TUTORIAL PROBLEMS
CHAPTER 1
1.1 In the paper ‘What can the Bohr–Sommerfeld model show
students of chemistry in the 21st century?’ (M. Niaz and L.
Cardellini, J. Chem. Educ., 2011, 88, 240) the authors use the
development of models of atomic structure to deliberate on
the nature of science. What were the shortcomings of the Bohr
model of the atom? How did Sommerfeld refine Bohr’s model?
How did Pauli resolve some of the new model’s shortcomings?
Discuss what these developments teach us about the nature of
science.
1.2 Survey the early and modern proposals for the construction
of the periodic table. You should consider attempts to arrange
the elements on helices and cones as well as the more practical
two-dimensional surfaces. What, in your judgement, are the
advantages and disadvantages of the various arrangements?
1.3 In their 2009 paper ‘Icon of chemistry: The periodic system
of chemical elements in the new century’ (Angew. Chem. Int. Ed.,
2009, 48, 3404), S. Wang and W. Schwarz claim that the periodic
system of elements has suffered from the ‘invention of scientific
facts’. Summarize their key arguments in relation to the electron
configurations of the transition elements.
1.4 The decision about which elements should be identified as
belonging to the f block has been a matter of some controversy.
A view has been expressed by W.B. Jensen (J. Chem. Educ., 1982,
59, 635). Summarize the controversy and Jensen’s arguments. An
alternative view has been expressed by L. Lavalle (J. Chem. Educ.,
2008, 85, 1482). Summarize the controversy and the arguments.
CHAPTER 2
2.1 In valence bond theory, hypervalence is usually explained in
terms of d-orbital participation in bonding. In the paper ‘On the
role of orbital hybridisation’ (J. Chem. Educ., 2007, 84, 783) the
author argues that this is not the case. Give a concise summary of
the method used and the author’s reasoning.
2.2 Develop an argument based on bond enthalpies for the
importance of Si−O bonds, in preference to Si−Si or Si−H bonds,
in substances common in the Earth’s crust. How and why does
the behaviour of silicon differ from that of carbon?
2.3 The van Arkel–Ketelaar triangle has been in use since the
1940s. A quantitative treatment of the triangle was carried out by
Gordon Sproul in 1994 (J. Phys. Chem., 1994, 98, 6699). How
many scales of electronegativity and how many compounds did
Sproul investigate? What criteria were used to select compounds
for the study? Which two electronegativity scales were found to
give the best separation between areas of the triangle? What were
the theoretical bases of these two scales?
1.5 During 1999 several papers appeared in the scientific
literature claiming that d orbitals of Cu2O had been observed
experimentally. In his paper ‘Have orbitals really been observed?’
(J. Chem. Educ., 2000, 77, 1494), Eric Scerri reviews these
claims and discusses whether orbitals can be observed physically.
Summarize his arguments briefly.
1.6 At various times the following two sequences have been
proposed for the elements to be included in Group 3: (a) Sc, Y,
La, Ac, (b) Sc, Y, Lu, Lr. Because ionic radii strongly influence the
chemical properties of the metallic elements, it might be thought
that ionic radii could be used as one criterion for the periodic
arrangement of the elements. Use this criterion to describe which
of these sequences is preferred.
1.7 In the paper ‘Ionization energies of atoms and atomic ions’
(P.F. Lang and B.C. Smith, J. Chem. Educ., 2003, 80, 938) the
authors discuss the apparent irregularities in the first and second
ionization energies of d- and f-block elements. Describe how these
inconsistencies are rationalized.
1.8 The electron configuration of the transition metals is
described by W.H.E. Schwarz in his paper ‘The full story of the
electron configurations of the transition elements’ (J. Chem.
Educ., 2010, 87, 444). Schwarz discusses five features that must
be considered to fully understand the electron configurations of
these elements. Discuss each of these five features and summarize
the impact of each on our understanding of the electronic
configurations.
2.4 In their short article ‘In defense of the hybrid atomic orbitals’
(P.C. Hiberty, F. Volatron, and S. Shaik, J. Chem. Educ., 2012,
89, 575), the authors defend the continuing use of the concept of
the hybrid atomic orbital. Summarize the criticisms that they are
addressing and present an outline of their arguments in favour of
hybrid orbitals.
2.5 In their article ‘Some observations on molecular orbital
theory’ (J.F. Harrison and D. Lawson, J. Chem. Educ., 2005,
82, 1205) the authors discuss several limitations of the theory.
What are these limitations? Sketch the MO diagram for Li2 given
in the paper. Why do you think this version does not appear in
textbooks? Use the data given in the paper to construct MO
diagrams for B2 and C2. Do these versions differ from those in
Fig. 2.17 in this textbook? Discuss any variations.
2.6 (a) Use a molecular orbital program or input and output from
software supplied by your instructor to construct a molecular
orbital energy-level diagram to correlate the MO (from the
2 Tutorial problems
output) and AO (from the input) energies and indicate the
occupancy of the MOs (in the manner of Fig. 2.17) for one of
the following molecules: HF (bond length 92 pm), HCl (127 pm),
or CS (153 pm). (b) Use the output to sketch the form of the
occupied orbitals, showing the signs of the AO lobes by shading
and their amplitudes by means of size of the orbital.
2.7 Use software to perform an MO calculation on H3 by using
the H energy given in Problem 2.6 and H–H distances from NH3
(N–H length 102 pm, HNH bond angle 107°) and then carry
out the same type of calculation for NH3. Use energy data for
N2s and N2p orbitals from Problem 2.6. From the output, plot
the molecular orbital energy levels with proper symmetry labels
and correlate them with the N orbitals and H3 orbitals of the
CHAPTER 3
3.1 Both ccp and hcp have identical close-packed volumes,
but the calculated Gibbs free energy of the two arrangements
shows that ccp is more stable by 0.002–0.012 kJ mol−1 at room
temperature (L.V. Woodcock, Nature, 1997, 385, 141, P.G.
Bolhuis, D. Frenkel, S-C Mau and D.A. Huse, Nature, 1997,
388, 235). Determine independently the number of neighbours
in the first five coordination shells for these two close-packed
structures and, thereby, describe the origin of this difference in
free energy.
3.2 Calculate the number of atoms present in a cubic gold
nanoparticle of dimensions 2 × 2 × 2 nm3; gold adopts an fcc unit
cell with lattice parameter of 400 pm. Discuss how the size of
silver and gold nanoparticles affects their colour and how this has
led to their historical application in stained glass.
3.3 The relative positons of tetrahedral and octahedral holes
between close-packed layers may be described using the PTOT
system, where P represents a close-packed layer, and T and O the
tetrahedral and octahedral holes, respectively. Use this description
and the formation of ‘stuffed’ PTOT arrangements (B.E. Douglas,
J. Chem. Educ., 2007, 84, 1846) to describe the structures of (a)
Li3Bi, (b) CdCl2, (c) MoS2, and (d) BeAl2O4.
3.4 By considering the rock-salt structure and the distances and
charges around one central ion, show that the first six terms of
the Na+ Madelung series are
6 12 8 6 24 24
− + − + − 19
1 2 3 4 5 6
 iscuss methods for showing that this series converges to 1.748
D 3.8 The following linear correlation, sometimes referred to as
by reference to R.P. Grosso, J.T. Fermann, and W.J. Vining, J.
Chem. Educ., 2001, 78, 1198.
3.5 Nanocrystals with dimensions of 1–10 nm are of increasing
importance in technological applications (see Chapter 24). The
calculation of the Madelung constant for a particular structure
type requires the summation of an infinite series of terms,
and this method is not applicable to a crystal of nanometre
dimensions. Discuss how the concept of a Madelung factor,
A*, may be used to describe the total ionic interactions in
nanocrystals. How does A* vary as a function of nanocrystal size
for (a) the NaCl structure type and (b) the CsCl structure type?
How might the properties of a nanocrystal differ from the bulk
appropriate symmetries. Compare the results of this calculation
with the qualitative description in Problem 2.6.
2.8 The effects of the nonbonding lone pair in the tin and
lead anions in compounds such as Sr(MX3)2.5H2O (M = Sn or
Pb, X = Cl or Br) have been studied by crystallography and by
electronic structure calculations (I. Abrahams et al., Polyhedron,
2006, 25, 996). Briefly outline the synthetic method used to
prepare the compounds and indicate which compound could not
be prepared. Explain how this compound was handled in the
electronic structure calculations as no experimental structural
data were available. State the shape of the [MX3]− anions and
describe how the effect of the nonbonding lone pair varies
between Sn and Pb in the gas phase and the solid phase.
solid as a result? See M.D. Baker and A.D. Baker, J. Chem. Educ.,
2010, 87, 280.
3.6 Discuss the thermodynamic factors behind the observation
that CuO is a well-known, stable oxide of Cu(II) but AgO is a
mixed-valence oxide, Ag(I)Ag(III)O2. See D. Tudela, J. Chem.
Educ., 2008, 85, 863. AgF2 is a stable compound of Ag(II);
discuss what factors might contribute to the stability of Ag(II) in
combination with fluoride.
3.7 The Kapustinskii equation shows that lattice enthalpies are
inversely proportional to the interionic distances. Later work has
shown that further simplification of the Kapustinskii equation
allows lattice enthalpies to be estimated from the molecular
(formula) unit volume (the unit cell volume divided by the
number of formula units, Z, that it contains) or the mass density
(see, for example, H.D.B. Jenkins and D. Tudela, J. Chem. Educ.,
2003, 80, 1482). How would you expect the lattice enthalpy to
vary as a function of (a) the molecular unit volume and (b) the
mass density? Given the following unit cell volumes (all in cubic
angstroms, Å3; 1 Å = 10−10 m) for the alkaline earth carbonates
MCO3 and oxides, predict the observed decomposition behaviour
of the carbonates.
MgCO3 CaCO3 SrCO3 BaCO3
47 61 64 76
MgO CaO SrO BaO
28 34 42
Bartlett’s relationship, has been found between lattice enthalpy
(kJ mol−1) and the inverse cube root of the formula unit volume V
(in nm3) for 1:1 MX salts.
232.8
∆H L = + 110
3
V
S how that this expression is related to the Kapustinskii equation.
Formula unit cell volumes are readily obtainable from X-ray
diffraction studies of crystalline, ionic MX structures and,
therefore, Bartlett’s relationship may be used where individual
thermochemical radii are not available. Discuss how application
of this relationship has been used to account for the inability to
synthesize [I2]+[AlCl4]− and the instability of [I3]+[AsF6]− (H.D.B.

Jenkins, H.K. Roobottom, J. Passmore, and L. Glasser, Inorg.
Chem., 1999, 38, 3609).
3.9 The analysis undertaken in Problem 4.8 may be extended
to give the ‘isomegethic rule’ which states that ‘The formula unit
volumes, Vm, of isomeric ionic salts are approximately the same’;
see H.D.B. Jenkins et al., Inorg. Chem., 2004, 43, 6238, and L.
Glasser, J. Chem. Educ., 2011, 88, 581. Discuss the basis for this
‘rule’ and its applications in solid-state chemistry.
CHAPTER 4
4.1 Consider a molecule IF3O2 (with I as the central atom). How
many isomers are possible? Assign point group designations to
each isomer.
4.2 How many isomers are there for ‘octahedral’ molecules with
the formula MA3B3, where A and B are monoatomic ligands?
What is the point group of each isomer? Are any of the isomers
chiral? Repeat this exercise for molecules with the formula
MA2B2C2.
4.3 Group theory is often used by chemists as an aid in the
interpretation of IR spectra. For example, there are four NH
+
bonds in NH 4 and four stretching modes are possible. There
is the possibility that several vibrational modes occur at the
same frequency, and hence are degenerate. A quick glance at the
character table will tell if degeneracy is possible. (a) In the case of
the tetrahedral NH 4+ ion, is it necessary to consider the possibility
of degeneracies? (b) Are degeneracies possible in any of the
vibrational modes of NH 2 D2+ ?
4.4 Determine whether the number of IR and Raman active
stretching modes could be used to determine uniquely whether a
sample of gas is BF3, NF3, or ClF3.
4.5 Reaction of AsCl3 with Cl2 at low temperature yields a
product, believed to be AsCl5, which shows Raman bands at 437,
369, 295, 220, 213, and 83 cm−1. Detailed analysis of the 369
and 295 cm−1 bands shows them to arise from totally symmetric
modes. Show that the Raman spectrum is consistent with a
trigonal-bipyramidal geometry.
4.6 Show how you would use Raman and infrared spectroscopy
to distinguish between regular octahedral and regular trigonal
prismatic geometries of a six-coordinate species, ML6. Discuss the
possible distortions that could occur in either case (you do not need
to determine the symmetries of vibrations for the distorted states).
CHAPTER 5
5.1 A paper by Gillespie and Liang entitled ‘Superacid solutions
in hydrogen fluoride’ (J. Am. Chem. Soc., 1988, 110, 6053)
discusses the acidity of various solutions of inorganic compounds
in HF. (a) Give the order of acid strength of the pentafluorides
determined during the investigation. (b) Give the equations for the
reactions of SbF5 and AsF5 with HF. (c) SbF5 forms an F-bridged
− Commun., 1990, 1213.)
dimer (Sb2F11 ) in HF: give the equation for the equilibrium
between the monomeric and the dimeric species.
Tutorial problems 3
3.10 Discuss the ‘water-bottle’ analogy in interpreting the
electronic properties of metallic, insulating and semiconducting
solids (P.F. Weller, J. Chem. Educ., 1967, 44, 391).
3.11 ‘Band theory is less helpful than Mott–Hubbard theory . . .
in explaining conductivity and semiconductivity to introductory
students’ (S.J. Hawkes, J. Chem. Educ., 2012, 89, 694). Describe
the Mott–Hubbard model and its applications in explaining how
metallic behaviour can arise in solids.
4.7 Consider the p orbitals on the four Cl atoms of tetrahedral
[CoCl4]2−, with one p orbital on each Cl pointing directly at the
central metal atom. (a) Confirm that the four p orbitals which
point at the metal transform in an identical manner to the four s
orbitals on the Cl atoms. How might these p orbitals contribute
to the bonding of the complex? (b) Take the remaining eight
p orbitals and determine how they transform. Reduce the
representation you derive to determine the symmetry of the
SALCs these orbitals contribute to. Which metal orbitals can these
SALCs bond with? (c) Generate the SALCs referred to in (b).
4.8 Consider all 12 of the p orbitals on the four Cl atoms of a
square planar complex like [PtCl4]2−. (a) Determine how these
p orbitals transform under D4h and reduce the representation.
(b) Which metal orbitals can these SALCs bond with? (c) Which
SALCs and which metal orbitals contribute to σ bonds? (d) Which
SALCs and which metal orbitals contribute to the in-plane π
bonds? (e) Which SALCs and which metal orbitals contribute to
the out-of-plane π bonds?
4.9 Consider an octahedral complex and construct all the σ- and
π-bonding SALCs.
4.10 Construct an approximate molecular orbital energy
diagram for a hypothetical planar form of NH3. You may refer
to Resource section 4 to determine the form of the appropriate
orbitals on the central N atom and on the triangle of H3 atoms.
From a consideration of the atomic energy levels, place the N
and H3 orbitals on either side of a molecular orbital energy-level
diagram. Then use your judgement about the effect of bonding
and antibonding interactions and energies of the parent orbitals
to construct the molecular orbital energy levels in the centre of
your diagram and draw lines indicating the contributions of the
atomic orbitals to each molecular orbital. Ionization energies are
I(H1s) = 13.6 eV, I(N2s) = 26.0 eV, and I(N2p) = 13.4 eV.
5.2 In the reaction of t-butyl bromide with Ba(NCS)2, the
product is 91 per cent S-bound tBu–SCN. However, if Ba(NCS)2
is impregnated into solid CaF2, the yield is higher and the product
is 99 per cent t-Bu–NCS. Discuss the effect of alkaline earth metal
salt support on the hardness of the ambident nucleophile SCN−.
(See T. Kimura, M. Fujita, and T. Ando, J. Chem Soc., Chem.
4 Tutorial problems
5.3 In their paper ‘The strengths of the hydrohalic acids’ (J. Chem.
Educ., 2001, 78, 116), R. Schmid and A. Miah discuss the validity of
literature values of the pKa values for HF, HCl, HBr, and HI. (a) On
what basis have the literature values been estimated? (b) To what is
the low acid strength of HF relative to HCl usually attributed? (c)
What reason do the authors suggest for the high acid strength of HCl?
5.4 Superacids are well established but superbases also exist and
are usually based on hydrides of Group 1 and Group 2 elements.
Write an account of the chemistry of superbases.
5.5 In a review article (Angew. Chem. Int. Ed., 2009, 48, 2100),
E.J. Corey describes asymmetric catalysis by chiral boranes. Show
how these chiral boranes, which are Lewis acids, are also able to
direct Brønsted acidity.
CHAPTER 6
6.1 The compound Na2IrCl6 reacts with triphenylphosphine in
diethylene glycol in an atmosphere of CO to give trans-[IrCl(CO)
(PPh3)2], known as ‘Vaska’s compound’. Excess CO gives a five-
coordinate species and treatment with NaBH4 in ethanol gives
[IrH(CO)2(PPh3)2]. Derive a formal name for Vaska’s compound.
Draw and name all isomers of the two five-coordinate complexes.
6.2 A pink solid has the formula CoCl3.5NH3.H2O. A solution of
this salt is also pink and rapidly gives 3 mol AgCl on titration with
silver nitrate solution. When the pink solid is heated, it loses 1 mol
H2O to give a purple solid with the same ratio of NH3:Cl:Co. The
purple solid, on dissolution and titration with AgNO3, releases
two of its chlorides rapidly. Deduce the structures of the two
octahedral complexes and draw and name them.
6.3 The hydrated chromium chloride that is available
commercially has the overall composition CrCl3·6H2O. On
boiling a solution, it becomes violet and has a molar electrical
conductivity similar to that of [Co(NH3)6]Cl3. By contrast,
another form of CrCl3·6H2O is green and has a lower molar
conductivity in solution. If a dilute acidified solution of the green
complex is allowed to stand for several hours, it turns violet.
Interpret these observations with structural diagrams.
6.4 The complex first denoted β-[PtCl2(NH3)2] was identified
as the trans isomer. (The cis isomer was denoted α.) It reacts
slowly with solid Ag2O to produce [Pt(NH3)2(OH2)2]2+. This
complex does not react with 1,2-diaminoethane to give a chelated
complex. Name and draw the structure of the diaqua complex. A
third isomer of composition PtCl2·2NH3 is an insoluble solid that,
when ground with AgNO3, gives a mixture containing [Pt(NH3)4]
(NO3)2 and a new solid phase of composition Ag2[PtCl4]. Give the
structures and names of each of the three Pt(II) compounds.
6.5 Air oxidation of Co(II) carbonate and aqueous ammonium
chloride gives a pink chloride salt with a ratio of 4NH3:Co.
On addition of HCl to a solution of this salt, a gas is rapidly
evolved and the solution slowly turns violet on heating. Complete
evaporation of the violet solution yields CoCl3·4NH3. When this
product is heated in concentrated HCl, a green salt can be isolated
with composition CoCl3·4NH3·HCl. Write balanced equations
for all the transformations occurring after the air oxidation.
Give as much information as possible concerning the isomerism
occurring, and the basis of your reasoning. Is it helpful to know
that the form of [Co(Cl)2(en)2]+ that is resolvable into enantiomers
is violet?
5.6 An article by Poliakoff and co-workers describes how a new
industrial chemical process was initiated, in which conventional
solvents were replaced by scCO2 (Green Chem., 2003, 5, 99).
Explain the advantages and challenges of introducing such
changes to traditional technology.
5.7 The reversible reaction of CO2 gas with aqueous emulsions
of long-chain alkyl amidine compounds has important practical
applications. Describe the chemistry that is involved in this
demonstration of ‘switchable surfactants’ (Science, 2006, 313, 958).
5.8 An article by Krossing and co-workers (J. Am. Chem. Soc.,
2006, 128, 13427) explains the behaviour of ionic liquids in terms
of a thermodynamic cycle approach. Describe the principles that
are applied and summarize the predictions that are made.
6.6 When cobalt(II) salts are oxidized by air in a solution
containing ammonia and sodium nitrite, a yellow solid,
[Co(NO2)3(NH3)3], can be isolated. In solution it is
nonconducting; treatment with HCl gives a complex that,
after a series of further reactions, can be identified as trans-
[Co(Cl)2(NH3)3(OH2)]+. It requires an entirely different route to
prepare cis-[Co(Cl)2(NH3)3(OH2)]+. Is the yellow substance fac or
mer? What assumption must you make to arrive at a conclusion?
6.7 The reaction of [ZrCl4(dppe)] with Mg(CH3)2 gives
[Zr(CH3)4(dppe)]. NMR spectra indicate that all methyl groups
are equivalent. Draw octahedral and trigonal prism structures for
the complex and show how the conclusion from NMR supports
the trigonal prism assignment (P.M. Morse and G.S. Girolami,
J. Am. Chem. Soc., 1989, 111, 4114).
6.8 The resolving agent d-cis[Co(NO2)2(en)2]Br can be converted
to the soluble nitrate by grinding in water with AgNO3. Outline
the use of this species for resolving a racemic mixture of the d and
l enantiomers of K[Co(edta)]. (The l-[Co(edta)]− enantiomer forms
the less soluble diastereomer; see F.P. Dwyer and F.L. Garvan,
Inorg. Synth., 1965, 6, 192.)
6.9 Show how the coordination of two MeHNCH2CH2NH2
ligands to a metal atom in a square-planar complex results in not
only cis and trans but also optical isomers. Identify the mirror
planes in the isomers that are not chiral.
6.10 Use a group-theory analysis to assign point groups to the all
cis and all trans isomers of [MA2B2C2]; use the character tables
associated with each to determine whether they are chiral or not.
6.11 BINAP is a chelating diphosphine ligand shown below.
Discuss the reasons for the observed chirality of BINAP, and of its
complexes.
PPh2
PPh2
6.12 The equilibrium constants for the successive reactions of
1,2-diaminoethane with Co2+, Ni2+, and Cu2+ are as follows:

[M(OH 2 )6 ]2+ + en  [M(en)(OH 2 )4 ]2+ + 2 H 2O K1
[M(en)(OH 2 )4 ]2+ + en  [M(en)2 (OH 2 )2 ]2+ + 2 H 2O K2
[M(en)2 (OH 2 )2 ]2+ + en  [M(en)3 ]2+ + 2 H 2O K3
Ion log K1 log K2 log K3
Co2+ 5.89 4.83 3.10
Ni2+
7.52 6.28 4.26
Cu2+ 10.72 9.31 −1.0
CHAPTER 7
7.1 Use standard potential data to suggest why permanganate
(MnO4−) is not a suitable oxidizing agent for the quantitative
estimation of Fe2+ in the presence of HCl but becomes so if
sufficient Mn2+ and phosphate ion are added to the solution. (Hint:
Phosphate forms complexes with Fe3+, thereby stabilizing it.)
7.2 Explain the significance of reduction potentials in inorganic
chemistry, highlighting their applications in investigations of
stability, solubility, and reactivity in water.
7.3 Using Resource sections 1–3, and data for atomization of
⦵
the elements ΔfH = 397 kJ mol−1 (Cr) and 664 kJ mol−1 (Mo),
construct thermodynamic cycles for the reactions of Cr or Mo
with dilute acids and thus consider the importance of metallic
bonding in determining the standard reduction potentials for
formation of cations from metals.
7.4 Enterobactin (Ent) is a special ligand secreted by some
bacteria to sequester Fe from the environment (Fe is an
essential nutrient for almost all living species, see Section
26.6). The equilibrium constant for formation of [Fe(III)(Ent)]
(1052 mol−1 dm3) is at least forty orders of magnitude higher than
the equilibrium constant for the corresponding Fe(II) complex.
Determine the feasibility of releasing Fe from [Fe(III)(Ent)] by its
reduction to Fe(II) under conditions of neutral pH, noting that the
strongest reducing agent normally available to bacteria is H2.
7.5 The reduction potential of an ion such as OH− can be
strongly influenced by the solvent. (a) From the review article by
D.T. Sawyer and J.L. Roberts (Acc. Chem. Res., 1988, 21, 469),
describe the magnitude of the change in the potential of the OH/
OH− couple on changing the solvent from water to acetonitrile,
CH3CN. (b) Suggest a qualitative interpretation of the difference
in solvation of the OH− ion in these two solvents.
7.6 Construct an Ellingham diagram for the thermal splitting of
water (H2O(g) → H2(g) + ½ O2(g)) by using ΔrH = +260 kJ mol−1;
⦵
⦵
ΔrS = +60 J K mol (you may assume that ΔrH is independent
−1 −1 ⦵
of temperature). Hence, calculate the temperature at which H2
may be obtained by spontaneous decomposition of water (Chem.
Rev., 2007, 107, 4048). Comment on the feasibility of producing
H2 by this means.
7.7 By reference to the paper by K. Shah, B. Moghtaderi, and T.
Wall (Energy Fuels, 2012, 26, 2038), discuss how the information
represented in Ellingham diagrams can be used to identify metal
oxides suitable for the production of pure O2 from air.
7.8 Discuss how the equilibrium Cu2+(aq) + Cu(s)  2 Cu+(aq)
can be shifted by complexation with chloride ions (see J.
Malyyszko and M. Kaczor, J. Chem. Educ., 2003, 80, 1048).
Tutorial problems 5
Discuss whether these data support the generalizations in the text
about successive formation constants. How do you account for
the very low value of K3 for Cu2+?
6.13 How may the aromatic character of a chelate ring provide
additional stabilization of a complex? See A. Crispini and M.
Ghedini, J. Chem. Soc., Dalton Trans., 1997, 75.
6.14 What are rotaxanes, and how do they differ from
pseudorotaxanes? Discuss how coordination chemistry might be
used to synthesize such molecules.
7.9 In their article ‘Variability of the cell potential of a given chemical
reaction’ (J. Chem. Educ., 2004, 81, 84), L.H. Berka and I. Fishtik
⦵
conclude that E for a chemical reaction is not a state function
because the half-reactions are arbitrarily chosen and may contain
different numbers of transferred electrons. Discuss this objection.
7.10 In their article ‘A thermochemical study of ceria: exploiting
an old material for new modes of energy conversion and CO2
mitigation’ (Philos. Trans. R. Soc. London, 2010, 368, 3269),
Chueh and Haile describe a way to convert water into H2 and O2
using CeO2. Explain the chemical and thermodynamic principles
of this innovation.
7.11 In their article ‘Enzymes and bio-inspired electrocatalysts in
solar fuel devices’ (Energy Environ. Sci., 2012, 5, 7470), Woolerton
et al. use a generic Frost diagram (Fig. 7.21) to illustrate the concept
of chemical energy storage and release. So-called ‘energy-rich
substances’ are compounds (fuels and oxidants) in which chemical
energy is stored: fuels (such as hydrocarbons, boranes, metal hydrides)
lie towards the upper left whereas strong oxidants such as O2 lie
towards the upper right. ‘Energy-poor substances’ are stable, reduced
compounds (e.g. H2O) lying towards the lower left and oxidized
compounds (e.g. CO2, components of ash) lying towards the lower
right. Energy release (whether by combustion or in a fuel cell or
battery) occurs when a species from the upper left reacts with a
species from the upper right to give products positioned diagonally
down their respective arrows. During energy storage (such as
photosynthesis or charging a battery) compounds from the lower
left and lower right are transformed using sunlight or electricity into
products that are positioned diagonally upwards along their respective
arrows. Using data from Resource section 3 assess the usefulness of
this concept for a methanol/oxygen system and a lead–acid battery.
Energy rich
Fuels Oxidants
Free energy
Reduced Oxidized
Energy poor
Oxidation number, N
FIGURE 7.21 A generic Frost diagram depicting the relationships
between fuels, oxidants, and energy-poor substances such as
water, carbon dioxide, and ash.
6 Tutorial problems

CHAPTER 8
8.1 Discuss the importance of X-ray crystallography in inorganic 10.0 ppm iron. The absorptions of the standards and the sample
chemistry. See, for example, W.P. Jensen, G.J. Palenik, and I.-H. solution were measured at the iron absorption wavelength.
Suh, The history of molecular structure determination viewed
through the Nobel Prizes, J. Chem. Educ., 2003, 80, 753. Concentration/ppm Absorbance
8.2 How is single-crystal neutron diffraction of use in inorganic 1.00 0.095
chemistry?
3.00 0.265
8.3 How may metal hydride materials, of interest for hydrogen
storage applications, be characterized using the various analytical 5.00 0.450
methods discussed in this Chapter? 7.00 0.632
8.4 Discuss the information available from the following 10.0 0.910
techniques in the analysis of inorganic pigments used in antique Sample 0.545
oil paintings: (i) powder X-ray diffraction, (ii) infrared and
Raman spectroscopies, (iii) UV–visible spectroscopy, (iv) X-ray
fluorescence. Calculate the mass of iron in the tablet.
8.5 Discuss how hydrogen bonding in inorganic compounds 8.12 A sample of water from a reservoir was analysed for
can be characterized using infrared spectroscopy. How does the copper content. The sample was filtered and diluted 10-fold with
strength of a hydrogen bond affect (a) OH stretching modes (b) deionized water. A set of standards was prepared with copper
OH bending modes? concentrations between 100 and 500 ppm. The standards and the
8.6 How may a consideration of 31P chemical shifts and 1H sample were aspirated into an atomic absorption spectrometer
coupling constants be used to distinguish the isomers of the and the absorbance was measured at the copper absorption
octahedral complex [Rh(CCR)2H(PMe3)3]? (See J.P. Rourke, wavelength. The results obtained are given below. Calculate the
G. Stringer, D.S. Yufit, J.A.K. Howard, and T.B. Marder, concentration of copper in the reservoir.
Organometallics, 2002, 21, 429.)
8.7 Discuss the importance of NMR spectroscopy in the Concentration/ppm Absorbance
development of Group 18 chemistry. (See M. Gerken and G.J. 100 0.152
Schrobilgen, Coord. Chem. Rev., 2000, 197, 335.)
200 0.388
8.8 Ionization techniques in mass spectrometry frequently
induce fragmentation and other undesirable reactions. However, 300 0.590
under some circumstances these reactions can be helpful. Using 400 0.718
fullerenes as an example, discuss this phenomenon. (See M.M. 500 0.865
Boorum, Y.V. Vasil’ev, T. Drewello, and L.T. Scott, Science, 2001,
294, 828.) Sample 0.751

8.9 Discuss how EXAFS can be used to follow the isomerization

of the spiked triangular cluster [Ru3Pt(µ-H)(µ4-η2-CCBut)
(CO)9(dppe)] (dppe = 1,2-bis(diphenylphosphino)ethane) to the
butterfly cluster [Ru3Pt(µ4-η2-C=CHBut)(CO)9(dppe)]. (See A.J.
Dent, L.J. Farrugia, A.G. Orpen, and S.E. Stratford, J. Chem. Soc.,
Chem. Commun., 1992, 1456.)
8.10 Discuss how you would carry out the following analyses
and determinations: (a) calcium levels in breakfast cereal, (b)
mercury in shellfish, (c) the geometry of BrF5, (d) the number and
type of organic ligands in a d-metal complex, (e) the number of
coordinated ammonia molecules in Mg(NH3)nCl2.
8.11 The iron content of a dietary supplement tablet was
determined using atomic absorption spectrometry. A tablet
(0.4878 g) was ground to a fine powder and 0.1123 g was
dissolved in dilute sulfuric acid and transferred to a 50 cm3
volumetric flask. A 10 cm3 sample of this solution was taken
and made up to 100 cm3 in another volumetric flask. A series of
standards was prepared that contained 1.00, 3.00, 5.00, 7.00, and
8.13 A sample from an effluent stream was analysed for
phosphate levels. Dilute hydrochloric acid and excess sodium
molybdate were added to a 50 cm3 sample of the effluent.
The molybdophosphoric acid, H3PMo12O40, that was formed
was extracted into two 10 cm3 portions of an organic solvent.
A molybdenum standard with a concentration of 10 ppm
was prepared in the same solvent. The combined extract
and the standard were aspirated into an atomic absorption
spectrometer that was set up to measure molybdenum. The
extracts gave an absorbance of 0.573 and the standard gave an
absorbance of 0.222. Calculate the concentration of phosphate
in the effluent.
8.14 The particles sizes determined using powder X-ray
diffraction data peak widths (using the Scherrer formula which
is widely described in the literature) and those obtained from
imaging using electron microscopy often differ, with electron
microscopy normally yielding a larger value. Find out why this is
the case.

CHAPTER 9
9.1 In January 2016 the International Union of Pure and Applied
Chemistry (IUPAC) announced the discovery of four new elements
with atomic numbers 113, 115, 117, and 118. These elements
are very unstable and form isotopes of more stable elements by
radioactive decay. Assuming that samples of these elements could
be made that were stable enough to be investigated use your
knowledge of periodic trends to predict some of the expected
physical and chemical properties of these elements.
9.2 In the paper ‘Diffusion cartograms for the display of periodic
table data’ (J. Chem. Educ., 2011, 88, 1507), M.J. Winter
describes a technique commonly used in geography to represent
periodic trends. Write a critique of this method by comparing two
of the cartograms with two of the figures used in this chapter.
CHAPTER 10
10.1 In their article ‘Hydrogen storage in metal–organic
frameworks’ (Chem. Soc. Rev., 2009, 38, 1294), Jeffrey Long and
co-workers discuss some of the design principles for hydrogen
storage materials. List the advantages and disadvantages of
storing H2 by using weak rather than strong binding interactions.
10.2 In his paper ‘The proper place for hydrogen’ (J. Chem.
Educ., 2003, 80, 947), M.W. Cronyn argues that hydrogen should
be placed at the head of Group 14 immediately above carbon.
Summarize his reasoning.
10.3 Spectroscopic evidence has been obtained for the existence
of [Ir(C5H5)(H3)(PR3)]+, a complex in which one ligand is
formally H3+. Devise a plausible molecular orbital scheme for
the bonding in the complex, assuming that an angular H3 unit
CHAPTER 11
11.1 It has been argued that a better diagonal relationship exists
between Li and Ca than between Li and Mg (T.P. Hanusa, J.
Chem. Educ., 1967, 64, 686). Summarize the arguments for and
against this viewpoint.
11.2 Francium has been described as ‘the last discovered
natural element’ (J.-P. Adloff and G.B. Kauffman, The Chemical
Educator, 2005, 10, 387). Discuss the justification for this
statement. Summarize the evidence and claims for the first
discovery of francium.
11.3 Under ambient conditions lithium and sodium adopt simple
bcc structures. Under high pressures these alkali metals undergo
a series of complex phase transitions to fcc and then lower-
symmetry structures (M.I. McMahon et al., Proc. Natl. Acad.
Sci. USA, 2007, 104, 17297; B. Rousseau et al., Eur. Phys. J. B,
2011, 81, 1). Discuss these phase transitions and the changes in
electronic properties that accompany them.
11.4 Discuss the industrial uses of lithium and likely future
demand for compounds of the metal. How are these demands
likely to be met? A useful resource is the United States Geological
Tutorial problems 7
9.3 In the paper ‘What and how physics contributes to
understanding the periodic law’ (Found. Chem., 2001, 3, 145),
V. Ostrovsky describes the philosophical and methodological
approaches taken by physicists to explain periodicity. Compare
and contrast the approaches of physics and chemistry to
explaining chemical periodicity.
9.4 P. Christiansen et al. describe ‘Relativistic effects in chemical
systems’ in their 1985 paper (Annu. Rev. Phys. Chem., 2001, 36,
407). How did they define relativistic effects? Briefly summarize
the most important consequences of relativistic effects in chemistry.
9.5 Many models of the periodic table have been proposed
since the version devised by Mendeleev. Review the more recent
versions and discuss the theoretical basis for each one.
occupies one coordination site and interacts with the eg and t2g
orbitals of the metal. An alternative formulation of the structure
of the complex, however, is as a trihydro species with very large
coupling constants (see J. Am. Chem. Soc., 1991, 113, 6074 and
the references therein, and especially J. Am. Chem. Soc., 1990,
112, 909 and 920). Review the evidence for this alternative
formulation.
10.4 In their article ‘Reversible, metal-free hydrogen activation’
(Science 2006, 314, 1124), Douglas Stephan and co-workers
describe how H2 is heterolytically cleaved at a molecule containing
only main group elements. By referring also to Section 5.10, explain
the principles of this reaction, the procedures used to investigate the
mechanism, and the possible implications for H2 storage.
Survey at https://minerals.usgs.gov/minerals/pubs/commodity/
lithium/ (accessed January 2018).
11.5 By 2020 ‘gigafactories’ in Europe and the US should each
produce lithium ion batteries with a capacity, per annum, of over
100 GWh. Review the chemistry involved in the development of
commercial lithium ion batteries (J.B. Goodenough and K.-S. Park,
J. Am. Chem. Soc., 2013, 135, 1167). Discuss the materials and
processes that have led to the reduction of Li-ion battery costs
over the last decade.
11.6 Summarize the chemistry of sodium that is being researched
for the development of rechargeable sodium ion batteries. See
M.D. Slater, D Kim, E. Lee, and C.S. Johnson, Adv. Func. Mater.,
2013, 23, 947.
11.7 Identify the incorrect phrase in each of the following
statements; explain your answer in each case. (a) Sodium
dissolves in ammonia and amines to produce the sodium cation
and solvated electrons or the sodide ion. (b) Sodium dissolved
in liquid ammonia will not react with NH +4 because of strong
hydrogen bonding with the solvent.
8 Tutorial problems
11.8 Z. Jedlinski and M. Sokol describe the solubility of alkali
metals in nonaqueous supramolecular systems (Pure Appl.
Chem., 1995, 67, 587). They dissolved the metals in THF
containing crown ethers or cryptands. Sketch the structure of
the 18-crown-6 ligand. Give the equations proposed for the
dissolution process. Outline the two methods used to prepare
the alkali metal solutions. What factors affect the stability of the
solutions?
11.9 Alkali metal halides can be extracted from aqueous solution
by solid-phase ditopic salt receptors (see J.M. Mahoney, A.M.
Beatty, and B.D. Smith, Inorg. Chem., 2004, 43, 7617). (a) What
is a ditopic receptor? (b) What is the order of selectivity to
CHAPTER 12
12.1 Marble and limestone buildings are eroded by contact with
acid rain. Define the term ‘acid rain’ and discuss the origins of the
acidity. Describe the processes by which the marble and limestone
are attacked.
12.2 Discuss the advantages and disadvantages of calcium
looping for CO2 capture in comparison with amine scrubbing.
12.3 In their paper ‘Noncovalent interaction of chemical bonding
between alkaline earth cations and benzene?’ (Chem. Phys. Lett.,
2001, 349, 113), X.J. Tan and co-workers carried out theoretical
calculations of complexes formed between beryllium, magnesium,
and calcium ions and benzene. To which orbital interactions were the
binding of the alkali metal to benzene attributed? How was the C–C
bond length in benzene affected by this interaction? Place the M–C
bonds in order of increasing bond enthalpy. How did the strength
of the bonds compare to those formed between Group 1 elements
and benzene? Sketch the geometry of the metal–benzene complexes.
12.4 Discuss beryllium fluoride glasses, noting how the chemistry
of BeF2 is analogous to that of SiO2.
12.5 P.C. Junk and J.W. Steed (J. Chem. Soc., Dalton. Trans.,
1999, 407) prepared crown ether complexes from the nitrates of
Mg, Ca, Sr, and Ba. Outline the general procedure that was used
for the syntheses. Sketch the structures of the two crown ethers
used. Comment on the structures of the complexes and how they
change with different cations.
12.6 Use your knowledge of chemical trends in Group 2 chemistry
and data from Table 12.1 to predict the chemistry of radium.
Compare your predictions with experimental observations. See,
for example, H.W. Kirby and M.L. Salutsky, The radiochemistry
of radium. Nuclear Science Series, National Academy of Sciences,
National Research Council. National Bureau of Standards, US
Department of Commerce (1964). http://library.lanl.gov/cgi-bin/
getfile?rc000041.pdf (accessed January 2018).
CHAPTER 13
13.1 Discuss the similarities in the chemistry of Tl(I) to those of
the alkali metals and particularly that of potassium.
13.2 Use suitable molecular-orbital software to calculate the
wavefunctions and energy levels for closo-[B6H6]2−. From that
output, draw a molecular orbital energy diagram for the orbitals
extraction of the alkali metal ions in aqueous solution? (c) What
is the order of selectivity to extraction from the solid phase? (d)
Explain the observed order of selectivity.
11.10 The molecular geometries of crown ether derivatives play
an important role in capturing and transporting alkali metal ions.
K. Okano and co-workers (see K. Okano, H. Tsukube, and K.
Hori, Tetrahedron, 2004, 60, 10877) studied stable conformations
of 12-crown-O3N and its Li+ complex in aqueous and acetonitrile
solutions. (a) Which three programs did the authors use in
their study and what did each program calculate? (b) Which
Li+ complex was found to be most stable in (i) aqueous and (ii)
acetonitrile solutions?
12.7 The aluminosilicates form a large group of minerals
based on linked AlO4 and SiO4 tetrahedra which includes
many clay and zeolite minerals whose compositions may be
written Mx+[AlxSi1−xO4]x−. Discuss the occurrence of the BeO4
unit in natural minerals. To what extent has it proved possible
to produce beryllophosphates based on linked BeO4 and PO4
tetrahedral units that are structural and compositional analogues
of Mx+[AlxSi1−xO4]x−, that is Mx+[BexP1−xO4]x−?
12.8 An experiment was carried out to determine the hardness
of domestic water. A few drops of pH = 10 buffer were added to
a 100 cm3 sample of the water. This sample was titrated against
0.01 M edta(aq) using Eriochrome Black T indicator and gave a
titre of 33.8 cm3. Under these circumstances both Mg2+ and Ca2+
ions react with edta. A second 100 cm3 sample was titrated against
the edta solution after 5.0 cm3 of 0.1 M NaOH(aq) and a few drops
of murexide indicator had been added. Under these conditions
only the Ca2+ ions react with the edta and a titre of 27.5 cm3 was
obtained. Determine the hardness of the water sample in terms of
the concentration of the Mg2+ and of the Ca2+ ions.
12.9 The synthesis of an Mg(I) compound has been reported
(Science, 2007, 318, 1754). Describe how this synthesis was carried
out and how this unusual Group 2 oxidation state was stabilized.
12.10 Discuss the bonding in the C–Be–C unit of zero valent
beryllium compounds (M. Arrowsmith et al., Nat. Chem., 2016,
8, 890).
12.11 ‘Nature is adept at controlling mineralisation processes
to produce single crystals and polycrystalline and amorphous
structures with remarkable morphologies and mechanical
properties’ (F. Meldrum, Int. Mater. Rev., 2003, 48, 187; F.
Meldrum and H Cölfen, Chem. Rev., 2008, 108, 4332). Calcium
carbonate is one of the most common biominerals. Summarize the
chemistry involved in the biomimetic engineering of CaCO3.
primarily involved in B–B bonding and sketch the form of the
orbitals. How do these orbitals compare qualitatively with the
qualitative description for this anion in this chapter? Is B–H
bonding neatly separated from the B–B bonding in the computed
wavefunctions?

13.3 In his paper ‘Covalent and ionic molecules: why are BeF2
and AlF3 high melting point solids whereas BF3 and SiF4 are
gases?’ (J. Chem. Educ., 1998, 75, 923), R.J. Gillespie makes
a case for the classification of the bonding in BF3 and SiF4 as
predominantly ionic. Summarize his arguments and describe how
these differ from the conventional view of bonding in gaseous
molecules.
13.4 Nanotubes of C and BN have been synthesized by C. Colliex
et al. (Science, 1997, 278, 653). (a) What are the advantageous
properties of these nanotubes over carbon analogues? (b) Outline
the method used for the preparation of these compounds. (c)
What was the main structural feature of the nanotubes, and how
could this be exploited in applications?
13.5 M. Montiverde discusses ‘Pressure dependence of the
superconducting temperature of MgB2’ (Science, 2001, 292,
75). (a) Describe the bases of the two theories that have been
postulated to explain the superconductivity of MgB2. (b) How
does the Tc of MgB2 vary with pressure? What insight does this
provide into the superconductivity?
CHAPTER 14
14.1 The chemical properties of flerovium, element 114, are
predicted to be significantly different from those of the other
members of Group 14 (P. Schwerdtfeger and M. Seth, J. Nucl.
Radiochem. Sci., 2002, 3, 133). Specifically, the only oxidation
state exhibited by Fl will be +2 and the element will be chemically
highly inert. Do these predictions follow the observed trends in
Group 14? Your discussion should include the role of relativistic
effects on the energies of the 7s and 7p orbitals in the superheavy
elements.
14.2 Discuss the solid-state chemistry of silicon in silicates with
reference to how the various structures can be built up from SiO4
tetrahedra linked into polymeric anions, chains, rings, sheets, and
three-dimensional networks.
14.3 One of your friends is studying English and is taking
a course in science fiction. A common theme in the sources
is silicon-based life forms. Your friend wonders why silicon
should be chosen and why all life is carbon-based. Prepare a
short article that presents arguments for and against
silicon-based life.
14.4 Karl Marx remarked in Das Kapital that ‘If we could
succeed, at a small expenditure of labour, in converting carbon
into diamonds, their value might fall below that of bricks.’ Review
current methods of synthesizing diamonds and discuss why these
developments have not resulted in a large decrease in the value of
diamonds.
14.5 In their paper ‘Mesoporous silica nanoparticles in
biomedical applications’, Li Zongxi et al. (Chem. Soc. Rev., 2012,
41, 2590) discuss the utility of mesoporous silica nanoparticles
(MSNPs) as supports for the delivery of therapeutic drugs in
the body. What are the properties of MSNPs that make them
particularly suitable for these applications? Describe how the
rate of drug release is controlled. Outline the synthetic methods
used to produce the MSNPs and identify the chemists who first
synthesized MSNPs.
Tutorial problems 9
13.6 Use the references in Z.W. Pan, Z.R. Dai, and Z.L. Wang
(Science, 2001, 291, 1947) as a starting point to write a review of
wire-like nanomaterials of Group 13 elements. Indicate how In2O3
nanobelts were prepared and give the dimensions of a typical
nanobelt.
13.7 Shuji Nakamura was awarded the 2014 Nobel Prize for
Physics in part for his invention of blue LEDs based on gallium
nitride. Discuss the chemistry of gallium nitride including its
synthesis, structures adopted and semiconducting chemistry
(including the doped forms).
13.8 In their paper ‘New structural motifs in metallaborane
chemistry: synthesis, characterization, and solid-state structures
of [(Cp*W)3(µ-H)B8H8], [(Cp*W)2B7H9], and [(Cp*Re)2B7H7]
(Cp* = η5-C5Me5)’ (Organometallics, 1999, 18, 853), A.S.
Weller, M. Shang, and T.P. Fehlner discuss the synthesis and
characterization of some novel boron-rich metallaboranes. Sketch
and explain the 11B- and 1H-NMR spectra of (Cp*W)2B7H9.
14.6 In the paper ‘Developing drug molecules for therapy with
carbon monoxide’ (Chem. Soc. Rev., 2012, 41, 3571), the authors
discuss the use of carbon monoxide as a therapeutic agent for
treating diseased tissue. Outline the problems associated with
using CO as a therapeutic agent and how the authors overcame
some of these.
14.7 One way of addressing the effects of CO2 emissions on the
atmosphere is to use it as a chemical feedstock in the production
of useful chemicals, fuels and polymers (M. Aresta and A.
Dibenedetto, Dalton Trans., 2007, 2975; C.-H. Huang and C.-S.
Tan, Aerosol Air Qual. Res., 2014, 14, 480). Summarize the
various approaches to using CO2 as a feedstock and the chemistry
involved in the production of organic compounds.
14.8 The paper ‘Metallacarboranes and their interactions:
theoretical insights and their applicability’ (P. Farràs et al.,
Chem. Soc. Rev., 2012, 41, 3445) discusses the properties
of metallacarboranes and how they can be analysed
using computational methods. Outline the properties of
metallacarboranes that were investigated and describe the
principles of the computational methods used to model them.
14.9 The combination of mesoporosity with semiconductivity
would produce materials with interesting properties. A
synthesis of such a material was discussed in ‘Hexagonal
mesoporous germanium’ by S. Gerasimo et al. (Science, 2006,
313, 5788). Summarize the expected advantages of such a
material and describe how the mesoporous germanium was
synthesized.
14.10 Many potentially useful semiconducting materials for
photovoltaic applications contain Group 14 elements in sulfides.
Examples include Cu2ZnSnS4 (CZTS) and SnS which have been
studied because they contain nontoxic elements that are relatively
abundant on Earth. Describe the structures and properties of these
sulfide materials and include a discussion of the sustainability of
these Group 14 element-based materials in comparison with CdTe
and CIGS (copper indium gallium sulfide).
10 Tutorial problems
14.11 Hybrid organic-inorganic lead and tin iodide perovskites
are potential low cost, solution-synthesized semiconductors for
solar cell applications (T.M. Brenner, D.A. Egger, L. Kronik, G.
Hodes, and D. Cahen, Nat. Rev. Mater., 2016, 1, Article 15007).
Summarize the recent advances made with these materials
focusing on their synthesis, structures, and chemical properties.
CHAPTER 15
15.1 Write a short review of the uses of bismuth compounds in
the treatment of gastric ulcers.
15.2 A paper published by J. Lee and co-workers (Sci. Rep., 2015,
5, 11512) describes the existence of two-dimensional honeycomb
sheet and ribbon forms of the Group 15 elements. (a) What methods
did the authors use to explore these structures? (b) Which Group 15
element was most reluctant to form the honeycomb structures?
(c) What properties and uses are these structures predicted to have?
(d) What is it about these structures of Group 15 elements that
makes them potentially more useful than graphene?
15.3 The structure of a butterfly-shaped P4 unit has been
reported by J. Bresien and co-workers (Dalton Trans., 2016, 45,
1998). (a) Sketch the P4 unit. (b) Give one example of a bicyclic
tetraphosphene synthesized from P4 with a Lewis acid and one
synthesized via self-assembly of P1 units. (c) Draw the two isomers
of Mes*P4Mes*. (d) Which isomer would give two triplets in the
31
P-NMR spectrum?
15.4 Nitrous oxide has been discovered to play a crucial role
in biological systems. A paper published by A.W. Carpenter and
M.H. Schoenfisch (Chem. Soc. Rev., 2012, 41, 3742) discusses
therapeutic applications of NO. Outline the main applications
and drawbacks of gaseous NO as a therapeutic agent. Discuss
how NO-donor molecules have been developed to enable NO
therapies for a wide range of medical conditions.
15.5 Describe sewage treatment methods that result in a decrease
in phosphate levels in wastewater. Outline a laboratory method
that could be used to monitor phosphate levels in water.
15.6 A compound containing five-coordinate nitrogen has been
characterized (A. Frohmann, J. Riede, and H. Schmidbaur, Nature,
CHAPTER 16
16.1 The isolation and characterization of a Se–Se species with
a three-electron sigma bond was described in a paper by Zhang
and co-workers (Nat. Commun., 2014, 5, 4127). (a) Who first
proposed the possibility of a three-electron sigma bond? (b) Sketch
the orbital interaction diagram for the formation of the bond.
(c) What was the Se–Se bond length? Discuss how this compares
to a single Se–Se bond and explain the difference between them.
(d) Which organic species was used to stabilize the Se–Se bond?
16.2 In their paper ‘Spiral chain O4 form of dense oxygen’
(Proc. Natl. Acad. Sci. U.S.A., 2012, 109, 3, 751), L. Zhu and
co-workers describe their predicted chain structure for oxygen.
Under what conditions is this structure predicted to exist? Which
14.12 In ‘An atomic seesaw switch formed by tilted asymmetric
Sn–Ge dimers on a Ge (001) surface’ (Science, 2007, 315, 1696),
K. Tomatsu et al. describe the synthesis and operation of a
molecular switch. Describe how such molecular switches operate
and summarize their current and potential applications.
1990, 345, 140). Describe (a) the synthesis, (b) the structure of the
compound, (c) the bonding.
15.7 Two articles (A. Lykknes and L. Kvittingen, Arsenic: not
so evil after all?, J. Chem. Educ., 2003, 80, 497; J. Wang and
C.M. Chien, Arsenic in drinking water: a global environmental
problem, J. Chem. Educ., 2004, 81, 207) present opposing
perspectives on the toxic nature of arsenic. Use these references
to produce a critical assessment of the beneficial and detrimental
effects of arsenic.
15.8 A paper published by N. Tokitoh et al. (Science, 1997,
277, 78) gives an account of the synthesis and characterization
of a stable bismuthene, containing Bi=Bi double bonds. Give the
equations for the synthesis of the compound. Name and sketch
the structure of the steric protecting group that was used. Why
was the isolation of the product simple? What methods were used
to determine the structure of the compound?
15.9 A paper published by Y. Zhang et al. (Inorg. Chem., 2006,
45, 10446) describes the synthesis of phosphazene cations as
precursors for polyphosphazenes. Polyphosphazenes are prepared
by ring-opening polymerization of the cyclic (NPCl2)3 and the
reaction is initiated by phosphazene cations. Discuss which Lewis
acids were used to produce the cations and give the reaction
scheme for the ring-opening polymerization of (NPCl2)3.
15.10 In their paper ‘Catalytic reduction of dinitrogen to
ammonia at single molybdenum center’ (Science, 2003, 301,
5629), D. Yandulov and R. Schrock describe the catalytic
conversion of nitrogen to ammonia at room temperature and
atmospheric pressure. Discuss why this development could be
important commercially. Review nonbiological methods of
nitrogen activation.
other Group 16 elements form this structure? How do the
predicted properties of this form of oxygen differ from those of
other forms of the element?
16.3 The article ‘Oxygen, sulfur, selenium, tellurium and
polonium’ by L. Myongwon Lee and I. Vargas-Baca (Annu. Rep.
Prog. Chem., Sect. A: Inorg. Chem., 2012, 108, 113) summarizes
highlights from the 2011 literature on the chemistry of the Group
16 elements. Use the references in this paper to (a) outline the
synthetic methods use to prepare [Te5Mo15O57]8−, (b) sketch the
structure of aryl tellurium monohalides, (c) sketch the structures
of AsSCl and AsS2, and (d) describe the products of the reaction
of ClP4S3 with sulfur.

16.4 In their paper ‘Formation of tellurium nanotubes through
concentration depletion at the surfaces of seeds’ (Adv. Mater.,
2002, 14, 279), B. Mayers and Y. Xia describe the synthesis
of tellurium nanotubes. Describe how their method differs
from those used to produce carbon nanotubes. What were the
dimensions of tellurium nanotubes produced? What applications
do the authors envisage for tellurium nanotubes?
16.5 In November 2006 the former KGB agent Alexander
Litvinenko was found to have been poisoned by radioactive
polonium-210. Write a review of the chemical and radiological
properties of Po and discuss its toxicity.
16.6 A mechanistic study of reaction between chloramine and
sulfite has been reported (B.S. Yiin, D.M. Walker, and D.W.
Margerum, Inorg. Chem., 1987, 26, 3435). Summarize the
observed rate law and the proposed mechanism. Accepting the
proposed mechanism, why should SO2(OH)− and HSO3− display
different rates of reaction? Explain why it was not possible to
distinguish the reactivity of SO2(OH)− from that of HSO3−.
16.7 Tetramethyltellurium, Te(CH3)4, was prepared in 1989
(R.W. Gedrige, D.C. Harris, K.R. Higa, and R.A. Nissan,
Organometallics, 1989, 8, 2817), and its synthesis was soon
followed by the preparation of the hexamethyl compound
(L. Ahmed and J.A. Morrison, J. Am. Chem. Soc., 1990, 112,
7411). Explain why these compounds are so unusual, give
CHAPTER 17
17.1 The paper ‘The consequences of excess iodine’ by A.
Leung and E Braverman (Nat. Rev., 2014, 10, 136) reviews the
health implications of excess iodine ingestion. (a) What is the
recommended daily intake of iodine? (b) What are the main
dietary sources of iodine? (c) What is usually the source of high
levels of iodine? (d) What are the symptoms of ingestion of high
levels of iodine? (d) What were the health benefits of a high
iodine diet in Japan in the period after 2011? (e) How is sufficient
dietary iodine ensured in most countries?
17.2 The phenomenon of the halogen bond has been known
for over a century. In the paper ‘The halogen bond in solution’
(Chem. Soc. Rev., 2012, 41, 3547), M. Erdelyi reviews the
current state of knowledge of the nature of the halogen bond.
Describe what is meant by halogen bonding. Work on the
halogen bond received the 1969 Nobel Prize in Chemistry.
Who were the recipients of this prize? Describe the relevance of
halogen bonding in biology. List the techniques that have been
used to probe the nature of halogen bonded interactions and
outline the molecular orbital description of such a bond. Explain
what is measured by the diiodide basicity scale and give the
assumptions on which the scale is based. Give the reference in
which this scale was first mentioned.
17.3 In their paper ‘Recent discoveries of polyhalogen anions—
from bromine to fluorine’ (Z. Anorg. Allg. Chem., 2014, 640,
7, 1281), H. Haller and S. Riedel described the synthesis and
structure elucidation of several new polyhalide ions. (a) Outline
the synthetic strategies that enabled these polyhalide ions to be
synthesized. (b) Sketch the structures of the Br5+, Br3− , and Cl7− ions.
13
(c) Referring to earlier work on polyiodides, discuss how I3− units
coordinate to build up polyiodides.
Tutorial problems 11
equations for their syntheses, and speculate on why these
synthetic procedures are successful. In relation to the last point,
speculate on why reaction of TeF4 with methyllithium does not
yield tetramethyltellurium.
16.8 The bonding in the square-planar ion E2+ is described in
4
Section 16.15. Explore this proposition in more detail by carrying
out computations, using software of your choice, on S24+ with S–S
bond distances of 200 pm (sulfur is recommended because its semi-
empirical parameters are more reliable than those of Se). From
the output (a) draw the molecular orbital energy-level diagram,
(b) assign the symmetry of each level, and (c) sketch the highest
energy molecular orbital. Is a closed-shell molecule predicted?
16.9 The nature of the sulfur cycle in ancient times has been
investigated (J. Farquhar, H. Bao, and M. Thiemen, Science, 2000,
289, 756). What three factors influence the modern-day cycle?
When did the authors establish that a significant change in the
cycle had occurred and how were the differences between the
ancient and modern cycles explained?
16.10 H. Keppler has investigated the concentration of sulfur
in volcano magma (Science, 1999, 284, 1652). In what forms
is sulfur erupted from volcanoes? What concentration of sulfur
was found in the magma erupted from Mount Pinatubo in 1991?
Discuss whether this concentration was expected and how any
deviation from the expected value was explained.
17.4 The potential of organofluoro compounds in materials
chemistry is discussed in a paper by R. Berger and co-workers (Chem.
Soc. Rev., 2011, 40, 3496). One group of compounds discussed is
the fluorinated fullerenes. Give an equation for the reaction of the
most commonly used fluorinated fullerene with an organic species to
form [18]trannulene and sketch the product. The use of fluorine in
pharmaceuticals is also described in the paper. Summarize the reasons
why fluorine finds wide application in pharmaceutical compounds.
17.5 The reaction of I− ions is often used to titrate ClO−, giving
deeply coloured I3− ions, along with Cl− and H2O. Although never
proved, it was once thought that the initial reaction proceeds by
O atom transfer from Cl to I. However, it is now believed that the
reaction proceeds by Cl atom transfer to give ICl as the intermediate
(K. Kumar, R.A. Day, and D.W. Margerum, Inorg. Chem., 1986, 25,
4344). Summarize the evidence for Cl atom transfer.
17.6 Until the work of K.O. Christe (Inorg. Chem., 1986, 25, 3721),
F2 could be prepared only electrochemically. Give chemical equations
for Christe’s preparation and summarize the reasoning behind it.
17.7 The use of templates to synthesize long-chain polyiodide
ions has been described (A.J. Blake et al., Chem. Soc. Rev.,
1998, 27, 195). (a) According to the authors, what is the longest
polyiodide that has been characterized? (b) How does the nature
of the cation influence the structure of the polyanion? (c) What
was the templating agent used for the synthesis of I7− and I12
−
? (c)
Which spectroscopic method was used for the characterization of
the polyanions in this study?
17.8 Review published studies on the fluoridation of drinking
water in your country. Summarize both the reasons for
continuing fluoridation and the main concerns expressed by
those opposed to it.
12 Tutorial problems
17.9 Write a review of the environmental problems associated
with the use of chlorine-based bleaches in industry, and suggest
possible solutions.
CHAPTER 18
18.1 In December 2015 the International Union of Pure and
Applied Chemistry (IUPAC) and the International Union of Pure
and Applied Physics (IUPAP) jointly announced their acceptance
of the evidence that demonstrated the existence of element 118.
What was the name and symbol of the element before it was given
its new name of oganesson? Which two institutions collaborated
to synthesize the new element? Outline the experiments that led
to the synthesis of oganesson. Outline the achievements of the
scientist after whom the element is named.
18.2 Argon has been found to react with CF32+ to form ArCF22+
(J. Phys. Chem. Lett. 2010, 1, 358). (a) What other Ar–C species
are formed during the reaction? (b) What are the Ar–C and C–F
bond lengths in the product? Give the point group of the dication.
(c) Why do He and Ne not form dications of this type with CF32+?
(d) Why do Kr and Xe not form dications of this type?
18.3 The paper ‘Exploring the effects on lipid bilayer induced by
noble gases via molecular dynamics simulations’ (Nature, 2015, 5,
17235) discusses the anaesthetic properties of noble gases. Which
noble gases cause anaesthesia? What is the order of their potency?
What is the mode of action of noble gas anaesthetics? Why is
xenon the most potent noble gas anaesthetic?
18.4 In the paper ‘Predicted chemical bonds between rare gases
and Au’ (J. Am. Chem. Soc., 1995, 117, 2067), P. Pyykkii used a
computational study of the species RgAuRg+ and AuRg+ (where
Rg refers to a ‘rare’ gas) to predict the bond energies and bond
lengths of the Au–Rg bond. Why did the author draw parallels
between the Au–Rg bonds and H–Rg bonds? Give the values of
bond energy and bond length for the series of Au–Rg bonds. How
would these values be expected to differ for Cu–Rg+ species? List
the values of the analogous Cu–Rg+ bonds and rationalize the
differences.
18.5 The paper ‘Atypical compounds of gases which have
been called “noble”’ (Chem. Soc. Rev., 2007, 36, 1632)
provides a thorough account of the range of compounds formed
by Group 18 elements. Among the compounds described are
XeF5Cl, HXeOOXeH, and ClXeFXeCl+. Sketch the structures
of these molecules. Outline the author’s rationale for classing
noble-gas atoms as Lewis bases and describe why XeF2 acts as
a ligand with metal cations. Only one compound of xenon with
mercury was described. Give the formula of this compound,
CHAPTER 19
19.1 Describe and account for the trends in the ionic radii and
the stability of high oxidation states upon moving from the
second to the third row of the transition series.
19.2 Discuss the benefits and the costs of using lightweight
titanium alloys over the more conventional steel in (a) motor cars
and (b) aeroplanes.
17.10 Write a review of the biological effects of excess iodine
in the body. Discuss how iodine is used as a therapy for (a) an
underactive and (b) an overactive thyroid gland.
outline its synthesis, and give the Hg–Xe bond energy and
bond length.
18.6 The first compound containing an Xe–N bond was reported
by R.D. LeBlond and K.K. DesMarteau (J. Chem. Soc., Chem.
Commun., 1974, 14, 554). Summarize the method of synthesis
and characterization. (The proposed structure was later confirmed
in an X-ray crystal structure determination.)
18.7 (a) Use the references in the paper by O.S. Jina, X.Z.
Sun, and M.W. George (J. Chem. Soc., Dalton Trans., 2003,
1773) to produce a review of the use of matrix isolation in
the characterization of organometallic noble-gas complexes.
(b) How did the methods used by these authors differ
from the usual techniques of matrix isolation? (c) Place the
complexes [MnCp(CO)2Xe], [RhCp(CO)Xe], [MnCp(CO)2Kr],
[Mo(CO)5Kr], and [W(CO)5Kr] in order of increasing stability
towards CO substitution.
18.8 In their paper ‘Xenon as a complex ligand: the tetra xenon
gold(II) cation in AuXe24+ (Sb2 F11− )2 ’, S. Seidel and K. Seppelt
(Science, 2000, 290, 117) describe the first synthesis of a stable
noble-gas coordination compound. Give details of the synthesis
and characterization of the compound.
18.9 The synthesis and characterization of the XeOF5− anion has
been described by A. Ellern and K. Seppelt (Angew. Chem., Int.
Ed. Engl., 1995, 34, 1586). (a) Summarize the similarities between
XeOF4 and IF5. (b) Give possible reasons for the differences in
structure between XeOF5− and IF6− . (c) Summarize how XeOF5− was
prepared.
18.10 In their paper ‘Helium chemistry: theoretical predictions
and experimental challenge’ (J. Am. Chem. Soc., 1987, 109, 5917),
W. Koch and co-workers used quantum mechanical calculations
to demonstrate that helium can form strong bonds with carbon
in cations. (a) Give the range of bond lengths calculated for these
He–C cations. (b) What are the requirements for an element to
form a strong bond with He? (c) To which branch of science do
the authors suggest that this work would be particularly relevant?
18.11 In their paper ‘Observation of superflow in solid helium’
(Science, 2004, 305, 1941), E. Kim and M. Chan described the
observed superfluidity of solid helium. Define superfluidity,
describe the experiment carried out by the authors to demonstrate
the property, and summarize their explanation of superfluidity.
19.3 TiO2 can be manufactured via the chloride process or the
sulfate process. Outline the advantages and disadvantages of
each of these processes in terms of the raw material required, the
nature of the pigment produced, and the environmental impact of
each process.

19.4 Iron is essential to all life forms. Assess the solubility
of Fe in +2 and +3 oxidation states; combine this with likely
stable oxidation state under normal conditions to assess the
bioavailability of iron. Consider how the atmosphere changed as
oxygenic photosynthesis took over (Box 16.1) and comment on
how this might have affected the bioavailability of iron.
19.5 Silica-supported compounds of chromium have been used as
catalysts for olefin polymerization for many years. Write a review
of this application of chromium chemistry. Include a discussion of
the Phillips and Union Carbide systems and discuss one published
paper on the topic from the past two years.
19.6 Gold, platinum, and palladium are all known as precious
metals. Review their uses in technology and other areas and
discuss why the prices of gold, platinum, and palladium have
varied over time.
19.7 Discuss the historical production and use of gold
nanoparticles. Account for the colour of the nanoparticles.
CHAPTER 20
20.1 In a fused magma liquid from which silicate minerals
crystallize, the metal ions can be four-coordinate. In olivine
crystals, the M(II) co-ordination sites are octahedral. Partition
coefficients, which are defined as Kp = [M(II)]olivine/[M(II)]melt,
follow the order Ni(II) > Co(II) > Fe(II) > Mn(II). Account for this
in terms of ligand-field theory. (See I.M. Dale and P. Henderson,
24th Int. Geol. Congress, Sect. 10, 1972, 105.)
20.2 In Problem 7.12 we looked at the successive formation
constants for 1,2-diaminoethane complexes of three different
metals. Using the same data, discuss the effect of the metal on
the formation constant. How might the Irving–Williams series
provide insight into these formation constants?
20.3 By considering the splitting of the octahedral orbitals as
the symmetry is lowered, draw the symmetry-adapted linear
combinations and the molecular orbital energy-level diagram for
σ bonding in a trans-[ML4X2] complex. Assume that the ligand X
is lower in the spectrochemical series than L.
20.4 Referring to Resource section 5, draw the appropriate
symmetry-adapted linear combinations and the molecular orbital
diagram for σ bonding in a square-planar complex. The point
group is D4h. Take note of the small overlap of the ligand with the
dz 2 orbital. What is the effect of π bonding?
20.5 Starting with Fig. 20.12, show how, using a crystal-field
approach, an extreme tetragonal distortion leads to the orbital
energy-level diagram in Fig. 20.10. Perform a similar analysis for
two-coordinate linear complexes.
20.6 Consider a trigonal prismatic six-coordinate ML6 complex
with D3h symmetry. Use the D3h character table (Resources
section 4) to divide the d orbitals of the metal into sets of defined
symmetry type. Assume that the ligands are at the same angle
relative to the xy-plane as in a tetrahedral complex.
20.7 In a trigonal bipyramidal complex the axial and equatorial
sites have different steric and electronic interactions with the
central metal ion. Consider a range of some common ligands and
decide which coordination site in a trigonal bipyramidal complex
they would favour. (See A.R. Rossi and R. Hoffmann, Inorg.
Chem., 1975, 14, 365.)
Tutorial problems 13
19.8 In their paper ‘Shape control in gold nanoparticle synthesis’
(Chem. Soc. Rev., 2008, 37, 1783), M. Grzelczak and co-workers
discuss the synthesis of gold nanoparticles with a range of
morphologies. Describe the different morphologies summarized in
this paper and outline the proposed growth mechanisms for the
nanoparticles when synthesized with and without the presence of
silver ions.
19.9 Discuss the side effects of protiodide and the risks of overdose.
19.10 Consider the 6d elements Rf–Cn. Make predictions of the
key features of their chemistry, were sufficient quantities ever to
be isolated.
19.11 A paper published in 2014 had the title ‘Identification of
an iridium-containing compound with a formal oxidation state of
IX’ (Nature, 2014, 514, 475), and one published in 2016 had the
title ‘Oxidation state 10 exists’ (Angew. Chem. Int. Ed., 2016, 55,
9004). Review these papers and comment on the veracity of their
titles.
20.8 Vanadium(IV) species that have the V=O group have
quite distinct spectra. What is the d-electron configuration of
V(IV)? The most symmetrical of such complexes are [VOL5]
with C4v symmetry, with the O atom on the z-axis. What are
the symmetry species of the five d orbitals in [VOL5] complexes?
How many d–d bands are expected in the spectra of these
complexes? A band near 24 000 cm−1 in these complexes shows
vibrational progressions of the V=O vibration, implicating
an orbital involving V=O bonding. Which d–d transition is a
candidate? (See C.J. Ballhausen and H.B. Gray, Inorg. Chem.,
1962, 1, 111.)
20.9 MLCT bands can be recognized by the fact that the energy
is a sensitive function of the polarity of the solvent (because the
excited state is more polar than the ground state). Two simplified
molecular orbital diagrams are shown in Fig. 20.45. In (a) is a
case with a ligand π level higher than the metal d orbital. In (b)
is a case in which the metal d orbital and the ligand level are at
the same energy. Which of the two MLCT bands should be more
solvent-sensitive? These two cases are realized by [W(CO)4(phen)]
and [W(CO)4(iPr-DAB)], respectively, where DAB = 1,4-diaza-
1,3-butadiene. (See P.C. Servas, H.K. van Dijk, T.L. Snoeck,
D.J. Stufkens, and A. Oskam, Inorg. Chem., 1985, 24, 4494.)
Comment on the CT character of the transition as a function of
the extent of backdonation by the metal atom.
20.10 Consider spin-crossover complexes and identify the
features that a complex would need for it to be used in (a) a
practical pressure sensor and (b) a practical information-storage
device (see P. Gütlich, Y. Garcia, and H.A. Goodwin, Chem. Soc.
Rev., 2000, 29, 419).
20.11 Consider the octahedral [NiF6]3− ion. What spin state
and magnetic moment could it have? How would the Jahn-
Teller effect affect the two spin states, and how might this
complicate an interpretation of the UV/vis absorption spectrum?
How has evidence from the magnetic moment and absorption
spectrum allowed a definitive assignment of the spin state? (See
T.I. Court and M.F.A. Dove, J. Chem. Soc., Dalton Trans., 1973,
1995.)
14 Tutorial problems

CHAPTER 21
21.1 Given the following mechanism for the formation of a large slope for S2O32− and zero slopes for Y − = N3− , I− , NO2−, and
chelate complex, SCN−. Propose a mechanism.
[Ni(OH 2 )6 ]2+ + L−L [Ni(OH 2 )6 ]2+,L−L KE , rapid 21.6 The activation enthalpy for the reduction of cis-
[Ni(OH 2 )6 ] ,L−L [Ni(OH 2 )5 L−L ] + H 2O
2+ 2+
ka , ka′ [CoCl2(en)2]+ by Cr2+ (aq) is −24 kJ mol−1. Explain the negative
value. (See R.C. Patel, R.E. Ball, J.F. Endicott, and R.G. Hughes,
[Ni(OH 2 )5 L−L ]2+ [Ni(OH 2 )4 L−L ]2+ + H 2O kb , kb′
Inorg. Chem., 1970, 9, 23.)
 erive the rate law for the formation of the chelate. Discuss the
d 21.7 Consider the complexes (18) and (19) discussed in the Brief
step that is different from that for two monodentate ligands. illustration in Section 21.11. Think about the potential routes of
The formation of chelates with strongly bound ligands occurs at the electron transfer in the two complexes and suggest why there
the rate of formation of the analogous monodentate complex, is such a difference in the rates of electron transfer between the
but the formation of chelates of weakly bound ligands is often two complexes.
significantly slower. Assuming an Id mechanism, explain this
21.8 Calculate the rate constants for outer-sphere reactions from
observation. (See R.G. Wilkins, Acc. Chem. Res., 1970, 3, 408.)
the following data. Compare your results to the measured values
21.2 Discuss the following set of rate constants (k) and activation in the last column.
parameters for water exchange reactions of metal aqua ions.
⦵
Reaction k11/dm3 k22/dm3 E /V kobs/dm3
Species k/s−1 Δ‡H/kJ mol−1 Δ‡V/cm3 mol−1 mol−1 s−1 mol−1 s−1 mol−1 s−1
[Ti(OH2)6]3+ 1.8 × 105 43.4 −12.1 Cr 2+ + Fe 3+ 2 × 10−5 4.0 +1.18 2.3 × 103
[V(OH2)6]2+ 87 61.8 −4.1 [W(CN)8 ]4− + Ce(IV) >4 × 104 4.4 +0.54 >108
[V(OH2)6] 3+
500 49.4 −12.1 [Fe(CN)6 ] + [MnO 4 ] 4− −
7.4 × 10 2
3 × 103
+1.30 1.7 × 105
[Cr(OH2)6]3+ 2.4 × 10−6 109 −9.6 [Fe(phen)3 ]2+ + Ce(IV) >3 × 107 4.4 +0.66 1.4 × 105
[Cr(OH2)5(OH)] 2+
1.8 × 10−4
111 +2.7
21.9 In the presence of catalytic amounts of [Pt(µ-P2O5H2)4]4−
[Mn(OH2)6] 2+
2.1 × 107
32.9 −5.4 (21) and light, 2-propanol produces H2 and acetone (E.L. Harley,
[Fe(OH2)6]3+ 1.6 × 102 63.9 −5.4 A.E. Stiegman, A. Vlcek, Jr, and H.B. Gray, J. Am. Chem. Soc.,
[Co(OH2)6] 2+
3.2 × 106
46.9 +6.1 1987, 109, 5233; D.C. Smith and H.B. Gray, Coord. Chem. Rev.,
1990, 100, 169). (a) Give the equation for the overall reaction.
[Ni(OH2)6]2+ 3.2 × 104 56.9 +7.2
(b) Give a plausible molecular orbital scheme for the metal–metal
[Cu(OH2)6] 2+
4.4 × 109
11.5 +2.0 bonding in this tetragonal-prismatic complex and indicate the
nature of the excited state that is thought to be responsible for the
21.3 The complex [PtH(PEt3)3]+ was studied in deuterated acetone photochemistry. (c) Indicate the metal complex intermediates and
in the presence of excess PEt3. In the absence of excess ligand the the evidence for their existence.
1
H-NMR spectrum in the hydride region exhibits a doublet of
triplets. As excess PEt3 ligand is added the hydride signal begins 2– –
12 SO3 + HSO3
to change, the line shape depending on the ligand concentration.
I–
Suggest a mechanism to account for the effects of excess PEt3. –
N3
kobs / 10–3 s–1

21.4 Solutions of [PtH2(PMe3)2] exist as a mixture of cis and NO2

–
8
trans isomers. Addition of excess PMe3 led to formation of SCN–
[PtH2(PMe3)3] at a concentration that could be detected using OH–
NMR. This complex exchanged phosphine ligands rapidly with 4 S2O3
2–

the trans isomer but not the cis. Propose a pathway. What are
the implications for the trans effect of H versus PMe3? (See D.L.
Packett and W.G. Trogler, Inorg. Chem., 1988, 27, 1768.) 0
21.5 Figure 21.24 (which is based on J.B. Goddard and F. Basolo, 0 10 20 30 40 50
Inorg. Chem., 1968, 7, 936) shows the observed first-order rate [Reactant] / 10–3 mol dm–3
constants for the reaction of [PdBrL]+ with various Y− to give
FIGURE 21.24 The data required for Problem 21.5.
[PdYL]+, where L is Et2NCH2CH2NHCH2CH2NEt2. Note the

CHAPTER 22
22.1 Propose the structure of the product obtained by the
reaction of [Re(CO)(η5-C5H5)(NO)(PPh3)]+ with Li[HBEt3]. The
latter contains a strongly nucleophilic hydride. (For full details
see W. Tam, G.Y. Lin, W.K. Wong, W.A. Kiel, V. Wong, and J.A.
Gladysz, J. Am. Chem. Soc., 1982, 104, 141.)
22.2 When several CO ligands are present in a metal carbonyl,
an indication of the individual bond strengths can be obtained
by means of force constants derived from the experimental IR
frequencies. In [Cr(CO)5(PPh3)] the cis-CO ligands have the higher
force constants, whereas in [Ph3SnCo(CO)4] the force constants

are higher for the trans-CO. Suggest why, and explain which
carbonyl C atoms should be susceptible to nucleophilic attack
in these two cases. (For details see D.J. Darensbourg and M.Y.
Darensbourg, Inorg. Chem., 1970, 9, 1691.)
22.3 Discuss the following data for M−M and M−CO bond
enthalpies in a series of metal carbonyl cluster compounds.
The enthalpies given in each case are average values for that
compound.
BM–M/kJ mol−1 BM–C/kJ mol−1
Fe(CO)5 117
Fe3(CO)12 65 126
Ru3(CO)12 78 182
Os3(CO)12 94 201
Co4(CO)12 74 140
Rh4(CO)12 86 178
Ir4(CO)12 117 196
22.4 It is often possible to assign different resonance structures
to an organometallic compound; for example, there can be
competition between carbene and zwitterionic forms. Suggest
ways of distinguishing the two forms and describe conditions
that might favour one form over the other. See N. Ashkenazi,
A. Vigalok, S. Parthiban, Y. Ben-David, L.J.W. Shimon, J.M.L.
Martin, and D. Milstein, J. Am. Chem. Soc., 2000, 122, 8797;
and C.P. Newman, G.J. Clarkson, N.W. Alcock, and J.P. Rourke,
Dalton Trans., 2006, 3321.
22.5 Agostic interactions are often thought of as weak. Discuss
examples where agostic interactions have been shown to displace
other ligand interactions. See B.L. Conley and T.J. Williams, J. Am.
Chem. Soc., 2010, 132, 1764; and S.H. Crosby, G.J. Clarkson,
R.J. Deeth, and J.P. Rourke, Dalton Trans., 2011, 40, 1227.
22.6 Describe how alkane complexes of d metals have been
unambiguously identified by NMR. What additional insights can
be gained from X-ray diffraction? See S. Geftakis and G.E. Ball,
J. Am. Chem. Soc., 1998, 120, 9953; W.H. Bernskoetter, C.K.
Schauer, K.I. Goldberg, and M. Brookhart, Science, 2009, 326,
553; and S.D. Pike, A.L. Thompson, A.G. Algarra, D.C. Apperley,
S.A. Macgregor, and A.S. Weller, Science, 2012, 337, 1648.
22.7 It is possible to distinguish two types of notionally agostic
interactions: agostic and anagostic. Describe the differences
between the two types. See M. Brookhart, M.L.H. Green, and G.
Parkin, Proc. Natl. Acad. Sci. U.S.A., 2007, 104, 6908.
22.8 The dinitrogen complex [Zr2(η5-Cp*)4(N2)3] has been
isolated and its structure determined by single-crystal X-ray
diffraction. Each Zr atom is bonded to two Cp* and one
terminal N2. The third N2 bridges between the Zr atoms in a
nearly linear ZrNNZr array. Before consulting the reference,
write a plausible structure for this compound that accounts
for the 1H-NMR spectrum obtained on a sample held at 27°C.
This spectrum shows two singlets, indicating that the Cp* rings
are in two different environments. At somewhat above room
temperature these rings become equivalent on the NMR timescale
and 15N-NMR indicates that N2 exchange between the terminal
ligands and dissolved N2 is correlated with the process that
interconverts the Cp* ligand sites. Propose a way in which this
equilibration could interconvert the sites of the Cp* ligands. (For
further details see J.M. Manriquez, D.R. McAlister, E. Rosenberg,
Tutorial problems 15
H.M. Shiller, K.L. Willamson, S.I. Chan, and J.E. Bercaw, J. Am.
Chem. Soc., 1978, 100, 3078.)
22.9 How might you unambiguously identify, in solution, an
organometallic complex containing a noble gas atom as a ligand?
See G.E. Ball, T.A. Darwish, S. Geftakis, M.W. George, D.J. Lawes,
P. Portius, and J.P. Rourke, Proc. Natl. Acad. Sci. U.S.A., 2005,
102, 1853.
22.10 What conclusions can you draw from the bonding and
reactivity of dihydrogen bound to a low-oxidation-state d-block
metal that might be applicable to the bonding of an alkane to
a metal? What implications might this have for the oxidative
addition of a hydrocarbon to a metal atom? (See, for example,
R.H. Crabtree, J. Organomet. Chem., 2004, 689, 4083.)
22.11 Compare and contrast Fischer and Schrock carbenes. See
E.O. Fischer, Adv. Organomet. Chem., 1976, 14, 1; and R.R.
Schrock, Acc. Chem. Res., 1984, 12, 98.
22.12 Rearrangements of ligands so that differing numbers
of carbons interact with the central metal atom are known as
haptotropic rearrangements. Consider the (fluorenyl)(cyclo-
pentadienyl)iron complex. What haptotropic isomers are possible?
See E. Kirillov, S. Kahlal, T. Roisnel, T. Georgelin, J. Saillard, and
J. Carpentier, Organometallics, 2008, 27, 387.
22.13 It is possible to consider bridging carbonyl ligands in
several different ways, with differing numbers of electrons donated
to metals. Describe how it is possible to account for the structure
of [Fe2(CO)9] as having an 18-electron count at both metals, but
without invoking the presence of an Fe–Fe bond. See J.C. Green,
M.L.H. Green, and G. Parkin Chem. Commun., 2012, 48, 11481.
22.14 A. Arbaoui and C. Redshaw (Polym. Chem., 2010, 1, 801)
review catalysts for the synthesis of biodegradable polymers via
ring opening metathesis polymerization. Summarize the need for
biodegradable polymers and why new catalysts are required. From
the details given identify which group of metals give the most active
catalysts with which types of ligands. Illustrate with examples.
22.15 When direct evidence for a mechanism is not available,
chemists frequently invoke analogies with similar systems.
Describe how J.E. Bäckvall, B. Åkermark, and S.O. Ljunggren
(J. Am. Chem. Soc., 1979, 101, 2411) inferred the attack of
uncoordinated water on η2-C2H4 in the Wacker process.
22.16 β-Pinene is a major component of natural turpentine and
its polymer is nontoxic and used in a wide variety of industrial
applications such as adhesives, varnishes, food packaging and
chewing gum. Novel catalysts for the polymerization of β-pinene
have been produced based on niobium and tantalum pentahalides
(M. Hayatifar et al., Catal. Today, 2012, 192, 177). Which
catalyst was the most effective for the polymerization and why are
the reaction conditions so attractive? Describe the nature of the
catalyst–β-pinene interaction.
22.17 The tethering of a homogeneous catalyst to a solid support
has been investigated as a method that allows easy separation of
the catalyst from the reaction mixture, with little loss in catalyst
activity. What are the advantages and disadvantages of this
approach? Choose an article from Chem. Rev., 2002, 102, issue
10 (start page 3215) to illustrate your discussion.
22.18 How may the use of two liquid phases that are not
miscible at room temperature be used to create catalytic systems
that have advantages over normal (single phase) systems? Discuss
this area, paying attention to either fluorous biphasic systems
(see J. Fluorine Chem., 1999, 100, 75) or ionic liquid systems
(see Chem. Rev., 2002, 102, 3667).
16 Tutorial problems
CHAPTER 23
23.1 Lanthanoid coordination compounds rarely exhibit
isomerism in solution. Suggest two factors that might cause this
phenomenon, explaining your reasoning. (See D. Parker, R.S.
Dickins, H. Puschmann, C. Crossland, and J.A.K. Howard, Chem.
Rev., 2002, 102, 1977.)
23.2 Neither lanthanoid nor actinoid organometallic compounds
obey the 18-electron rule. Discuss the reasons, using the structures
of the tris(Cp) and tris(Cp*) Ln and An complexes as examples.
(See W.J. Evans and B.L. Davis, Chem. Rev., 2002, 102, 2119.)
23.3 The catalytic activity of many organolanthanoids is controlled
by the ionic radius of Ln3+. In general Ln(Cp*)2X complexes
that are catalysts for olefin polymerization show decreasing
reactivity as La is replaced by Lu. In contrast, some reactions
proceed more rapidly as the catalyst is changed from La to Lu.
Discuss the principles involved in tuning the catalytic activities of
organolanthanoid catalysts in terms of rates and selectivity. (See
C.J. Weiss and T.J. Marks, Dalton Trans., 2010, 39, 6576.)
23.4 ‘Quantum cutting’ is a process by which absorption of a
single high-energy photon, corresponding to incident light in the
UV spectral region, results in the emission of two photons of
lower energy, in the visible region. The process is highly efficient
and has important applications for improving the spectral range
of solar photovoltaic cells, as well as providing more efficient
domestic lighting. With reference to articles by Huang et al.
(Chem. Soc. Rev. 2013, 42, 173) and Lorbeer et al. (Chem.
Commun., 2010, 46, 571), explain why Gd, in conjunction with
other lanthanoids, is important for developing this technology.
23.5 ‘Single molecule magnets’ (abbreviated SMMs) offer intriguing
new possibilities for storing and processing data: lanthanoids, due to
their large number of unpaired electrons, are attracting a great deal
of interest. The triangular complex [Dy3(OH)2(o-van)3(H2O)5Cl]3+
(25) consists of three Dy3+, each coordinated by a molecule of
vanillin and interlinked by hydroxide ions. With reference to the
article by R. Sessoli and A.K. Powell (Coord. Chem. Rev., 2009,
253, 2328), explain why Dy(III) triangles are particularly interesting
to those working in the SMM field.
Cl
O Dy
25
CHAPTER 24
24.1 Describe the inorganic chemistry involved in the operation
of a lambda sensor (an exhaust-gas oxygen sensor) in a vehicle
engine.
23.6 The existence of a maximum oxidation number of +6
for both uranium (Z = 92) and tungsten (Z = 74) prompted
the placement of U under W in early periodic tables. When the
element after uranium, neptunium (Z = 93), was discovered in
1940, its properties did not correspond to those of rhenium (Z
= 75), and this cast doubt on the original placement of uranium.
(See G.T. Seaborg and W.D. Loveland, The elements beyond
uranium. Wiley-Interscience (1990), p. 9 et seq.) Using standard
potential data from Resource section 2, discuss the differences in
oxidation state stability between Np and Re.
23.7 In their review on new commercial applications of Ln
chemistry (Acc. Chem. Res., 2016, 49, 844), Guillou and co-
workers explain how the coordination of different Ln(III) ions
within metal–organic frameworks can be exploited to produce
unique luminescent inks for anti-counterfeiting signatures. Discuss
the principles of this technology.
23.8 The processing of spent nuclear fuel and separation of
the lighter actinoid elements, U, Np, and Pu, is an important
industrial process. Discuss the chemistry involved in the various
methods used to extract and separate these elements.
23.9 The 24-membered U ring complex shown below is
very unusual as it is rigid and contains both bridging azido
and bridging nitrido ligands. Describe how this complex was
synthesized and the significance of the bonding that is observed.
(See W.J. Evans, S.A. Kozimor, and J.W. Ziller, Science, 2005, 309,
1835.)
U N U N N N U N U
N N
N N
N N
U N U N N N U N U
24.2 To obtain high oxidation states for first row d metals in
complex oxides, e.g. Sr2Fe(IV)O4, compounds are normally
prepared at as low a temperature as possible commensurate with

the reaction. Discuss the thermodynamic reasons for the use of
these conditions and explain why the optimum temperature for
producing YBCO involves a final annealing stage at about 450°C
under pure oxygen.
24.3 Heating a complex oxide under ammonia can lead to
nitridation (with nitrogen replacing oxygen) or reduction (with
the production of nitrogen and water). Describe possible products
that might be formed when SrWO4 is heated in ammonia. By
consideration of the relative entropy changes for the two reactions,
explain how the reaction temperature might affect the outcome.
24.4 What are the advantages of sol–gel routes, in comparison
with direct high-temperature reaction methods, in the synthesis
of complex metal oxides? Why are sol–gel routes used to prepare
finely divided or nanoparticulate material?
24.5 Describe the delafossite structure type adopted by some
compounds of the stoichiometry MM′X2. Which elemental
combinations are known to form this structure type? Discuss their
electronic properties when X = O, and potential applications as
photocatalysts.
24.6 Superconductors are often classified as type I or II. Describe
the physical characteristic that determines the classification of
a superconductor into one or the other of these types. Classify
the following materials in their superconducting state (a) Hg,
(b) TaSi2, (c) YBCO, and (d) Nb3Ge.
24.7 Discuss how various chemical substitutions led to the
discovery, and subsequent optimization of the properties, of the
superconducting materials with the LnFeOAs structure type.
Describe the compositional and structural chemistry of other
recently discovered iron-based superconducting materials.
24.8 Discuss differences in the properties of zeolites, zeotypes
(frameworks built from oxotetrahedral species other than AlO4
and SiO4), and metal–organic frameworks (MOFs).
24.9 Describe recent progress towards the commercialization of
MOFs. (See N. Notman, Chem. World, 2017, 5, 44.)
24.10 One target for a material of use for hydrogen storage in
transport applications is that it should contain 10 weight per
cent hydrogen. Which class of material is the most promising for
this application? What are the different requirements of a static
system that might be used to store hydrogen produced from
renewable energy?
24.11 What are the properties of an ideal inorganic pigment?
24.12 Discuss the recent advances in perovskite solar cell
chemistry that have driven device efficiencies to over 20 per cent.
(See S. Yang, W. Fu, Z. Zhang, H. Chen and C.-Z. Li, J. Mater.
Chem. A, 2017 , 5, 11462.)
24.13 Summarize recent research efforts directed towards finding
improved materials for the photocatalytic splitting of water.
24.14 Compare and contrast the chemistries of graphite and C60
with respect to their compounds in association with the alkali
metals.
24.15 ‘The increased reactivity that allows the design and
synthesis of materials based on molecular units also means that
these compounds are unsuitable for many applications that
currently use inorganic materials.’ Discuss this remark.
24.16 Explain whether vapour-phase or solution-based
techniques typically lead to (a) larger size distributions in
nanoparticle synthesis, (b) agglomerated particles that are strongly
bonded to one another in so-called hard agglomerates.
Tutorial problems 17
24.17 (a) Discuss the difference between homogeneous and
heterogeneous nucleation from the vapour phase. (b) Which type
of nucleation is preferred for the growth of a thin film in this
process? (c) Which type of nucleation is preferred for the growth
of nanoparticles in this process?
24.18 Describe the difference between a physical vapour and
a chemical vapour with respect to the type and stability of the
vapour species.
24.19 (a) Give a definition for scanning probe microscopy that
makes clear both what it is and why it is called scanning probe
microscopy. (b) Using a material of interest to you, pick any
scanning probe microscopy method and describe how you might
use it to characterize an important aspect of your material.
24.20 Compare and contrast the band energies for a quantum
dot nanocrystal and a bulk semiconductor.
24.21 (a) Give two examples of applications of quantum wells.
(b) Describe why quantum wells are used and if either molecular
materials or traditional solid-state materials can exhibit similar
properties. (c) How are quantum wells made?
24.22 (a) What is the relevance of self-assembly to the fabrication
of nanomaterials? (b) What role will it play in nanotechnology?
24.23 (a) Describe the two classes of inorganic–organic
nanocomposites based on their bonding types. (b) Give one
example of a nanocomposite in each class.
24.24 Discuss the synthesis, properties, and potential applications
of ultrathin two-dimensional nanosheets of layered transition
metal dichalcogenides. (See M. Chhowalla, et al., Nat. Chem.,
2013, 5, 263.)
24.25 The synthesis method described in this chapter for
generating CdSe quantum dots involves the use of rather toxic
compounds. Explore the chemical literature to find a more recent
example that uses less toxic substances. Describe the solvation
step, the nucleation step, and the growth step in each case.
Comment on the size dispersions in each case. (See the following
articles as a start: G.C. Lisensky and E.M. Boatman, J. Chem.
Educ., 2005, 82, 1360; W. William Yu and X.-G. Peng, Angew.
Chem., Int. Ed., 2002, 41, 2368.)
24.26 The Grätzel cell has been described as a useful
photoelectrochemical cell. Describe how the photoelectrochemical
cell differs from the conventional photovoltaic cell. Describe
why the nanostructure TiO2 is important for the improved
performance. What other inorganic species play an important role
in functionalizing the Grätzel cell? (See M. Grätzel, Nature,
2001, 414, 338.)
24.27 Discuss how the various physical properties of graphene may
lead to the incorporation of this material into future technologies.
24.28 Carbon nanotubes have been suggested for use as wires in
molecular electronics. Describe the challenges of using nanotubes
as wires in terms of connecting two functional electronic
devices. Describe a possible technique to overcome some of these
problems.
24.29 Nanotubes are widely known for carbon. Find an example
of an inorganic nanotube not based on carbon and describe its
synthesis and properties as compared to the corresponding bulk
material. Compare its structure to the carbon nanotubes discussed
in this chapter.
24.30 Summarize the potential impact of heterogeneous
oxidation catalysts in chemistry. (See J.M. Thomas and R. Raja,
Catal. Today, 2006, 117, 22.)
18 Tutorial problems
24.31 Discuss the applications and mechanisms of oxidation
and ammoxidation catalysts such as bismuth molybdate. (See,
for example, R.K. Grasselli, J. Chem. Educ., 1986, 63, 216.)
24.32 Discuss the advantages of a solid support in catalysis
by reference to the use of [Ni(POEt)3]4 in alkene isomerization.
(See A.J. Seen, J. Chem. Educ., 2004, 81, 383; and K.R.
Birdwhistell and J. Lanza, J. Chem. Educ., 1997, 74, 579.)
24.33 J.A. Botas et al. discuss the catalytic conversion of
vegetable oils into hydrocarbons suitable for use as biofuels
CHAPTER 25
25.1 In an article on the detection of Zn(II) that is released from
neuronal tissue (brain, nerves) following trauma, E. Tomat and
S.J. Lippard describe the development of special ligands that are
highly selective for Zn and allow it to be imaged by a technique
called confocal microscopy (Curr. Opin. Chem. Biol., 2010, 14,
225). Using your knowledge of the coordination chemistry of Zn,
explain the principles underlying this research.
25.2 In justifying research into small molecule catalysts for
producing NH3 from N2, it is sometimes stated that nitrogenase
is an ‘efficient’ enzyme: how true is this statement? Comment
critically on the argument that ‘knowing the 3D structure of
CHAPTER 26
26.1 In their article ‘Targeting and delivery of platinum-based
anticancer drugs’ (Chem. Soc. Rev. 2012, 42, 202), X. Wang and
Z. Guo review the expanding field of nanoparticle-based drug
delivery. Summarize the various ways that metal-containing drugs
are attached to nanostructures and the advantages of modifying a
drug in such a way.
(Catal. Today, 2012, 195, 1, 59). What are the most
important features of catalysts that are used for these reactions?
How was the incorporation of transition metals expected to
modify catalyst properties? Outline how the modified catalysts
were prepared and characterized. What reactions occurred in the
reactor in addition to catalytic cracking? Which reactions led to
aromatic products? Which of the modified catalysts produced
most coke build-up? Explain why this did not deactivate the
catalyst.
nitrogenase has not enlightened us as to its mechanism of action’
and discuss how this view might be valid more generally for
enzymes for which a structure is known.
25.3 ‘In Mo enzymes, the bond between a terminal oxo anion
and Mo(VI) is usually written as a double bond, whereas it is
more correctly assigned as a triple bond.’ Discuss this statement.
Suggest how a terminal oxido ligand influences the reactivity
of other coordination sites on the Mo atom and explain how a
terminal sulfido ligand (as occurs in xanthine oxidase) would alter
the properties of the active site.
26.2 Write an essay on the different ways that metallocenes are
being used in medicine.