPh3)2]?
22.12 Using the 18-electron rule as a guide,
indicate the probable number of carbonyl (a) Reflux Mo(CO)6 with cycloheptatriene to
ligands in (a) W(6-C6H6)(CO)n, (b) Rh(5- give [Mo(6-C7H8)(CO)3]; treat with the trityl
C5H5)(CO)n, and (c) Ru3(CO)n. tetrafluoroborate to give [Mo(7-
(a) 3 (b) 2 (c) 12 C7H7)(CO)3]BF4.
(b) React [IrCl(CO)(PPh3)2] with MeCl, then
22.13 Propose two syntheses for MnMe(CO)5,
expose to CO atmosphere to give
both starting with Mn2(CO)10, with one
[IrCl2(COMe)(CO)(PPh3)2].
using Na and one using Br2? You may use
other reagents of your choice. (i) Reduce 22.18 When Fe(CO)5 is refluxed with
Mn2(CO)10 with Na to give Mn(CO)5; react cyclopentadiene compound A is formed
with MeI to give MnMe(CO)5. (ii), Oxidize which has the empirical formula C8H6O3Fe
with Br2. to give MnBr(CO)5; displace the and a complicated 1H NMR spectrum.
bromide with MeLi to give MnMe(CO)5. Compound A readily loses CO to give
compound B with two 1H-NMR resonances,
22.14 Give the probable structure of the product
one at negative chemical shift (relative
obtained when Mo(CO)6 is allowed to react
intensity one) and one at around 5ppm
first with LiPh and then with the strong
(relative intensity 5). Subsequent heating of
carbocation reagent, CH3OSO2CF3.
B results in the loss of H2 and the
Mo(CO)5(C(OCH3)Ph)
formation of compound C. Compound C
22.15 Na[W(5-C5H5)(CO)3] reacts with 3- has a single 1H-NMR resonance and the
chloroprop-1-ene to give a solid, A, which empirical formula C7H5O2Fe. Compounds
has the molecular formula A, B, and C all have 18 valence electrons:
W(C3H5)(C5H5)(CO)3. Compound A loses identify them and explain the observed
carbon monoxide on exposure to light and spectroscopic data.
forms compound B, which has the formula -2 C O -C O -H
+ F e (C O ) 5
W(C3H5)(C5H5)(CO)2. Treating compound Fe
Fe
A with hydrogen chloride and then

OC CO
CO H
OC
CO
potassium hexafluorophosphate, K+PF6,

A B
results in the formation of a salt, C. [-C5H5Fe(CO)2]2

C
Compound C has the molecular formula
The compound B shows two 1H NMR
[W(C3H6)(C5H5)(CO)3]PF6. Use this
resonances due to Fe-H proton and the
information and the 18-electron rule to
aromatic Cp ring. C shows a single 1H NMR
identify the compounds A, B, and C.
resonance because of aromatic Cp ring.
Sketch a structure for each, paying
particular attention to the hapticity of the
22.19 When Mo(CO)6 is refluxed with
hydrocarbon.
cyclopentadiene compound D is formed
which has the empirical formula
+ C8H5O3Mo and an absorption in the IR
W W CO W CO spectrum at 1960 cm1. Compound D can
CO
A: CO
B: CO C: CO be treated with bromine to yield E or with
CO CO Na/Hg to give compound F. There are
absorptions in the IR spectra of E and F at
1 3 2 2090 and 1860 cm1, respectively.
Compounds D, E, and F all have 18 valence
22.16 Treatment of TiCl4 at low temperature electrons: identify them and explain the
with EtMgBr gives a compound that is observed spectroscopic data.
unstable above 270C. However, treatment
of TiCl4 at low temperature with MeLi or D = C5H5Mo(CO)3. E = C5H5Mo(CO)3Br.
LiCH2SiMe3 gives compounds that are F = C5H5Mo(CO)3Na.
stable at room temperature. Rationalize
these observations. 22.20 Which compound would you expect to be
The compounds formed are TiR4; ethyl has more stable,RhCp2 or RuCp2? Give a
the low energy -hydride elimination plausible explanation for the difference in
decomposition. terms of simple bonding concepts
RuCp2 has 18 electrons. (b) Can these CVE values be derived from
22.21 Give the equation for a workable reaction the 18-electron rule? No.
for the conversion of Fe(5-C5H5)2 to Fe(5-
(c) Determine the probable geometry of
C5H5) (5-C5H4COCH3) and (b) Fe(5-
[Fe6(C)(CO)16]2 and [Co6(C)(CO)15]2-
C5H5) (5-C5H4CO2H)
? The iron complex probably contains an
(a) Fe(5 C5H5)2 + CH3COCl octahedral Fe6 array. The cobalt complex
Fe( C5H5)(5 C5H4COCH3) + HCl
5
probably contains a trigonal-prismatic Co6
array.
(b) 22.27 Based on isolobal analogies, choose the

groups that might replace the group in
Cl O O
Cl
C O 2H boldface in (a) Co3(CO)9CH OCH3,
Cl
N(CH3)2, or SiCH3? SiCH3.
H 2 O , t-B u O K
Fe + A lC l 3 Fe Fe
C H 2C l2 DME
(b) (OC)5MnMn(CO)5 I, CH2, or

CCH3? I.
22.22 Sketch the a1 symmetry-adapted orbitals 22.28 Ligand substitution reactions on metal
for the two eclipsed C5H5 ligands stacked clusters are often found to occur by associative
together with D5h symmetry. Identify the s, mechanisms, and it is postulated that these occur by
p, and d orbitals of a metal atom lying initial breaking of an M-M bond, thereby providing
between the rings that may have nonzero an open coordination site for the incoming ligand. If
overlap, and state how many a1 molecular the proposed mechanism is applicable, which would
orbitals may be formed. you expect to undergo the fastest exchange with
The symmetry-adapted orbitals of the two added13CO, Co4(CO)12 or Ir4(CO)12? Suggest an
eclipsed C5H5 rings in a metallocene are
explanation. Co. This is because metalmetal bond
shown in Resource Section 5, the dz2 orbital
strengths increase down a group in the d block.
on the metal has a1 symmetry, as does s.
Three a1 MOs will be formed.
22.23 The compound Ni(5-C5H5)2 readily adds CHAPTER 23
one molecule of HF to yield [Ni(5-
C5H5)(4-C5H6)]+ whereas Fe(5-C5H5)2
reacts with strong acid to yield [Fe(5- Self-tests
C5H5)2H]+. In the latter compound the H
atom is attached to the Fe atom. Provide a S23.1 Derive the ground state of the Tm3+ ion
3
reasonable explanation for this difference. H6.
Protonation of FeCp2 at iron does not change
its number of valence electrons. S23.2 The product of the reaction above is in fact
a hydride bridged dimer (9). Suggest a
22.24 Write a plausible mechanism, giving your strategy to ensure that the hydride is
reasoning, for the reactions: (a) monomeric. A simple approach would be to
[Mn(CO)5(CF2)]+ + H2O [Mn(CO)6]+ + use the Cp rings substituted by bulky groups
2HF? and examine rate of formation.
(i) The F atoms render the C atom subject to S23.3 Use the Frost diagrams and data in
nucleophilic attack Resource section 2 to determine the most
(ii)two equivalents of HF are eliminated stable uranium ion in acid aqueous solution
in the presence of air and give its
(b) Rh(C2H5) (CO) (PR3)2 formula. UO22+ if sufficient oxygen is
RhH(CO)(PR3)2 + C2H4? A -hydrogen present.
elimination reaction.
22.25 Given mechanism of CO insertion, what
rate constant can be extracted from rate Exercises
data? Rate = ka[RMn(CO)5] 23.1 (a) Give a balanced equation for the
reaction of any of the lanthanoids with
22.26 (a) What cluster valence electron (CVE) aqueous acid. (b) Justify your answer with
count is characteristic of octahedral and redox potentials and with a generalization
trigonal prismatic complexes? on the most stable positive oxidation states
octahedral M6, 86; trigonal prismatic M6, 90. for the lanthanoids. (c) Name the two
lanthanoids that have the greatest tendency
to deviate from the usual positive oxidation
state and correlate this deviation with 23.10 Predict a structure type for BkN based on
electronic structure. ? (a) Balanced the ionic radii r(Bk3+) = 96 pm and r(N3) =
equation 2 Ln(s) + 6 H3O+(aq) 146 pm.
The rock-salt structure.
2 Ln3+(aq) + 3 H2(g) + 6 H2O(l)
23.11 Describe the general nature of the
(b) Redox potentials The potentials for the
distribution of the elements formed in the
Ln0/Ln3+ oxidations in acid solution range thermal neutron fission of 235U, and
from a low of 1.99 V for europium to 2.38 V. decide which of the following highly
(c) Two unusual lanthanides Ce4+, Eu2+. radioactive nuclides are likely to present
the greatest radiation hazard in the spent
23.2 Explain the variation in the ionic radii fuel from nuclear power reactors: (a) 39Ar,
between La3+ and Lu3+. (b) 228Th, (c) 90Sr, (d) 144Ce. 90Sr and 144Ce.
The lanthanide contraction.
23.3 From a knowledge of their chemical CHAPTER 24
properties, speculate on why Ce and Eu
were the easiest lanthanoids to isolate Self-tests
before the development of ion-exchange
chromatography. Ce4+ and Eu2+, unusual S24.1 Synthesis for Sr2MoO4? Sealed tube, high
oxidation states were used in separation temperature, 6 SrO(s) + Mo(s) + 2 MoO3(s)
procedures. 3 Sr2MoO4.
23.4 How would you expect the first and second S24.2 Why does increased pressure reduce the
ionization energies of the lanthanoids to conductivity of K+ more than that of Na+ in
vary across the series? Sketch the graph
-alumina? Because K+ is larger than Na+.
that you would get if you plotted the third
ionization energy of the lanthanoids versus
atomic number? Identify elements at any
S24.3 Rationalize the observation that FeCr2O4 is
peaks or troughs and suggest a reason for
a normal spinel? The A2+ ions (Fe2+ in this
their occurrence? First and second IEs
example) occupy tetrahedral sites and the B3+
would show general increase across the
ions (Cr3+) occupy octahedral sites.
lanthanoids. With the third, anomalies arise.
7
23.5 Derive the ground state of the Tb3+ ion. F6
Exercises
23.6 Predict the magnetic moment of a 24.1 NiO doped with Li2O? The electronic
compound containing the Tb3+ ion. conductivity of the solid increases owing to
= 9.72 B formation of Ni1xLix)O.
24.2 What is a crystallographic shear plane?
23.7 Explain why stable and readily isolable Both.
carbonyl complexes are unknown for the 24.3 How might you distinguish between a solid
lanthanoids? Carbonyl compounds need solution and a series of discrete
back-bonding from metal orbitals of the crystallographic shear plane structures? A
appropriate symmetry. solid solution would contain a random
collection of crystallographic shear planes.
23.8 Suggest a synthesis of neptunocene from
NpCl4? 24.4 Wurtzite crystal structure and bottleneck?
Np(COT)2 was prepared by the reaction of The wurtzite structure is shown in Figure
K2COT with NpCl4 under inert 3.35. The normal sites for cations in this
atmosphere. structure are the tetrahedral holes. The
bottleneck involves the space formed by three
23.9 Account for the similar electronic spectra close packed anions.
of Eu3+ complexes with various ligands and
the variation of the electronic spectra of 24.5 Synthesis of? (a) MgCr2O4 - heat
Am3+ complexes as the ligand is varied. (NH4)2Mg(CrO4)2 gradually to 1100-1200C;
The 5f orbitals of the actinide ions interact (b) SrFeO3Cl - heat SrO + SrCl2 + Fe2O3 in a
strongly with ligand orbitals, and the splitting sealed tube; (c) Ta3N5 - heat Ta2O5 under
of the 5f subshell, as well as the color of the NH3 at 700C.
complex, varies as a function of ligand.
24.6 Products of reactions? (a) LiNiO2, (b)
Sr2WMnO6.
24.7 Where might intercalated Na+ ions reside

in the ReO3 structure? The unit cell for 24.21 Order of band gaps? BN > C(diamond) >
ReO3 is shown in Figure 24.16(a), the AlP > InSb.
structure is very open.
24.22 Fulleride structures? In Na2C60, all of the
24.8 Antiferromagnet ordering? In an
tetrahedral holes are filled with sodium
antiferromagnetic substance, the spins on
cations. In Na3C60, all of the tetrahedral holes
different metal centers are coupled into an
and all of the octahedral holes are filled with
antiparallel alignment. As the temperature
sodium cations.
approaches 0 K, the net magnetic moment
goes to zero.
24.9 Magnetic measurements on ferrite? inverse CHAPTER 25
spinel.
24.10 Using LFSEs determine site preference for

Self-tests
A= Ni(II) and B = Fe(III)? Better ligand
field stabilization and a strong preference for S25.1 Synthesis of core-shell nanoparticles? The
inverse spinel. thermodynamic driving force is adjusted to a
level that allows for heterogeneous nucleation
24.11 High-temperature superconductors? All of the shell material on the core but prevents
except Gd2Ba2Ti2Cu2O11, which contains only homogeneous nucleation of the shell material.
Cu2+, are superconductors.
S25.2 Hemispherical imprint for 2 nm
24.12 Classify oxides as glass-forming or nanoparticle? The radius is 4.21 nm and the
nonglass-forming? BeO, B2O3, and to some diameter is 8.42 nm.
extent GeO2, glass forming. Transition metal
and rare earth oxides are typically nonglass- S25.3 Host for QDs? MCM-41.
forming.
Exercises
24.13 Which metal sulfides might be glass
forming? Metalloid and nonmetal sulfides. 25.1 (a) Surface areas? 3.14 102 nm2 versus
3.14 106 nm2 (a factor of 104). (b)
24.14 Examples of spinels containing? (a) Nanoparticles based on size? The 10 nm
sulfide? Zn(II)Cr(III)2S4 (b) fluoride? particle. (c) Nanoparticles based on
Li2NiF4 properties? A nanoparticle should exhibit
properties different from those of a molecule
24.15 Synthesis of LiTaS2? Direct reaction of TaS2 or an extended solid.
with BuLi, or through electrochemical
insertion of Li ions. 25.2 Electron length and quantum
confinement? A characteristic length is the
24.16 Oxotetrahedral species in framework exciton Bohr radius.
structures? Be, Ga, Zn, and P.
25.3 Why are QDs better for bioimaging? One
24.17 Formulas for structures isomorphous with light source can be used to excite different
SiO2 containing Al, P, B, and Zn replacing quantum dots.
Si? (AlP)O4, (BP)O4, (ZnP2)O6.
24.18 Mass percent of hydrogen in NaBH4 and 25.4 Band energies for QD versus bulk
hydrogen storage? 10.7 %, it is a good semiconductor? The energies of the band
candidate to consider. edges for a QD nanocrystal are more widely
separated.
24.19 Formula for this lithium aluminium
magnesium dihydride and structures?
25.5 (a) Top-down versus bottom-up? The top-
Mg1-x(M)xH2y (M=Al, Li), The Li and Al will down approach requires one to carve out
be incorporated as metal hydride solid nanoscale features from a larger object. The
solutions. bottom-up approach requires one to build
24.20 Color intensity differences in Egyptian blue up nanoscale features from smaller entities.
pale versue blue-green spinel? The Cu site (b) Advangtages and disadvantages? Top-
in Egyptian blue is square planar. In copper down methods allow for precise control over
aluminate spinel blue, the site is tetrahedral. the spatial relationships. Bottom-up methods
allow for the precise spatial control over 25.11 (a) Homogeneous versus heterogeneous?
atoms and molecules. Homogeneous nucleation leads to solid
formation throughout the vapour phase. (b)
25.6 (a) What are SPMs? A method to image the thin film? Heterogeneous nucleation is
microscale features by scanning a very small preferred in thin-film growth. (c)
probe over the surface and measuring some nanoparticles? Homogeneous nucleation is
physical interaction between the tip and the generally preferred for nanoparticle synthesis.
material. (b) SPM and a specific
nanomaterial? Local magnetic domains of 25.12 PVD versus CVD? In CVD, the atomic
magnetic nanomaterials, such as nanorods of species of interest are bound chemically to
iron oxide, can be imaged using magnetic other species. Also, their thermal energies are
force microscopy. typically rather low. In PVD, the atomic
species of interest are typically atomic.
25.7 SEM versus TEM? SEM, an electron beam
is scanned over a material, and an image is 25.13 (a) Purpose of QD layers? Multiple layers of
generated by recording the intensity of quantum dots can increase the intensity of any
secondary or back-scattered electrons. TEM, optical absorption or emission. They can also
an electron beam is transmitted through the be used to form quantum cascade lasers. (b)
materials, and the image is the spatial Limitations? The limitations come from the
variation in the number of transmitted requirements on how coherent the interface
electrons. between the two materials must be.
SEM sample preparation, ensure the material
is conductive. In TEM, the sample needs to be 25.14 (a) Applications of quatum wells? Lasers
made transparent to the electron beam.. and optical sensors. (b) Why are they used
over other materials? They exhibit
25.8 (a) Steps in solutions synthesis of properties that are not observed in molecular
nanoparticles? (i) solvation; (ii) stable nuclei or traditional solid state materials. (c) How
of nanometer dimensions formed; (iii) growth are they made? Molecular beam epitaxy.
of particles to desired size occurs.
(b) Why should the last two steps occur 25.15 Superlattices and improved properties?
independently? So that nucleation fixes the AlN and TiN - different elastic constants,
total number of particles and growth leads to large number of interfaces spaced on the
controlled size and narrow size distribution. nanoscale.
(c) Stabilizers? Prevent surface oxidation and Results are much improved hardness values.
aggregation, and they limit traps for the holes
and electrons, and improve quantum yields 25.16 (a) Self-assembly? (a) Offers methods to
and luminescence. bridge bottom-up and top-down approaches to
synthesis. (b) In nanotechnology? Offers a
25.9 Vapor-phase versus solution-based route to assemble nanosized particles into
techniques? (a) Vapor-phase, large sizes. (b) macroscopic structures.
Vapor-phase, more agglomeration.
25.17 Common features of self-assembly?
25.10 (a) What is a core-shell nanoparticle? (i) molecular or nanoscale subunits; (ii)
spontaneous assembly of the subunits; (iii)
Shell noncovalent interactions between the
assembled subunits; (iv) longer-range
Core structures arising from the assembly process.
25.18 Static versus dynamic self-assembly? Static

(b) How are they made? Nucleation in one self-assembly is when a system self-
solution, then grow the particle in another. (c) assembles to a stable state, eg. a liquid crystal.
Purpose? In biosensing, the dielectric Dynamic self-assembly is when the system is
property of the shell can control the surface oscillating between states and is dissipating
plasmon of the core. In drug delivery, the energy in the process, eg. an oscillating
shell could react with a specific location and chemical reaction.
the core could be used as a treatment.
25.19 Compare SAMs and cell membranes? SAM S26.4 Demonstate that the polymerization of
can structurally resemble a phospholipid propene with a simple Cp2ZrCl2 catalyst
bilayer. would give rise to atactic polypropene?
25.20 What is morphosynthesis? Control of
Without R groups attached to the Zr center
nanoarchitectures in inorganic materials
there is no preference for specific binding
through changes in synthesis parameters.
during polymerization.
25.21 (a) What are the two classes of inorganic-
organic nanocomposites? Class I, hybrid Exercises
materials where no covalent or ionic bonds
are present. Class II, at least some of the 26.1 Which of the following constitute catalysis?
components are linked through chemical (a) H2 and C2H4 in contact with Pt? An
bonds. (b) Examples? Class I, block example of genuine catalysis.
copolymers. Class II, polymer/clay (b) H2 plus O2 plus an electrical arc? Not
nanocomposites. catalysis..
25.22 (a) Why is dispersion important in (c) The production of Li3N and its reaction
nanocomposites? They lead to increased with H2O? Not catalysis.
exposed surface areas. (b) Why is dispersion 26.2 Define the following terms? (a) Turnover
difficult? The often nonpolar organic frequency? The amount of product formed
polymers do not have strong interactions with per unit time per unit amount of catalyst.
the polar or ionic inorganic components.
(b) Selectivity? How much of the desired
25.23 A bionanomaterial and its application? product is formed relative to by-products.
PPF/PPF-DA is an injectable bionanomaterial (c) Catalyst? A substance that increases the
used for bone-tissue engineering. rate of a reaction but is not itself consumed.
25.24. (a) Biomimetics? Designing nanomaterials (d) Catalytic cycle? Sequence of chemical
that mimic biological systems. (b) example of reactions involving the catalyst that transform
biomimetics? Cellulose fibers in paper have the reactants into products.
been used to template the growth of titanium (e) Catalyst support? Generally a ceramic
oxide nanotubes. like -alumina or silica gel.
25.25 Bionanocomposites and improved 26.3 Classify the following as homogeneous or

mechanical strength? Biomimetics need heterogeneous catalysis? (a) The increased
trabecular and cortical bone tissues, which rate of SO2 oxidation in the presence of
combine compressibility and tensile strength. NO? Homogeneous.
Hybrid alumoxane nanoparticles dispersed in (b) The hydrogenation of oil using a finely
PPF/PPF-DA shows enhanced strength. divided Ni catalyst? Heterogeneous.
(c) The conversion of D-glucose to a D,L
mixture by HCl? Homogeneous.
CHAPTER 26
26.4 Which of the following processes would be
Self-tests worth investigating? (a) The splitting of
H2O into H2 and O2? Not worthwhile.
S26.1 The effect of added phosphine on the (b) The decomposition of CO2 into C and
catalytic activity of RhH(CO)(PPh3)3? O2? A waste of time.
Added phosphine will result in a lower (c) The combination of N2 with H2 to
concentration of the catalytically active 16- produce NH3? Very worthwhile reaction to
electron complex. try to catalyze efficiently at 80C.
S26.2 -Alumina heated to 900C, cooled, and (d) The hydrogenation of double bonds in
exposed to pyridine vapor? complete vegetable oil? The process can be readily
dehydroxylation. set up with existing technology.
S26.3 Would a pure silica analog of ZSM-5 be an 26.5 Why does the addition of PPh3 to
active catalyst for benzene alkylation (see RhCl(PPh3)3 reduce the hydrogenation
Figure 26.24)? No.
turnover frequency? The catalytic species exchange of the methyl group in the
that enters the cycle is RhCl(PPh3)2(Sol) (Sol chemisorbed CHR(CH3) group (R =
= a solvent molecule). C(CH3)2(C2H5)).
26.6 Explain the trend in rates of H2 absorption 26.14 Why does CO decrease the effectiveness of
by various olefins catalyzed by Pt in catalyzing the reaction 2H+(aq) + 2e
RhCl(PPh3)3? In both cases, the alkene that H2(g)? Platinum has a strong tendency to
is hydrogenated more slowly has a greater chemisorb CO.
degree of substitution and so is sterically
26.15 Describe the role of an electrocatalyst?
more demanding.
Platinum is the most efficient electrocatalyst
26.7 Hydroformylation catalysis with and for accelerating oxygen reduction at the fuel
without added P(n-Bu)3? The cell cathode, but is expensive.
transformation of (E) into CoH(CO)4 must be
the rate-determining step in the absence of
added P(n-Bu)3. In the presence of added
P(n-Bu)3, the formation of either (A) or (E) is CHAPTER 27
the rate-determining step.
Self-tests
26.8 How does starting with MeCOOMe instead
of MeOH lead to ethanoic anhydride S27.1 Is Iron (II) expected to be present in the
instead of ethanoic acid using the cell as uncomplexed ions? No.
Monsanto acetic acid process? The reaction S27.2 Unusual coordination of Mg? The proteins
of the ethanoate ion with the acetyl iodide 3D structure can place any particular atom in
leads to ethanoic anhydride. a suitable position for axial coordination.
S27.3 Why does saline contain NaCl? Osmotic
26.9 Suggest a reason why? (a) Ring opening balance.
alkene metathesis polymerization (ROMP)
proceeds? ROMP can result in reduced S27.4 Explain the significance of the Calcium ion
steric strain. (b) Ring-closing metathesis pumps activation by calmodulin? The
(RCM) reaction proceeds? RCM results in binding of calmodulin is a signal informing
the loss of ethane. the pump that the cytoplasmic Ca2+ level has
risen above a certain level.
26.10 (a) Attack by dissolved hydroxide?
Structure C in Figure 26.11 (b) Attack by S27.5 Why are iron-porphyrin complexes unable
coordinated hydroxide? Structure E given in to bind O2 reversibly? The Fe(II) gets
Figure 26.11 (c) Can one differentiate the oxidized to Fe(III), yielding an oxo-Iron(III)
stereochemistry? Yes. porphyrin complex.
26.11 (a) Enhanced acidity? When Al3+ replaces
Si4+ on lattice site charge is balanced by S27.6 What is the nature of binding at Cu blue
H3O+. centers as indicated by the EPR spectrum?
There is greater covalence in blue Cu centers
(b) Three other ions? Ga3+, Co3+, and Fe3+. than in simple Cu(II) compounds.
26.12 Why is the platinum-rhodium in S27.7 What is the nature of an active site with
automobile catalytic converters dispersed Copper (III)? Diamagnetic with square-
on the surface of a ceramic rather than planar geometry.
used in the form of thin foil? A thin foil of S27.8 Why mercury is so toxic because of the
action of enzymes containing cobalamin?
platinum-rhodium will not have as much
Cobalamins are very active methyl transfer
surface area as an equal amount of small
reactions, which can methylate anything in
particles finely dispersed on the surface of a
the cell.
ceramic support.
26.13 Devise a plausible mechanism to explain S27.9 Suggest experiments that could establish
the deuteration of 3,3-dimethylpentane? the structure of the MoFe cofactor? EPR,
(i) The mechanism of deuterium exchange is single-crystal X-ray diffraction, and EXAFS.
probably related to the reverse of the last two S27.10 Why might Cu sensors be designed to bind
reactions in Figure 26.20. Cu(I) rather than Cu(II)? Cu(I) has an
almost unique ability to undergo linear
(ii) The second observation can be explained coordination by sulphur-containing ligands.
by invoking a mechanism for rapid deuterium
Exercises
27.1 Lanthanides versus calcium? They are hard

Lewis acids and prefer coordination by hard
bases. Gd3+ has excellent fluorescence.
27.2 Substituting Co2+ for Zn2+? Co(II)
commonly adopts distorted tetrahedral and
five-coordinate geometries typical of Zn(II) in
enzymes. Co(II) is paramagnetic, enabling Zn
enzymes to be studied by EPR.
27.3 Compare the acid/base catalytic activities
of Zn(II), Fe(III), and Mg(II)? Acid
strengths: Fe(III) > Zn(II) > Mg(II). Ligand
binding rates are Mg(II) > Zn(II) > Fe(III).
27.4 Propose a physical method for the
determination of Fe(V)? EPR or
Mossbauer.
27.5 Interpret the Mossbauer spectra of
ferredoxin? In the spectrum, the oxidized
spectrum is consistent with the iron atoms
having the same valence, intermediate
between the 3+ and the 2+ states, with one
pair spin-up and the other pair spin-down.
27.6 Explain the differences in the structures of
the oxidized and reduced forms of the P-
cluster in nitrogenase? The change in
structure suggest that the coupling of proton
and electron transfer can also occur at the P-
cluster, by controlling protonation of the
exchangeable ligands.
27.7 What metals are involved in the synthesis
of acetyl groups? Co(II), Fe(II) and Cu(I).

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Shriver & Atkins: Inorganic Chemistry 5e

Answers to self-tests and exercises

CHAPTER 1 1.7 Take the summation of the rest masses of all

S1.6 Ni :[Ar]3d 8 4s 2 , Ni 2+ :[Ar]3d 8 1 1 1 7 1

S1.8 Going down a group the atomic radius 1 1 1 7 1

1.17 The 1s electrons shield the positive charge

2 ANSWERS TO SELF-TESTS AND EXERCISES

1.18 See Figs 1.11 through 1.16 1.30

ANSWERS TO SELF-TESTS AND EXERCISES 3

(b) square planar (b) one

2.10 (a) 0 2.21 (a-c)

2.12 (a) covalent

4 ANSWERS TO SELF-TESTS AND EXERCISES

(b) electron precise 3.4 XA2

S3.13 MgSO4 < CaSO4 < SrSO4 < BaSO4.

S3.16 Phosphorus and aluminium. 3.18 (a) MgSO4

3.2 Points on the cell corners at (0,0,0), (1,0,0),

ANSWERS TO SELF-TESTS AND EXERCISES 5

3.25 Yes. S4.9 Identify the acids and bases?

S4.1 (a) HNO3 + H2O H3O+ + NO3

S4.3 Calculate the pH of a 0.20 M tartaric acid

6 ANSWERS TO SELF-TESTS AND EXERCISES

Cl (c) Si(OH)4 or Ge(OH)4?

ANSWERS TO SELF-TESTS AND EXERCISES 7

(b) CO2 and CaCO3? (aq) + 2Cl(aq)? >1

H2SO4 + HF H3SO4+ + F- The phosphorus atom in Me2NPF2 is the

8 ANSWERS TO SELF-TESTS AND EXERCISES

SiO2 + 6HF 2H2O + H2SiF6 (c) C6H5COOH?

ANSWERS TO SELF-TESTS AND EXERCISES 9

5.3 Write balanced equations, if a reaction

10 ANSWERS TO SELF-TESTS AND EXERCISES

(d) I2 2I? Acid or base, no difference.

ANSWERS TO SELF-TESTS AND EXERCISES 11

CHAPTER 6 SF6 has Oh symmetry. Analysis of the

12 ANSWERS TO SELF-TESTS AND EXERCISES

6.7 PF5? (a) Point group? D3h.

ANSWERS TO SELF-TESTS AND EXERCISES 13

7.2 Write the formulas for the following

14 ANSWERS TO SELF-TESTS AND EXERCISES

7.4 Four-coordinate complexes? (a) Sketch the

tetrahedral square planar

Trigonal Bipyramidal Square based pyramid

7.13 Which complexes have isomers?

(a) [Pt(ox)(NH3)2] no isomers

(b) [PdBrCl(PEt3)2] has two isomers.

ANSWERS TO SELF-TESTS AND EXERCISES 15

N N N N 8.4 Wavelength of neutron at 2.20 km/s? 1.80

S8.1 Main features of the CrO2 powder XRD

16 ANSWERS TO SELF-TESTS AND EXERCISES

CHAPTER 9 9.5 Inert pair effect beyond Group 15? The

ANSWERS TO SELF-TESTS AND EXERCISES 17

CHAPTER 10 (iii) CO(g) + H2O CO2(g) + H2 (g)

18 ANSWERS TO SELF-TESTS AND EXERCISES

10.21.1 Dihydrogen as an oxidizing agent? Its

H3O+ should be trigonal pyramidal.

ANSWERS TO SELF-TESTS AND EXERCISES 19

(b) Why are group 1 metals poor CHAPTER 12

20 ANSWERS TO SELF-TESTS AND EXERCISES

BeBr2 should be covalent. MgBr2 should be the preparation of N, N, N-trimethyl-

and 2,4,6-(CH ) C H MgBr dissolve in THF.

What differences would be expected in the

12.13 Predict the products of the following

ANSWERS TO SELF-TESTS AND EXERCISES 21