Black plate (338,1)

Chapter

13 The group 14 elements

TOPICS
& Occurrence, extraction and uses & Oxides and oxoacids and hydroxides, including
& Physical properties silicates

& The elements

& Silicones

& Hydrides
& Sulfides

& Carbides, silicides, germides, stannides and

& Cyanogen, silicon nitride and tin nitride
plumbides & Aqueous solution chemistry of germanium, tin
& Halides and complex halides and lead

1 2 13 14 15 16 17 18 semi-metals† and we have already discussed their semi-

conducting properties (see Section 5.9).
H He All members of group 14 exhibit an oxidation state of þ4,
but the þ2 oxidation state increases in stability as the group is
Li Be B C N O F Ne descended. Carbenes exemplify the C(II) state but exist only
as reaction intermediates, silicon dihalides are stable only at
Na Mg Al Si P S Cl Ar
high temperatures, the Ge(II) and Sn(II) states are well estab-
K Ca Ga Ge As Se Br Kr lished, and Pb(II) is more stable than the Pb(IV) state. In this
respect, Pb resembles its periodic neighbours, Tl and Bi, with
Rb Sr d-block In Sn Sb Te I Xe the inertness of the 6s electrons being a general feature of the
last member of each of groups 13, 14 and 15 (see Box 12.3).
Cs Ba Tl Pb Bi Po At Rn
Carbon is essential to life on Earth, and most of its
Fr Ra compounds lie within the remit of organic chemistry. None-
theless, compounds of C that are formally classified as
‘inorganic’ abound and extend to organometallic species
(see Chapters 18 and 23).

13.1 Introduction
13.2 Occurrence, extraction and uses
The elements in group 14 – carbon, silicon, germanium, tin
and lead – show a gradation from C, which is non-metallic,
to Pb, which, though its oxides are amphoteric, is mainly Occurrence
metallic in nature. The so-called ‘diagonal line’ which is
Figure 13.1 illustrates the relative abundances of the group
often drawn through the p-block to separate metallic from
14 elements in the Earth’s crust. The two long-established
non-metallic elements passes between Si and Ge, indicating
crystalline allotropes of carbon, diamond and graphite,
that Si is non-metallic and Ge is metallic. However, this
occur naturally, as does amorphous carbon (e.g. in coal).
distinction is not definitive. In the solid state, Si and Ge
Diamonds occur in igneous rocks (e.g. in the Kimberley
possess a covalent diamond-type lattice (see Figure 5.19a),
but their electrical resistivities (see Section 5.8) are
significantly lower than that of diamond, indicating †
Under IUPAC recommendations, the term ‘semi-metal’ is preferred
metallic behaviour. Silicon and germanium are classed as over ‘metalloid’.
 Black plate (339,1)

Chapter 13 . Occurrence, extraction and uses 339

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.1 Recycling: tin and lead

Recycling of tin and lead, particularly the latter, takes place Lead–acid storage batteries represent a major source of
on a huge scale. In Box 5.1, we described steel-can recycling metal that is recovered. In 2001,
78% of refined Pb
operations. The tin used to coat steel cans is recovered using manufactured in the US originated from recycled metal,
specialized detinning processes. In Europe, about one-third much of it (
1 Mt) coming from spent batteries from
of tinplate produced is currently recycled, while in the US vehicle and industrial sources.
in 2001, 58% of tin-plated steel cans were recycled.

volcanic pipes, South Africa). Carbon dioxide constitutes Tin is obtained from cassiterite (SnO2 ) by reduction with
only 0.04% of the Earth’s atmosphere, and, although vital C in a furnace (see Section 7.8), but a similar process
for photosynthesis, CO2 is not a major source of carbon. cannot be applied to extract Pb from its sulfide ore since
During the 1990s, it was discovered that molecular allotropes
f Go (CS2 ,g) is þ67 kJ mol1 ; thermodynamically viable
of carbon, the fullerenes (see Section 13.4), occur naturally processes involve reactions 13.1 or 13.2 at high temperatures.
in a number of deposits in Australia, New Zealand and Both Sn and Pb are refined electrolytically. Recycling of Sn
North America; however, laboratory synthesis remains the and Pb is highlighted in Box 13.1.
chief means of accessing these new allotropes. 9
2PbS þ 3O2  2PbO þ 2SO2 >
"

Elemental Si does not occur naturally, but it constitutes >

>
PbO þ C  Pb þ CO
"
=
25.7% of the Earth’s crust (Si is the second most abundant ð13:1Þ
or >
>
element after O) in the form of sand, quartz, rock crystal, >
;
flint, agate and silicate minerals (see Section 13.9). In PbO þ CO  Pb þ CO2
"

contrast, Ge makes up only 1.8 ppm of the Earth’s crust, PbS þ 2PbO  3Pb þ SO2
"
ð13:2Þ
being present in trace amounts in a range of minerals (e.g.
zinc ores) and in coal. The principal tin-bearing ore is Uses
cassiterite (SnO2 ). Important ores of lead are galena (PbS),
anglesite (PbSO4 ) and cerussite (PbCO3 ). Diamond is the hardest known substance, and apart from
its commercial value as a gemstone, it has applications in
Extraction and manufacture cutting tools and abrasives (see Box 13.5). The structural
differences between diamond and graphite lead to remark-
Sources of natural graphite are supplemented by manu-
able differences in physical properties (see Section 13.3)
factured material formed by heating powdered coke (high- and uses. The properties of graphite that are exploited
temperature carbonized coal) with silica at
2800 K.
Approximately 30% of diamonds for industrial use in the
US are synthetic (see Box 13.5). Diamond films may be
grown using a chemical vapour deposition method (see
Section 27.6), and hydrothermal processes are currently
being investigated.† The manufacture of amorphous
carbon (carbon black, used in synthetic rubbers) involves
burning oil in a limited supply of air.
Silicon (not of high purity) is extracted from silica, SiO2 ,
by heating with C or CaC2 in an electric furnace. Impure
Ge can be obtained from flue dusts collected during the
extraction of zinc from its ores, or by reducing GeO2 with
H2 or C. For use in the electronic and semiconductor
industries, ultrapure Si and Ge are required, and both can
be obtained by zone-melting techniques (see Box 5.3 and
Section 27.6).

†
See for example: X.-Z. Zhao, R. Roy, K.A. Cherian and A. Badzian
(1997) Nature, vol. 385, p. 513 – ‘Hydrothermal growth of diamond in Fig. 13.1 Relative abundances of the group 14 elements in the
metal–C–H2 O systems’; R.C. DeVries (1997) Nature, vol. 385, p. 485 – Earth’s crust. The data are plotted on a logarithmic scale. The
‘Diamonds from warm water’. units of abundance are parts per million (ppm).
 Black plate (340,1)

340 Chapter 13 . The group 14 elements

charcoal (produced by charring treated bones) are micro-

crystalline forms of graphite, supported, in the case of
animal charcoal, on calcium phosphate. The adsorption
properties of activated charcoal render it commercially
important (see Box 13.2). Carbon fibres of great tensile
strength (formed by heating oriented organic polymer
fibres at 1750 K) contain graphite crystallites oriented
parallel to the fibre axis, and are used to strengthen mate-
rials such as plastics. Carbon-composites are fibre-rein-
forced, chemically inert materials which possess high
Fig. 13.2 Uses of natural graphite in the US in 2001. [Data: strength, rigidity, thermal stability, high resistance to
US Geological Survey.]
thermal shock and retain their mechanical properties at
high temperature. Such properties have led to their use
commercially (see Figure 13.2) are its inertness, high in external body parts of the space shuttle (see Section
thermal stability, electrical and thermal conductivities 27.7).
(which are direction-dependent, see Section 13.4) and Silicon has major applications in the steel industry (see
ability to act as a lubricant. Its thermal and electrical prop- Box 5.1) and in the electronic and semiconductor industries
erties make graphite suitable as a refractory material (see (see Sections 5.8, 5.9 and 27.6, and Box 13.3). Silica, SiO2 ,
Section 11.6) and for uses in batteries and fuel cells. The is an extremely important commercial material; it is the main
growing importance of fuel-cell technology (see Box 9.2) component of glass, and large quantities of sand are
will result in a growth in demand for high-purity graphite. consumed worldwide by the building industry. Quartz glass
Other new technologies are having an impact on the (formed on cooling fused SiO2 ) can withstand sudden
market for graphite. For example, graphite cloth (‘flexible temperature changes and has specialist uses; we discuss
graphite’) is a relatively new product and applications are different types of glasses in Section 13.9. Silica gel (an
increasing. Charcoal (made by heating wood) and animal amorphous form of silica, produced by treating aqueous

APPLICATIONS

Box 13.2 Activated charcoal: utilizing a porous structure

Activated charcoal is a finely divided form of amorphous phosgene (equation 13.42), and in laboratory syntheses, it
carbon and is manufactured from organic materials (e.g. has many uses, e.g.:
peat, wood) by heating in the presence of reagents that
4CoCl2 þ O2 þ 4½NH4 Cl þ 20NH3
promote both oxidation and dehydration. Activated char-
coal possesses a pore structure with a large internal surface activated charcoal
 4½CoðNH3 Þ6 Cl3 þ 2H2 O
"

area: microporous materials exhibit pores <2 nm wide,

macroporous refers to activated charcoals with a pore size The porous skeleton of activated carbon can be used as a
>50 nm, and mesoporous materials fall in between these template on which to construct other porous materials, for
extremes. The largest internal surface areas are found for example, SiO2 , TiO2 and Al2 O3 . The oxide is first dissolved
microporous materials (>700 m2 g1 ). The ability of the in supercritical CO2 (see Section 8.13) and then the activated
hydrophobic surface to adsorb small molecules is the key carbon template is coated in the supercritical fluid. The
to the widespread applications of activated charcoal. carbon template is removed by treatment with oxygen
(Comparisons should be made with the porous structures plasma or by calcination in air at 870 K, leaving a nano-
and applications of zeolites: see Sections 13.9 and 26.6.) porous (‘nano’ refers to the scale of the pore size) metal
Early large-scale applications of activated charcoal were in oxide with a macroporous structure that mimics that of the
gas masks in World War I. Various gas-filters including those activated carbon template.
in cooker extractors and mobile or bench-top laboratory
fume-hoods contain activated charcoal filters. About 20%
of the activated charcoal that is produced is consumed in
Further reading
the sugar industry, where it is used as a decolouring agent. A.J. Evans (1999) Chemistry & Industry, p. 702 – ‘Cleaning
Water purification uses large amounts of activated charcoal. air with carbon’.
The porous structure means that activated charcoal is an H. Wakayama, H. Itahara, N. Tatsuda, S. Inagaki and Y.
excellent heterogeneous catalyst, especially when impreg- Fukushima (2001) Chemistry of Materials, vol. 13,
nated with a d-block metal such as palladium. On an indus- p. 2392 – ‘Nanoporous metal oxides synthesized by the
trial scale, it is used, for example, in the manufacture of nanoscale casting process using supercritical fluids’.
 Black plate (341,1)

Chapter 13 . Occurrence, extraction and uses 341

APPLICATIONS

Box 13.3 Solar power: thermal and electrical

Harnessing energy from the Sun is, of course, an environ- the number of daylight hours are key factors that have to
mentally acceptable method of producing power. Conversion be accommodated if adequate solar power is to be generated
via heat exchange units (often referred to as solar panels) for domestic or similar uses.
provides thermal energy to raise the temperature of swim- Other semiconductors in use in solar cells include GaAs
ming pools or to provide domestic hot water. Conversion (e.g. in space satellites), CdTe (a promising newcomer to
via photovoltaic systems (often termed solar cells) produces solar cell development) and TiO2 (used in the Grätzel cell
electricity and involves the use of semiconductors. Initially, which involves a novel design in which a TiO2 film is
NASA’s space programme was the driving force behind the coated with an organic dye).
development of solar cells, and applications in satellites
and other space vessels remain at the cutting edge of design
technology. However, we all now feel the benefits of solar
Further reading
cells which are used in items such as solar-powered calcula-
tors. Silicon has been the workhorse of this commercial M.A. Green (2001) Advanced Materials, vol. 13, p. 1019 –
operation. The thickness of a typical cell is 200–350 mm, ‘Crystalline silicon photovoltaic cells’.
and is constructed of an n-doped layer (which faces the M. Hammonds (1998) Chemistry & Industry, p. 219 –
sun), a p-doped layer and a metal-contact grid on the top ‘Getting power from the sun’.
and bottom surfaces. The latter are connected by a K. Kalyanasundaram and M. Grätzel (1999) in Optoelectronic
conducting wire. At the n–p junction, electrons move from Properties of Inorganic Compounds, ed. D.M. Roundhill
the p-type to the n-type silicon, and ‘holes’ (see Section and J.P. Fackler, Plenum Press, New York, p. 169 –
5.9) move in the opposite direction; this leads to a flow of ‘Efficient photovoltaic solar cells based on dye sensitization
electricity around the circuit. Power output per cell is of nanocrystalline oxide films’.
small, and a large number of cells must operate together to J. Wolfe (1998) Chemistry & Industry, p. 224 – ‘Capitalising
produce a viable voltage supply. Weather conditions and on the sun’.

sodium silicate with acid) is used as a drying agent, a opacifier used in enamels and paints (also see Section
stationary phase in chromatography, and a heterogeneous 27.4), and its applications in gas sensors are the topic of
catalyst. Caution! Inhalation of silica dusts may lead to the Box 13.11. The use of tin-based chemicals as flame retar-
lung disease silicosis. Hydrated silica forms the exoskeletons dants (see Box 16.1) is increasing in importance.
of marine diatoms, but the role of Si in other biological Lead is a soft metal and has been widely used in the
systems is less well defined.† The applications of silicates plumbing industry; this use has diminished as awareness of
and aluminosilicates are discussed in Section 13.9. the toxicity of the metal has grown (see Box 13.4). Similarly,
The commercial demand for Ge is small, and the most uses of Pb in paints have been reduced, and ‘environmentally
important applications are those in fibre infrared optics friendly’ lead-free fuels are replacing leaded counterparts
and arise from the optical properties of GeO2 . About half (Figure 13.3). Lead oxides are of great commercial impor-
of the Ge used in optical devices is recycled. Applications tance, e.g. in the manufacture of ‘lead crystal’ glass. Red
of Ge as a semiconductor are gradually becoming fewer lead, Pb3 O4 , is used as a pigment and a corrosion-resistant
as new and more efficient semiconducting materials are coating for steel and iron. By far the greatest demand for
developed. About 28 000 kg of Ge was used in the US in lead is in lead–acid batteries. The cell reaction is a combination
2001. Compared with this, the demand for tin and lead is of half-reactions 13.3 and 13.4; a normal automobile 12 V
far greater (41 200 t of Sn and 1.6 Mt of Pb in 2001 in the battery contains six cells connected in series.
US). Tin-plating of steel cans improves corrosion resistance PbSO4 ðsÞ þ 2e Ð PbðsÞ þ ½SO4 2 ðaqÞ Eo ¼ 0:36 V
and is a major use of Sn. The metal is, however, soft and tin
ð13:3Þ
alloys such as pewter, soldering metal, bronze and
þ 2 
die-casting alloy have greater commercial value than pure PbO2 ðsÞ þ 4H ðaqÞ þ ½SO4  ðaqÞ þ 2e
Sn. High-quality window glass is usually manufactured by Ð PbSO4 ðsÞ þ 2H2 OðlÞ Eo ¼ þ1:69 V ð13:4Þ
the Pilkington process which involves floating molten glass
on molten tin to produce a flat surface. Tin dioxide is an Lead–acid storage batteries are used not only in the auto-
mobile industry but also as power sources for industrial
forklifts, mining vehicles and airport ground services, and
†
For a thought-provoking account, see: J.D. Birchall (1995) Chemical for independent electrical power sources in, for example,
Society Reviews, vol. 24, p. 351 – ‘The essentiality of silicon in biology’. hospitals.
 Black plate (342,1)

342 Chapter 13 . The group 14 elements

Fig. 13.3 The declining use of leaded fuels in motor vehicles is illustrated by these statistics from the US. [Data: US Geological Survey.]

. the discontinuities (i.e. increases) in the trends of values of

13.3 Physical properties IE3 and IE4 at Ge and Pb.
The sums of the first four ionization energies for any element
Table 13.1 lists selected physical properties of the group 14 suggest that it is unlikely that M4þ ions are formed. For
elements. A comparison with Table 12.1 shows there to be example, although both SnF4 and PbF4 are non-volatile
some similarities in trends down groups 13 and 14. solids, neither has a symmetrical lattice structure in the
solid state. Both SnO2 and PbO2 adopt the rutile lattice,
Ionization energies and cation formation but the fact that PbO2 is brown argues against a formulation
On descending group 14, the trends in ionization energies of Pb4þ (O2 )2 . Agreement between values of lattice energies
reveal two particular points: determined using a Born–Haber cycle and calculated from
an electrostatic model is good for SnO2 , but is poor for
. the relatively large increases between values of IE2 and PbO2 . Thus, values of the M4þ ionic radii (Table 13.1)
IE3 for each element; should be treated with some caution.

Table 13.1 Some physical properties of the group 14 elements, M, and their ions.

Property C Si Ge Sn Pb

Atomic number, Z 6 14 32 50 82
Ground state electronic configuration [He]2s2 2p2 [Ne]3s2 3p2 [Ar]3d 10 4s2 4p2 [Kr]4d 10 5s2 5p2 [Xe]4f 14 5d 10 6s2 6p2
Enthalpy of atomization, 717 456 375 302 195

a H o (298 K) / kJ mol1
Melting point, mp / K >3823‡ 1687 1211 505 600
Boiling point, bp / K 5100 2628 3106 2533 2022
Standard enthalpy of fusion, 104.6 50.2 36.9 7.0 4.8

fus H o (mp) / kJ mol1
First ionization energy, IE1 / kJ mol1 1086 786.5 762.2 708.6 715.6
Second ionization energy, 2353 1577 1537 1412 1450
IE2 / kJ mol1
Third ionization energy, 4620 3232 3302 2943 3081
IE3 / kJ mol1
Fourth ionization energy, 6223 4356 4411 3930 4083
IE4 / kJ mol1
Metallic radius, rmetal / pm – – – 158 175
Covalent radius, rcov / pm 77 118 122 140 154
Ionic radius, rion / pm – – 53 (Ge4þ ) 74 (Sn4þ ) 78 (Pb4þ )
93 (Sn2þ ) 119 (Pb2þ )
Standard reduction potential, – – – 0.14 0.13
E o ðM2þ =MÞ / V
Standard reduction potential, – – – þ0.15 þ1.69
E o ðM4þ =M2þ Þ / V
13 29 73 117 207
NMR active nuclei (% abundance, C (1.1, I ¼ 12 ) Si (4.7, I ¼ 12 ) Ge (7.8, I ¼ 92 ) Sn (7.6, I ¼ 12 ); Pb (22.6, I ¼ 12 )
119
nuclear spin) Sn (8.6, I ¼ 12 )

‡
For diamond.

Values for C, Si, Ge and Sn refer to diamond-type structures and thus refer to 4-coordination; the value for Pb also applies to a 4-coordinate centre.

Values are for 6-coordination.

This value is for the half-reaction: PbO2 ðsÞ þ 4Hþ ðaqÞ þ ½SO4 2 ðaqÞ þ 2e Ð PbSO4 ðsÞ þ 2H2 OðlÞ.
 Black plate (343,1)

Chapter 13 . Physical properties 343

Table 13.2 Some experimental covalent bond enthalpy terms common. However, it must be stressed that kinetic as well
(kJ mol1 ); the values for single bonds refer to the group 14 as thermodynamic factors may be involved, and any detailed
elements in tetrahedral environments. discussion of kinetic factors is subject to complications:

CC C¼C CC CH CF CCl CO C¼O . Even when CC bond breaking is the rate-determining
step, it is the bond dissociation energy (zero point
346 598 813 416 485 327 359 806
energy: see Section 2.9) rather than the enthalpy term
SiSi SiH SiF SiCl SiO Si¼O that is important.
226 326 582 391 466 642
. Reactions are often bimolecular processes in which bond-
GeGe GeH GeF GeCl GeO making and bond-breaking occur simultaneously, and in
186 289 465 342 350
such cases, the rate of reaction may bear no relationship
SnSn SnH SnCl to the difference between bond enthalpy terms of the
151 251 320 reactants and products.
PbCl
244 In contrast to the later elements in group 14, C tends not to
expand its valence octet of electrons, and, while complexes
such as [SiF6 ]2 and [Sn(OH)6 ]2 are known, carbon
analogues are not. The fact that CCl4 is kinetically inert
Aqueous solution chemistry involving cations of the group towards hydrolysis but SiCl4 is readily hydrolysed by water
14 elements is restricted mainly to Sn and Pb (see Section has traditionally been ascribed to the availability of 3d
13.13), and so Table 13.1 gives E o values only for these orbitals on Si, which can stabilize an associative transition
metals. state. This view has been challenged with the suggestion
that the phenomenon is steric in origin associated purely
Some energetic and bonding considerations with the lower accessibility of the C centre arising from the
shorter CCl bonds with respect to the SiCl bonds.
Table 13.2 lists some experimentally determined values for The possible role of (p–d)
-bonding for Si and the later
covalent bond enthalpy terms. When we try to interpret elements in group 14 has been a controversial issue (see
the chemistry of the group 14 elements on the basis of such Section 4.7) and we return to this in Section 13.6. On the
bond energies, caution is necessary for two reasons: other hand, (p–p)
-bonding leading to double to triple homo-
. many thermodynamically favourable reactions are kineti- nuclear bonds, which is so common in carbon chemistry, is
cally controlled; relatively unimportant later in the group. A similar situation
. in order to use bond enthalpy terms successfully, complete is observed in groups 15 and 16. The mesityl derivative 13.1
reactions must be considered. was the first compound containing an Si¼Si bond to be char-
acterized; in the Raman spectrum, an absorption at 529 cm1
The first point is illustrated by considering that although the
is assigned to the (Si¼Si) mode, and in the solid state struc-
combustions of CH4 and SiH4 are both thermodynamically
ture, the SiSi bond distance of 216 pm is less than twice the
favourable, SiH4 is spontaneously inflammable in air,
value of rcov (2  118 pm). Such species are stabilized with
whereas CH4 explodes in air only when a spark provides
respect to polymerization by the presence of bulky substituents
the energy to overcome the activation barrier. In respect of
such as mesityl (in 13.1), CMe3 or CH(SiMe3 )2 . The central
the second point, consider reaction 13.5.
Si2 C4 -unit in 13.1 is planar, allowing overlap of orthogonal
H H 3p orbitals for
-bond formation; the bulky mesityl substitu-
ents adopt a ‘paddle-wheel’ conformation minimizing steric
H C H Cl Cl H C Cl H Cl interactions.† In contrast, theoretical studies on Si2 H4 (mass
spectrometric evidence for which has been obtained), indicate
H H
that the non-planar structure is energetically favoured. The
(13.5) same trans-bent conformation has been observed experi-
Inspection of Table 13.2 shows that E(CH) > E(CCl), mentally for Sn2 R4 compounds (see Figure 18.15 and
but the fact that the HCl bond (431 kJ mol1 ) is signifi- accompanying text). Silicon–silicon triple bonds remain
cantly stronger than the ClCl bond (242 kJ mol1 ) results unknown. Theoretical studies on the hypothetical HSiSiH
in reaction 13.5 being energetically favourable. suggest that a non-linear structure is energetically preferred
over an ethyne-like structure. Experimental efforts to realize
Catenation is the tendency for covalent bond formation the SiSi bond continue (see end-of-chapter reading).
between atoms of a given element, e.g. CC bonds in
hydrocarbons or SS bonds in polysulfides.
†
In a second structurally characterized polymorph, the orientations of
The particular strength of the CC bond contributes the mesityl groups differ, see: R. Okazaki and R. West (1996) Advances
towards the fact that catenation in carbon compounds is in Organometallic Chemistry, vol. 39, p. 231.
 Black plate (344,1)

344 Chapter 13 . The group 14 elements

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.4 Toxicity of lead

Lead salts are extremely toxic. The ingestion of a soluble lead (e.g. low melting, easily worked and inexpensive) and it is a
salt can cause acute poisoning, and long-term exposure to a challenge for research and development initiatives to find
source of the metal (e.g. old water pipes, Pb-based paints) alloys for lead-free solders that replicate these properties.
may result in chronic poisoning. Organolead(IV) compounds Solders based on Sn with Ag, Bi, Cu and Zn as alloying
such as Et4 Pb, used as an anti-knock additive to leaded metals are the most promising candidates, and of these
motor fuels, attack the nervous system. In a relevant piece SnAgCu (3–4% by weight of Ag and 0.5–0.9% by weight
of research, analysis of wines produced between 1962 and of Cu) solders are the front runners for use in the electronics
1991 from grapes grown in roadside vineyards has shown industry.
some correlation between a decrease in Pb content and the
introduction of unleaded fuels. Sequestering agents such as
Further reading
[EDTA]4 (see equation 6.75 and accompanying text) are
used to complex Pb2þ ions in the body, and their removal R.A. Goyer (1988) in Handbook on Toxicity of Inorganic
follows by natural excretion. Compounds, eds H.G. Seiler, H. Sigel and A. Sigel,
Joints between metals, including those in electronic Marcel Dekker, New York, p. 359 – ‘Lead’.
components, have traditionally used SnPb solders. How- R. Lobinski et al. (1994) Nature, vol. 370, p. 24 – ‘Organo-
ever, in the European Union, new environmental legislation lead in wine’.
aims to phase out this use of lead by 2006 or 2007; a move to K. Suganuma (2001) Current Opinion in Solid State and
lead-free solders is also being made in Japan and the US. Materials Science, vol. 5, p. 55 – ‘Advances in lead-free
Eutectic SnPb solder exhibits many desirable properties electronics soldering’.

The first Ge¼C double bond was reported in 1987, since

when a number of examples have been reported, including
Mes2 Ge¼CHCH2 t Bu which is stable at 298 K. The forma-
tion of Ge¼Ge bonds is described in Section 18.5.

Si Si NMR active nuclei

Table 13.1 lists NMR active nuclei for the group 14 elements.
Although the isotopic abundance of 13 C is only 1.1%, use of
13
C NMR spectroscopy is very important. The low
abundance means that, unless a sample is isotopically
enriched, satellite peaks in, for example, a 1 H NMR
Mesityl = Mes = 1,3,5-trimethylphenyl
spectrum, will not be observed and application of 13 C as
(13.1)
an NMR active nucleus lies in its direct observation. The
appearance of satellite peaks due to coupling of an observed
The formation of ( p–p)
-bonds between C and Si is also
nucleus such as 1 H to 29 Si or 119 Sn is diagnostic (see case
rare; an example is shown in equation 13.6. In 1999, the
study 5 in Section 2.11). Direct observation of 29 Si nuclei
first examples of a CSi bond were confirmed in the gas-
is a routine means of characterizing Si-containing
phase molecules HCSiF and HCSiCl. These species
compounds. Tin-119 NMR spectroscopy (119 Sn being
were detected using neutralization–reionization mass
generally favoured over 117 Sn for direct observation) is also
spectrometry, but have not been isolated.
valuable; the chemical shift range is large and, as with
Mes2FSi H many heteronuclei,  values may provide an indication of
coordination environments.
C C + tBuLi

H H
Mössbauer spectroscopy
The 119 Sn nucleus is suitable for Mössbauer spectroscopy
Mes H
(see Section 2.12) and isomer shift values can be used to
Si C + LiF (13.6) distinguish between Sn(II) and Sn(IV) environments. The
spectroscopic data may also provide information about the
Mes tBu
coordination number of the Sn centre.
 Black plate (345,1)

Chapter 13 . Allotropes of carbon 345

Worked example 13.1 NMR spectroscopy

most stable form of the element but is metastable. At room
temperature, the conversion of diamond into graphite is
The 1 H NMR spectrum of SnMe4 consists of a singlet with two thermodynamically favoured (equation 13.7), making
superimposed doublets. The coupling constants for the doublets graphite the standard state of C at 298 K. However, reaction
are 52 and 54 Hz, and the overall five-line signal exhibits an 13.7 is infinitely slow.
approximately 4 : 4 :84 :4 :4 pattern. Use data from Table 13.1 CðdiamondÞ  CðgraphiteÞ
"

to interpret the spectrum.

r Go ð298 KÞ ¼ 2:9 kJ mol1 ð13:7Þ
In Me4 Sn, all twelve protons are equivalent and one signal
is expected. Sn has two NMR active nuclei: 117 Sn (7.6%, A state is metastable if it exists without observable change
I ¼ 12) and 119 Sn (8.6%, I ¼ 12). The 1 H nuclei couple to even though it is thermodynamically unstable with respect to
the 117 Sn nucleus to give a doublet, and to the 119 Sn another state.
nucleus to give another doublet. The relative intensities of
the lines in the signal reflect the abundances of the spin- Diamond has a higher density than graphite (graphite ¼ 2:25;
active nuclei: diamond ¼ 3:51 g cm3 ), and this allows artificial diamonds
to be made from graphite at high pressures. There are
. 83.8% of the 1 H nuclei are in molecules containing two structural modifications of graphite. The ‘normal’
isotopes of Sn that are not spin-active, and these form is a-graphite and can be converted to the b-form by
protons give rise to a singlet; grinding; a b  a-transition occurs above 1298 K. Both
"

. 7.6% of the 1 H nuclei are in molecules containing 117 Sn forms possess layered structures and Figure 13.4a shows
and these protons give rise to a doublet; ‘normal’ graphite. (Compare the structure of graphite
. 8.6% of the 1 H nuclei are in molecules containing 117 Sn with that of boron nitride in Figure 12.18.) The intralayer
and these protons give rise to a doublet. CC bond distances are equal (142 pm) while the interlayer
distances are 335 pm; a comparison of these distances with
The coupling constants for the doublets are 52 and 54 Hz.
the values for C of rcov ¼ 77 pm and rv ¼ 185 pm indicates
From the data given, it is not possible to assign these to
that while covalent bonding is present within each layer,
coupling to a particular isotope. (In fact, J(117 Sn–
1 only weak van der Waals interactions operate between
H) ¼ 52 Hz, and J(119 Sn–1 H) ¼ 54 Hz.)
adjacent layers. Graphite cleaves readily and is used as a
lubricant; these facts follow directly from the weak
Self-study exercises interlayer interactions. The electrical conductivity (see
Section 5.8) of a-graphite is direction-dependent; in a direc-
Data: see Table 13.1; 1 H and 19 F, 100%, I ¼ 12.
tion parallel to the layers, the electrical resistivity is
1. The 13 C NMR spectrum of Me3 SnCl contains five lines in a
non-binomial pattern; the separation between the outer lines 1:3  105  m (at 293 K) but is
1  m in a direction
is 372 Hz. Interpret these data. perpendicular to the layers. Each C atom has four valence
[Ans. As in the worked example; J(119 Sn–13 C) ¼ 372 Hz] electrons and forms three -bonds, leaving one electron to
participate in delocalized
-bonding. The molecular
-
2. Apart from the chemical shift value, how do you expect well-
orbitals extend over each layer, and while the bonding
resolved 1 H NMR spectra of Me4 Sn and Me4 Si to differ?
MOs are fully occupied, the energy gap between them and
[Ans. Take into account the % abundances of
spin-active nuclei] the vacant antibonding MOs is very small, allowing the
electrical conductivity in the direction parallel to the
3. Explain why the 29 Si NMR spectrum of SiH3 CH2 F consists layers to approach that of a metal. In contrast, the electrical
of a quartet (J 203 Hz) of doublets (J 25 Hz) of triplets resistivity of diamond is 1  1011  m, making diamond an
(J 2.5 Hz).
excellent insulator.
[Ans. 29 Si couples to directly bonded 1 H, two-bond
Graphite is more reactive than diamond; it is oxidized by
coupling to 19 F, and two-bond coupling to 1 H]
atmospheric O2 above 970 K whereas diamond burns at
>1170 K. Graphite reacts with hot, concentrated HNO3 to
give the aromatic compound C6 (CO2 H)6 . We consider
some specific types of reactions below.
13.4 Allotropes of carbon
Graphite: intercalation compounds
Graphite and diamond: structure and Graphite possesses the remarkable property of forming
properties many intercalation (lamellar or graphitic) compounds, the
formation of which involves movement apart of the carbon
We have already described the rigid structure of diamond layers and the penetration of atoms or ions between them.
(Figure 5.19a). Diamond is not the thermodynamically There are two general types of compound:
 Black plate (346,1)

346 Chapter 13 . The group 14 elements

APPLICATIONS

Box 13.5 Diamonds: gemstones and more

The commercial value of diamonds as gemstones is well X-ray diffraction equipment to study high-pressure
recognized, and the world production of gem-quality phases of minerals.
diamonds in 2001 is shown in chart (a) below. The Industrial demand for diamond is met in part by synthetic
chart also shows the production of diamonds (non- diamonds, the 2001 world production of which is shown in
gemstone quality) used for industrial purposes. Because chart (b). Under conditions of pressures greater than
diamond is the hardest known substance, it has wide- 12:5  103 MPa and a temperature of
3000 K, graphite
spread applications as an abrasive and in cutting-tools transforms into diamond. Synthetic diamonds are produced
and drill-bits. These applications extend from drill-bits by dissolving graphite in a melted metal (e.g. Fe) and
for mining to diamond saws for cutting crystals into crystallizing the mixture under appropriate high P and T
wafer-thin slices for the electronics industry. Diamond conditions. After being cooled, the metal is dissolved into
exhibits electrical, optical and thermal properties (it has acid, leaving synthetic diamonds of sizes ranging between
the highest thermal conductivity of any material at
0.05 and 0.5 mm. Major uses of these industrial diamonds
298 K) that make it suitable for use in corrosion and include grinding, honing (e.g. smoothing cylinder bores),
wear-resistant coatings, in heat sinks in electrical circuits, saw-blades and polishing powders. The relative importance
and in certain types of lenses. An application in the of synthetic diamond production (which has risen dramati-
laboratory is in diamond anvil cells in which diamonds cally since 1950) compared with mining of the natural
on the tips of pistons are compressed together, achieving material is clearly seen by comparing the scales of the two
pressures up to 200 GPa. Such pressures are comparable charts below. The US leads the world in the manufacture
with those in the centre of the Earth. A stainless-steel of synthetic diamonds, while the main reserves of gemstone
gasket placed between the diamonds provides a sample diamonds are in Africa, Australia, Canada and Russia;
chamber. Diamonds are transparent to IR, visible, near- exploitation of the Canadian reserves is being expanded
UV and X-ray radiation, and therefore diamond anvil and the first underground diamond mine should begin
cells can be used in conjunction with spectroscopic and production in 2005.
 Black plate (347,1)

Chapter 13 . Allotropes of carbon 347

[Data: US Geological Survey using a conversion factor of 5 carats ¼ 1 g]

. colourless, non-conductors of electricity in which the indicated in structure 13.2, forming layers of centred-
carbon layers become buckled owing to saturation of hexagonal motifs.
the C atoms and loss of the
-system;
. coloured, electrical conductors in which the planarity and

-delocalization of the layers are retained.
Polymeric carbon monofluoride, CFn (n  1), is a widely
studied example of the first type of compound. It is formed
when F2 reacts with graphite at 720 K (or at lower tempera-
tures in the presence of HF), although at 970 K, the product
is monomeric CF4 . The fluorine content in materials formu-
lated as CFn is variable and their colour varies, being white (13.2)
when n
1:0. Carbon monofluoride possesses a layer struc-
ture, and is used as a lubricant, being more resistant to The electrical conductivity of KC8 is greater than that of
atmospheric oxidation at high temperatures than graphite. a-graphite, consistent with the addition of electrons to the
Part of one layer is shown in Figure 13.4b; in the idealized delocalized
-system. Heating KC8 leads to the formation
compound CF, each C atom is tetrahedral; each CC of a series of decomposition products as the metal is elimi-
bond distance within a layer is 154 pm, and between layers nated (equation 13.8). The structures of these materials are
is 820 pm, i.e. more than double that in a-graphite. related, there being one, two, three, four or five carbon
The second class of intercalation compound includes the layers respectively between layers of Kþ ions.
blue graphite salts formed with strong acids in the presence





of oxidizing agents, and the metallic-looking red or blue KC8  KC24  KC36  KC48  KC60
" " " "

compounds formed when graphite reacts with group 1 copper-coloured blue

metals. For example, when graphite is treated with an excess ð13:8Þ
of K (and unreacted metal is washed out with Hg), a para-
magnetic copper-coloured material formulated as Kþ [C8 ] Such alkali metal intercalates are extremely reactive, igniting
results. The penetration of Kþ ions between the layers in air and exploding on contact with water. Potassium can be
causes structural changes in the graphite framework: the replaced by a d-block metal by reaction of KC8 with metal
initially staggered layers (Figure 13.4a) become eclipsed, and chloride, but the choice of solvent for the reactions is critical,
the interlayer spacing increases from 335 to 540 pm. The Kþ as is the nature of the d-block metal salt (e.g. CuCl2 2H2 O,
ions lie above (or below) the centres of alternate C6 -rings, as MnCl2 4H2 O for sources of Cu2þ and Mn2þ ). Examples
 Black plate (348,1)

348 Chapter 13 . The group 14 elements

Reaction of graphite with [O2 ]þ [AsF6 ] results in the forma-

tion of the salt [C8 ]þ [AsF6 ] . The catalytic properties of
some graphite intercalation compounds render them of
practical importance; e.g. KC8 is a hydrogenation catalyst.

Fullerenes: synthesis and structure

In 1985, Kroto, Smalley and coworkers discovered that, by
subjecting graphite to laser radiation at >10 000 K, new
allotropes of carbon were formed. The fullerenes are
named after architect Buckminster Fuller, known for
designing geodesic domes. Each fullerene is molecular and
the family includes C60 , C70 , C76 , C78 , C80 and C84 . Several
synthetic routes to fullerenes have been developed; C60 and
C70 are the major components of the mixture formed when
graphitic soot is produced as graphite rods are evaporated
(by applying an electrical arc between them) in a helium
atmosphere at
130 bar and the vapour condensed. Extrac-
tion of the soot into benzene yields a red solution from which
C60 and C70 can be separated by chromatography. Hexane or
benzene solutions of C60 are magenta, while those of C70 are
red. Both C60 and C70 are now available commercially, and
this has encouraged rapid exploration of their chemical
properties.
Figure 13.5a shows the structure of C60 . Although a
number of X-ray diffraction studies of C60 have been
carried out, the near-spherical shape of the molecule has
led to frustrating orientational disorder (see Section 18.3)
problems. The C60 molecule belongs to the Ih point group
and consists of an approximately spherical network of
atoms which are connected in 5- and 6-membered rings;
Fig. 13.4 (a) Part of the infinite layered-lattice of a-
all the C atoms are equivalent, as indicated by the fact
graphite (‘normal’ graphite); the layers are co-parallel, that the 13 C NMR spectrum of C60 exhibits one signal
and atoms in alternate layers lie over each other. This is ( þ143). The rings are arranged such that no 5-membered
emphasized by the yellow lines in the diagram. (b) Part of one rings are adjacent to each other. Thus, C60 (the smallest
layer of the structure of CFn for n ¼ 1. fullerene that can be isolated as a stable species) satisfies
the Isolated Pentagon Rule (IPR).† The separation of the
include MnC16 , FeC24 and CuC16 which contain Mn(II), 5-membered rings by 6-membered rings is easily seen in the
Fe(III) and Cu(II) respectively. schematic representation of C60 shown in Figure 13.5b
In the metal-containing intercalation compounds, the which also gives a bonding scheme. Each C atom is
carbon layers are reduced and become negatively charged. covalently bonded to three others in an approximately
In contrast, in intercalation compounds formed with trigonal planar arrangement; the relatively large surface of
strong acids in the presence of oxidizing agents, the carbon the ‘sphere’ means that there is only slight deviation from
layers lose electrons and become positively charged, e.g. planarity at each C centre. There are two types of CC
graphite hydrogensulfate, [C24 ]þ [HSO4 ] 24H2 O, which is bond: those at the junctions of two hexagonal rings (6,6-
produced when graphite is treated with concentrated edges) are of length 139 pm, while those between a
H2 SO4 and a little HNO3 or CrO3 . A related product hexagonal and a pentagonal ring (5,6-edges) are longer,
forms when the acid is HClO4 ; in this intercalate, the 145.5 pm. These differences indicate the presence of localized
planar layers of carbon atoms are 794 pm apart and are double and single bonds, and similar bonding descriptions
separated by [ClO4 ] ions and acid molecules. Cathodic are appropriate for other fullerene cages. We consider
reduction of this material, or treatment with graphite, gives chemical evidence for the presence of C¼C double bonds
a series of compounds corresponding to the sequential below. After C60 , the next smallest fullerene to satisfy the
elimination of HClO4 . These materials are better electrical IPR is C70 . The C70 molecule has D5h symmetry and is
conductors than graphite, and this can be explained in
terms of a positive-hole mechanism (see Section 5.9).
Other intercalation compounds include those formed with †
For the origins of the IPR, see: H.W. Kroto (1985) Nature, vol. 318,
Cl2 , Br2 , ICl and halides such as KrF2 , UF6 and FeCl3 . p. 354.
 Black plate (349,1)

Chapter 13 . Allotropes of carbon 349

Fig. 13.5 (a) The structure of the fullerene C60 ; the approximately spherical molecule is composed of fused 5- and
6-membered rings of carbon atoms. [X-ray diffraction at 173 K of the benzene solvate C60 4C6 H6 , M.F. Meidine et al.
(1992) J. Chem. Soc., Chem. Commun., p. 1534.] (b) A representation of C60 , in the same orientation as is shown in (a), but
showing only the upper surface and illustrating the localized single and double carbon–carbon bonds.

approximately ellipsoidal (Figure 13.6); it comprises 6- research. We provide a brief introduction to the chemical
and 5-membered rings organized so that, as in C60 , properties of C60 ; organometallic derivatives are covered in
5-membered rings are never adjacent. The 13 C NMR Section 23.10, and the reading list at the end of the
spectrum of C70 confirms that there are five C environments chapter gives more in-depth coverage.
in solution, consistent with the solid state structure (Figure The structural representation in Figure 13.5b suggests
13.6a). connected benzene rings, but the chemistry of C60 is not
reminiscent of benzene. Although C60 exhibits a small
degree of aromatic character, its reactions tend to reflect the
Fullerenes: reactivity
presence of localized double and single CC bonds, e.g. C60
Since efficient syntheses have been available, fullerenes (in undergoes addition reactions. Birch reduction gives a
particular C60 ) have been the focus of an explosion of mixture of polyhydrofullerenes (equation 13.9) with C60 H32

Fig. 13.6 The structure of C70 determined from an X-ray diffraction study of C70 6S8 [H.B. Bürgi et al. (1993) Helv. Chim.
Acta, vol. 76, p. 2155]: (a) a ball-and-stick representation showing the five carbon atom types, and (b) a space-filling
diagram illustrating the ellipsoidal shape of the molecule.
 Black plate (350,1)

350 Chapter 13 . The group 14 elements

Fig. 13.7 Halogenation reactions of C60 . Although the number of possible isomers for products C60 Xn where 2  n  58 is, at the
very least, large, some of the reactions (such as fluorination using NaF and F2 ) are surprisingly selective.

being the dominant product; reoxidation occurs with the add to remote C atoms. Thus, in C60 Br8 and in C60 Br24
quinone shown. Reaction 13.10 shows a selective route to (Figure 13.8a), the Br atoms are in 1,3- or 1,4-positions
C60 H36 ; the hydrogen-transfer agent is 9,10-dihydroanthra- with respect to each other. Just as going from benzene to
cene (DHA). In addition to being a selective method of cyclohexane causes a change from a planar to boat- or
hydrogenation, use of 9,9’,10,10’-[D4 ]dihydroanthracene chair-shaped ring, addition of substituents to C60 causes
provides a method of selective deuteration. deformation of the near-spherical surface. This is illustrated
in Figure 13.8 with the structures of C60 Br24 and C60 F18 . The
1. Li / liquid NH3 C60 -cage in C60 Br24 includes both boat and chair C6 -rings.
2. tBuOH Addition of a Br to a C atom causes a change from sp2 to
C60 C60H18 + ...... + C60H36 (13.9)
sp3 hybridization. The arrangement of the Br atoms over
O
the surface of the C60 cage is such that they are relatively
NC Cl far apart from each other. In contrast, in C60 F18 (Figure
13.8b), the F atoms are in 1,2-positions with respect to
NC Cl each other and the C60 -cage suffers severe ‘flattening’ on
O
the side associated with fluorine addition. At the centre of
the flattened part of the cage lies a planar, C6 -ring (shown
623 K, sealed tube, at the centre of the lower part of Figure 13.8b). This ring
623 K, sealed tube,
120-fold excess of 120-fold excess of has equal C–C bond lengths (137 pm) and has aromatic char-
DHA, 24 h DHA, several min acter. It is surrounded by sp3 hybridized C atoms, each of
C60H18 C60 C60H36
which bears an F atom.
The ene-like nature of C60 is reflected in a range of reac-
DHA = tions such as the additions of an O atom to give an
epoxide (C60 O) and of O3 at 257 K to yield an intermediate
ozonide (C60 O3 ). In hydrocarbon solvents, addition occurs
(13.10) at the junction of two 6-membered rings (a 6,6-bond), i.e.
at a C¼C bond, as shown in scheme 13.11. Loss of O2
Additions of F2 , Cl2 and Br2 also occur, the degree and selec- from C60 O3 gives C60 O but the structure of this product
tivity of halogenation depending on conditions (Figure 13.7). depends on the reaction conditions. At 296 K, the product
Because F atoms are small, addition of F2 to adjacent C is an epoxide with the O bonded across a 6,6-bond. In
atoms in C60 is possible, e.g. to form 1,2-C60 F2 . However, contrast, photolysis opens the cage and the O atom bridges
in the addition of Cl2 or Br2 , the halogen atoms prefer to a 5,6-edge (scheme 13.11).
 Black plate (351,1)

Chapter 13 . Allotropes of carbon 351

Fig. 13.8 The structure of C60 Br24 determined by X-ray diffraction at 143 K [F.N. Tebbe et al. (1992) Science, vol. 256, p. 822].
The introduction of substituents results in deformation of the C60 surface; compare the structure of C60 Br24 with that of C60 in
Figure 13.5a which shows the C60 cage in a similar orientation. (b) The structure (X-ray diffraction at 100 K) of C60 F18 [I.S. Neretin et
al. (2000) Angew. Chem. Int. Ed., vol. 39, p. 3273]. Note that the F atoms are all associated with the ‘flattened’ part of the fullerene
cage. Colour code: C, grey; Br, gold; F, green.

Reactions of C60 with free radicals readily occur, e.g.

photolysis of RSSR produces RS
which reacts with C60 to
give C60 SR
, although this is unstable with respect to regen-
eration of C60 . The stabilities of radical species C60 Y
are

tBu

ð13:11Þ
tBu•
2 2

Other reactions typical of double-bond character include tBu

the formation of cycloaddition products (exemplified
schematically in equation 13.12), and some have been
developed to prepare a range of rather exotic derivatives.
R R
tBu
C60 + C60

R R

(13.12) (13.13)
 Black plate (352,1)

352 Chapter 13 . The group 14 elements

highly dependent on the steric demands of Y. When the Me2N NMe2

reaction of t Bu
(produced by photolysis of a tert-butyl No solvent
halide) with C60 is monitored by ESR spectroscopy (which + C60 [C2(NMe2)4]+ [C60]–
Dissolve in
detects the presence of unpaired electrons), the intensity of Me2N NMe2 toluene
the signal due to the radical C60 t Bu
increases over the
(Liquid at 298 K)
temperature range 300–400 K. These data are consistent
with equilibrium 13.13, with reversible formation and (13.15)
cleavage of an inter-cage CC bond.
The formation of methanofullerenes, C60 CR2 , occurs The electrochemical reduction of C60 results in the formation
by reaction at either 5,6- or 6,6-edges in C60 . For the 6,6- of a series of fulleride ions, [C60 ]n where n ¼ 1–6. The mid-
addition products, the product of the reaction of C60 with point potentials (obtained using cyclic voltammetry and
diphenylazomethane is C61 Ph2 (equation 13.14) and, measured with respect to the ferrocenium/ferrocene couple,
initially, structural data suggested that the reaction was an Fcþ /Fc ¼ 0 V, ferrocene; see Section 23.13) for the reversible
example of ‘cage expansion’ with the addition of the CPh2 one-electron steps at 213 K are given in scheme 13.16.
unit being concomitant with the cleavage of the CC bond –0.81 V –1.24 V –1.77 V
C60 [C60]– [C60]2– [C60]3–
marked a in equation 13.14. This conclusion was at
odds with NMR spectroscopic data and theoretical calcula-
–2.22 V –2.71 V –3.12 V
tions, and a low-temperature X-ray diffraction study of [C60]4– [C60]5– [C60]6– (13.16)
compound 13.3 has confirmed that 6,6-edge-bridged
By titrating C60 in liquid NH3 against an Rb/NH3 solution
methanofullerenes should be described in terms of the C60
(see Section 8.6) at 213 K, five successive reduction steps
cage sharing a common CC bond with a cyclopropane ring.
are observed and the [C60 ]n anions have been studied by
Ph vibrational and electronic spectroscopies. At low tempera-
Ph tures, some alkali metal fulleride salts of type [Mþ ]3 [C60 ]3
C
become superconducting (see Section 27.4). The structures
a of the M3 C60 fullerides can be described in terms of Mþ
ions occupying the interstitial holes in a lattice composed
Ph2C–N≡N
C60 (13.14) of close-packed, near-spherical C60 cages. In K3 C60 and
– N2 Rb3 C60 , the [C60 ]3 cages are arranged in a ccp lattice, and
the cations fully occupy the octahedral and tetrahedral
holes (Figure 13.9). The temperature at which a material
becomes superconducting is its critical temperature, Tc .
SiMe3 Values of Tc for K3 C60 and Rb3 C60 are 18 K and 28 K
C
respectively, and for Cs3 C60 (in which the C60 cages adopt
a bcc lattice), Tc ¼ 40 K. Although Na3 C60 is structurally
C

C SiMe3
C C
C
C
C

157.4 pm

(13.3)

Theoretical studies on C60 show that the LUMO is triply

degenerate and the HOMO–LUMO (see Section 1.17)
separation is relatively small. It follows that reduction of
C60 should be readily achieved. A number of charge transfer
complexes have been prepared in which a suitable donor Fig. 13.9 A representation of the structures of K3 C60 and
Rb3 C60 in which the [C60 ]3 cages are arranged in an fcc
molecule transfers an electron to C60 as in equation 13.15. lattice with the Mþ ions occupying all the octahedral (grey)
This particular product is of importance because, on and tetrahedral (red) holes. Some of the cations in the unit cell
cooling to 16 K, it becomes ferromagnetic (see Figure 20.25). shown are hidden by [C60 ]3 anions.
 Black plate (353,1)

Chapter 13 . Structural and chemical properties of silicon, germanium, tin and lead 353

related to K3 C60 and Rb3 C60 , it is not superconducting. The . diamond-type lattice of Si, Ge and a-Sn (Section 5.11
paramagnetic [C60 ]2 anion has been isolated as the and Figure 5.19);
[K(crypt-222)]þ salt (reaction 13.17 and Section 10.8). . polymorphism of Sn (Section 5.4);
DMF=K . structure of Pb (Section 5.3);
toluene=crypt-222 . semiconducting properties (Section 5.9).
C60  ½Kðcrypt-222Þ2 ½C60 
"
ð13:17Þ
2
In the solid state, the [C60 ] cages are arranged in layers Chemical properties
with hexagonal packing, although the cages are well separ-
Silicon is much more reactive than carbon. At high tempera-
ated; [K(crypt-222)]þ cations reside between the layers of
tures, Si combines with O2 , F2 , Cl2 , Br2 , I2 , S8 , N2 , P4 , C and
fulleride anions.
B to give binary compounds. Silicon liberates H2 from
The coupling of C60 molecules through [2 þ 2] cycloaddition
aqueous alkali (equation 13.18), but is insoluble in acids
to give C120 (13.4) can be achieved by a solid state reaction that
other than a mixture of concentrated HNO3 and HF.
involves high-speed vibration milling of C60 in the presence of
catalytic amounts of KCN. When heated at 450 K for a short Si þ 4½OH  ½SiO4 4 þ 2H2
"
ð13:18Þ
period, the C120 molecule dissociates into C60 .
On descending group 14, the electropositivity and reac-
tivity of the elements increase. In general, Ge behaves in a
similar manner to Si, but, being more electropositive,
reacts with concentrated HNO3 (forming GeO2 ), and does
not react with aqueous alkali. Reactions between Ge and
HCl or H2 S yield GeCl4 or GeS2 respectively. Although
high temperatures are needed for reactions between Sn and
(13.4) O2 (to give SnO2 ) or sulfur (giving SnS2 ), the metal reacts
readily with halogens to yield SnX4 . Tin is little affected by
Endohedral metallofullerenes are a remarkable series of
dilute HCl or H2 SO4 , but reacts with dilute HNO3 (to give
compounds in which metal atoms are encapsulated within
Sn(NO3 )2 and NH4 NO3 ) and with concentrated acids
a fullerene cage; the general family is denoted as Mx @Cn .
yielding SnCl2 (from HCl) and SnSO4 and SO2 (from
Examples of these compounds include Sc2 @C84 , Y@C82 ,
H2 SO4 ). Hot aqueous alkali oxidizes the metal to Sn(IV)
La2 @C80 and Er@C60 . In general, the larger fullerenes
according to equation 13.19.
produce more stable compounds than C60 . The compounds
are prepared by vaporizing graphite rods impregnated with 2–
OH
an appropriate metal oxide or metal carbide. By use of 13 C
and 139 La NMR spectroscopies, it has been shown that the –2H2 HO OH
Sn + 2[OH]– + 4H2O Sn (13.19)
two lanthanum atoms in La2 @C80 undergo circular HO OH
motion within the fullerene cage. OH

Carbon nanotubes A pyrophoric material is spontaneously inflammable.

Carbon nanotubes were discovered in 1991 and consist of
elongated cages, best thought of as rolled graphite-like When finely divided, Pb is pyrophoric, but bulk pieces are
sheets, i.e. in contrast to the fullerenes, nanotubes consist passivated by coatings of, for example, PbO, and reaction
of networks of fused 6-membered rings. Nanotubes are with O2 in air occurs only above
900 K. Lead reacts very
very flexible and have great potential in materials science. slowly with dilute mineral acids, slowly evolves H2 from
As a result, research in this area is a ‘hot topic’ but is hot concentrated HCl, and reacts with concentrated HNO3
beyond the scope of this book; the end-of-chapter reading to give Pb(NO3 )2 and oxides of nitrogen. For reactions of
list provides an entry into the area. Pb with halogens, see Section 13.8.

Worked example 13.2 Reactivity of the group 14

13.5 Structural and chemical properties elements with halogens
of silicon, germanium, tin and lead
Write an equation for the reaction that takes place when Si is
heated in F2 . The product of the reaction is a gas for which
Structures
f H o (298 K) ¼ 1615 kJ mol1 . Use this value and appro-
The solid state structures of Si, Ge, Sn and Pb and the trends priate data from the Appendices in the book to calculate a
from semiconductor to metal on descending the group have value for the Si–F bond enthalpy. Compare the value obtained
already been discussed: with that in Table 13.2.
 Black plate (354,1)

354 Chapter 13 . The group 14 elements

F2 oxidizes Si to Si(IV) and the reaction is: . catenation is more common for C than the later group 14
SiðsÞ þ 2F2 ðgÞ  SiF4 ðgÞ
" elements, and hydrocarbon families are much more
diverse than their Si, Ge, Sn and Pb analogues.
To find the bond enthalpy term, start by writing an equation
for the dissociation of gaseous SiF4 into gaseous atoms,
and then set up an appropriate thermochemical cycle that Worked example 13.3 Bond enthalpies and group 14
incorporates
f H o (SiF4 ,g). hydrides
∆Ho
SiF4(g) Si(g) + 4F(g)
Suggest why catenation is more common for C than for Si, Ge
and Sn. Why is this relevant to the formation of families of
∆fHo(SiF4,g) ∆aHo(Si) + 4∆aHo(F) saturated hydrocarbon molecules?

Si(s) + 2F2(g)
The much higher CC bond enthalpies (see Table 13.2)

H o corresponds to the enthalpy change (gas-phase reac- compared with those of SiSi, GeGe and SnSn bonds
tion) when the four SiF bonds are broken. By Hess’s Law: means that the formation of compounds containing bonds
between carbon atoms is thermodynamically more favour-

H o þ
f H o ðSiF4 ;gÞ ¼
a H o ðSi;gÞ þ 4
a H o ðF;gÞ
able than analogous compounds containing SiSi, GeGe
The atomization enthalpies are listed in Appendix 10. and SnSn bonds. On descending group 14, orbital

H o ¼
a H o ðSi;gÞ þ 4
a H o ðF;gÞ 
f H o ðSiF4 ;gÞ overlap becomes less efficient as the valence orbitals
become more diffuse, i.e. as the principal quantum number
¼ 456 þ ð4  79Þ  ð1615Þ increases.
¼ 2387 kJ mol1 The backbones of saturated hydrocarbons are composed
2387 of CC bonds, i.e. their formation depends on catenation
SiF bond enthalpy ¼ ¼ 597 kJ mol1 being favourable. An additional factor that favours the
4
This compares with a value of 582 kJ mol1 listed in Table formation of hydrocarbons is the strength of the CH
13.2. bonds (stronger than SiH, GeH or SnH (see Table
13.2). On descending group 14, the hydrides become thermo-
dynamically less stable, and the kinetic barriers to reactions
Self-study exercises such as hydrolysis of EH bonds become lower.
1. Germanium reacts with F2 to give gaseous GeF4 . Use data from
Table 13.2 and Appendix 10 to estimate a value of Self-study exercises

f H o (GeF4 ,g). [Ans. 1169 kJ mol1 ]
1. Using bond enthalpies from Table 13.2, calculate values of
2. Suggest reasons why PbCl2 rather than PbCl4 is formed when
H o for the reactions:
Pb reacts with Cl2 . [Ans. See Box 12.3]
SiH4 ðgÞ þ 4Cl2 ðgÞ  SiCl4 ðgÞ þ 4HClðgÞ
"

CH4 ðgÞ þ 4Cl2 ðgÞ  CCl4 ðgÞ þ 4HClðgÞ

"

Additional data: see Appendix 10; the bond dissociation

enthalpy of HCl is 432 kJ mol1 . Comment on the results.
13.6 Hydrides [Ans. 1020; 404 kJ mol1 ]
2. Use the fact that CH4 is kinetically stable, but thermodynami-
Although the extensive chemistry of hydrocarbons (i.e. cally unstable, with respect to oxidation by O2 at 298 K to
carbon hydrides) lies outside this book, we note several sketch an approximate energy profile for the reaction:
points for comparisons with later group 14 hydrides:
CH4 ðgÞ þ 3O2 ðgÞ  2CO2 ðgÞ þ 2H2 OðlÞ
"

. Table 13.2 illustrated the relative strength of a CH bond Comment on the relative energy changes that you show in the
compared with CCl and CO bonds, and this trend is diagram.
not mirrored by later elements; [Ans. Plot E versus reaction coordinate, showing relative
. CH4 is chlorinated with some difficulty, whereas SiH4 energy levels of reactants and products;
r H is negative; Ea
reacts violently with Cl2 ; is relatively large]
. CH4 is stable with respect to hydrolysis, but SiH4 is
readily attacked by water;
. SiH4 is spontaneously inflammable in air and, although
it is the kinetic stability of CH4 with respect to reaction
Binary hydrides
with O2 at 298 K that is crucial, values of
c H o show Silane, SiH4 , is formed when SiCl4 or SiF4 reacts with
that combustion of SiH4 is more exothermic than that Li[AlH4 ] and is a source of pure Si (equation 13.20) for semi-
of CH4 ; conductors (see Section 5.9, Box 5.2 and Section 27.6).
 Black plate (355,1)

Chapter 13 . Hydrides 355

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.6 Methane hydrates

A gas hydrate is an example of a clathrate, a crystalline solid

comprising a host (a three-dimensional assembly of H2 O
molecules which form cage-like arrays) and guest molecules
(small molecules such as CH4 which occupy the cavities in
the host lattice). Gas hydrates occur naturally in the Arctic
and in deep-sea continental margins, and their importance
lies in their ability to trap gases within crystalline masses,
thereby acting rather like natural gas ‘storage tanks’. It is
possible that such deposits could be tapped for fuel
sources, but on the other hand, any uncontrolled release of
the huge amounts of CH4 that is presently trapped inside [Data: US Geological Survey]
these clathrates could add to the ‘greenhouse’ effect (see
Box 13.8). The total amount of naturally occurring Further reading
organic compound-based carbon on Earth is estimated to
be about 19 000  1015 t. In addition to this, carbon occurs S.-Y. Lee and G.D. Holder (2001) Fuel Processing Tech-
widely in inorganic minerals such as carbonates. The chart nology, vol. 71, p. 181 – ‘Methane hydrates potential as a
opposite shows the relative importance of methane hydrates future energy source’.
as a potential source of carbon from organic-based carbon M. Max and W. Dillon (2000) Chemistry & Industry, p. 16 –
materials. ‘Natural gas hydrate: A frozen asset?’

Silanes Sin H2n þ 2 with straight or branched chains are known type M[SiH3 ] with Na, K (equation 13.23), Rb and Cs.
for 1  n  10, and Figure 13.10 compares the boiling points The crystalline salt K[SiH3 ] possesses an NaCl structure
of the first five straight-chain silanes with their hydrocarbon and is a valuable synthetic reagent, e.g. equation 13.24.
analogues. Silanes are explosively inflammable in air (equa-
SiH4 þ 2KOH þ H2 O  K2 SiO3 þ 4H2
"
ð13:22Þ
tion 13.21).
in MeOCH2 CH2 OMe


SiH4  Si þ 2H2
"
ð13:20Þ 2SiH4 þ 2K  2K½SiH3  þ H2
"
ð13:23Þ
Me ECl MeI
SiH4 þ 2O2  SiO2 þ 2H2 O
"
ð13:21Þ Me3 ESiH3 þ KCl 3 K½SiH3   MeSiH3 þ KI
3 "

E ¼ Si; Ge; Sn

A mixture of SiH4 , Si2 H6 , Si3 H8 and Si4 H10 along with traces ð13:24Þ
of higher silanes is obtained when Mg2 Si reacts with aqueous Germanes Gen H2n þ 2 (straight and branched chain
acid, but the non-specificity of this synthesis renders it of isomers) are known for 1  n  9. GeH4 is less reactive
little practical value. By irradiating SiH4 with a CO2 laser, than SiH4 ; it is a colourless gas (bp 184 K, dec 488 K),
SiH4 can be converted selectively into Si2 H6 . Silane is a insoluble in water, and prepared by treating GeO2 with
colourless gas which is insoluble in water, reacts rapidly Na[BH4 ] although higher germanes are also formed.
with alkalis (equation 13.22) and forms compounds of the Discharges of various frequencies are finding increased use
for this type of synthesis and have been used to convert
GeH4 into higher germanes, or mixtures of SiH4 and GeH4
into Ge2 H6 , GeSiH6 and Si2 H6 . Mixed hydrides of Si and
Ge, e.g. GeSiH6 and GeSi2 H8 , are also formed when an
intimate mixture of Mg2 Ge and Mg2 Si is treated with acid.
Reactions between GeH4 and alkali metals, M, in liquid
NH3 produce M[GeH3 ], and, like [SiH3 ] , the [GeH3 ] ion
is synthetically useful. The reaction of SnCl4 with Li[AlH4 ]
gives SnH4 (bp 221 K) but this decomposes at 298 K into
Sn and H2 ; note the variation in reactivities: SiH4 > GeH4
< SnH4 . Plumbane, PbH4 , is poorly characterized and may
not actually have been isolated. Significantly, however,
Fig. 13.10 Boiling points of the straight-chain silanes, replacement of H atoms by alkyl or aryl substituents is
Sin H2n þ 2 , and hydrocarbons Cn H2n þ 2 . accompanied by increased stability (see Section 18.5).
 Black plate (356,1)

356 Chapter 13 . The group 14 elements

Fig. 13.11 Representative reactions of SiH3 Cl. The structures of N(SiH3 )3 (determined by X-ray diffraction at 115 K) and
(H3 Si)2 O (determined by electron diffraction).

Halohydrides of silicon and germanium Appendix 6); similarly, in (H3 Si)2 O, the SiOSi bond
angle of 1448 is large (compare 1118 in Me2 O) and the
Of compounds of the type SiHn X4  n (X ¼ halogen, n ¼ 1–3), SiO bonds of 163 pm are shorter than rcov . Trigermyl-
SiHCl3 is of particular importance in the purification of Si in amine is isostructural with N(SiH3 )3 , but P(SiH3 )3 is
the semiconductor industry (equation 13.25). The success of pyramidal with PSi bonds of length 225 pm. In (H3 Si)2 S,
the second step in scheme 13.25 depends on the precursor the SiSSi bond angle is 978 and the SiS bond distances
being volatile. SiHCl3 (mp 145 K, bp 306 K) is ideally suited (214 pm) are consistent with a bond order of 1. For many
to the process, as is SiH4 (mp 88 K, bp 161 K). years, these data have been taken as an indication that N
670 K and O take part in ( p–d )
-bonding with Si (diagram 13.5),
SiðimpureÞ þ 3HCl  SiHCl3 "
there being no corresponding interactions in SiP or SiS
H2
bonds. However, recent arguments centre around the
1: Purification
by distillation planarity of N(SiH3 )3 (and related strengthening of SiN
 Siðpure; polycrystallineÞ
"
ð13:25Þ and SiO bonds) being due to n(N)   (SiH) electron
"

2: CVD ðchemical
vapour depositionÞ donation, where n(N) represents the non-bonding (lone
pair) electrons of the N atom. This is so-called negative
Another application of SiHCl3 is hydrosilation (equation hyperconjugation,† and is analogous to the donation of
13.26), a method of introducing an SiCl3 group and an electrons from a d-block metal centre to a  -orbital of a
entry to organosilicon chemistry. PR3 ligand that we describe in Section 20.4. A stereo-
RCH¼CH2 þ SiHCl3  RCH2 CH2 SiCl3
"
ð13:26Þ electronic effect also contributes to N(SiH3 )3 being planar.
The polarity of the NSi bonds (P (Si) ¼ 1.9, P (N) ¼ 3.0)

; AlCl3 is such that there are significant long-range electrostatic
SiH4 þ nHX  SiH4  n Xn þ nH2
"

repulsions between the SiH3 groups. These are minimized

n ¼ 1 or 2 ð13:27Þ if the NSi3 -skeleton in N(SiH3 )3 adopts a trigonal
planar, rather than pyramidal, geometry. The possibility of
The halo-derivatives SiH2 X2 and SiH3 X (X ¼ Cl, Br, I) can
(p–d)
-bonding in N(SiH3 )3 should not be confused with
be prepared from SiH4 (equation 13.27) and some reactions
the (p–p)
-bonding which occurs in, for example, Si¼N
of SiH3 Cl (bp 243 K) are shown in Figure 13.11. The ease
bonds (with a formal bond order of 2) in compounds such
with which SiHn X4  n compounds hydrolyse releasing HX
as t Bu2 Si¼NSit Bu3 , 13.6. Notice that in 13.6 the nitrogen
means that they must be handled in moisture-free conditions.
atom is in a linear environment and can be considered to
The preparation and reactivity of GeH3 Cl resemble those of
have a stereochemically inactive lone pair, possibly involved
SiH3 Cl.
in
-interactions.
The structures of trisilylamine, N(SiH3 )3 , and disilyl ether,
(H3 Si)2 O, are shown in Figure 13.11. The NSi3 skeleton in †
Negative hyperconjugation: see Y. Mo, Y. Zhang and J. Gao (1999)
N(SiH3 )3 is planar and the NSi bond distance of 173 pm Journal of the American Chemical Society, vol. 121, p. 5737 and
is shorter than the sum of the covalent radii, rcov (see references cited in this paper.
 Black plate (357,1)

Chapter 13 . Carbides, silicides, germides, stannides and plumbides 357

CaNCN þ 3H2 O  CaCO3 þ 2NH3

"
ð13:29Þ

Equations 13.30 and 13.31 show syntheses of Na2 C2 ,

Ag2 C2 and Cu2 C2 ; the group 11 carbides are heat- and
shock-sensitive, and explosive when dry.
in liquid NH3
2NaNH2 þ C2 H2  Na2 C2 þ 2NH3
"
ð13:30Þ
þ þ
2½MðNH3 Þ2  þ C2 H2  M2 C2 þ 2½NH4  þ 2NH3
"

M ¼ Ag; Cu ð13:31Þ

(13.5) (13.6)
Carbides of formula MC2 do not necessarily contain the
acetylide ion. The room temperature form of ThC2 (Th is an
actinoid metal, see Chapter 24) adopts an NaCl lattice but is
not isostructural with CaC2 . In ThC2 , the C2 -units
13.7 Carbides, silicides, germides, (dCC ¼ 133 pm) in alternating layers lie in different orienta-
stannides and plumbides tions. The solid state structure of LaC2 contains C2 -units with
dCC ¼ 129 pm. Unlike CaC2 which is an insulator, ThC2 and
LaC2 have metallic appearances and are electrical conductors.
Carbides The CC bond lengths can be rationalized in terms of struc-
tures approximating to Th4þ [C2 ]4 and La3þ [C2 ]3 ; compared
Classifying carbides is not simple, but some useful categories
with [C2 ]2 , the extra electrons in [C2 ]4 and [C2 ]3 reside in
are:
antibonding MOs, thus weakening the CC interaction.
. saline (salt-like) carbides which produce mainly CH4 However, the conducting properties and diamagnetism of
when hydrolysed; ThC2 and LaC2 show that this is an oversimplified description
. those containing the [CC]2 ion; since electron delocalization into a conduction band (see
. those containing the [C¼C¼C]4 ion; Section 5.8) must occur. Hydrolysis of these carbides is also
. interstitial carbides; atypical of a [C2 ]2 -containing species, e.g. the reaction of
. solid state carbides with other lattice structures; ThC2 and H2 O yields mainly C2 H2 , C2 H6 and H2 .
. fulleride salts (see Section 13.4); Carbides containing [C¼C¼C]4 are rare; they include
. endohedral metallofullerenes (see Section 13.4). Mg2 C3 (see end of Section 11.4) which liberates propyne
upon hydrolysis.
Examples of saline carbides are Be2 C (see Section 11.4 and The structures of the so-called interstitial carbides (formed
equation 11.14) and Al4 C3 , both made by heating the by heating C with d-block metals having rmetal > 130 pm, e.g.
constituent elements at high temperatures. Although their Ti, Zr, V, Mo, W) may be described in terms of a close-
solid state structures contain isolated C centres which are packed metal lattice with C atoms occupying octahedral
converted to CH4 on reaction with H2 O, it is unlikely that holes (see Figure 5.5). In carbides of type M2 C (e.g. V2 C,
the ‘C4 ’ ion is present since the interelectronic repulsion Nb2 C) the metal atoms are in an hcp lattice and half of the
energy would be enormous. octahedral sites are occupied; in the MC type (e.g. TiC and
Carbides containing the [CC]2 (acetylide) ion include WC), the metal atoms adopt a ccp structure and all the
Na2 C2 , K2 C2 , MC2 (M ¼ Mg, Ca, Sr, Ba), Ag2 C2 and octahedral holes are occupied. These interstitial carbides
Cu2 C2 ; they evolve C2 H2 when treated with water (see are important refractory materials; characteristically they
equation 11.15). Calcium carbide is manufactured (see are very hard and infusible, have melting points >2800 K
Box 11.3) as a grey solid by heating CaO with coke at and, in contrast to the acetylide derivatives, do not react

2300 K, and when pure, it is colourless. It adopts a with water. Tungsten carbide, WC, is one of the hardest
distorted NaCl lattice, the axis along which the [CC]2 substances known and is widely used in cutting tools and
are aligned being lengthened; the CC bond distance is dies. Although TiC, WC, V2 C, Nb2 C and related compounds
119 pm, compared with 120 pm in C2 H2 . The reaction are commonly described as interstitial compounds, this
between CaC2 and N2 (equation 13.28) is used commercially does not imply weak bonding. To convert solid carbon into
for the production of calcium cyanamide, a nitrogenous isolated carbon atoms is a very endothermic process and
fertilizer (equation 13.29). The cyanamide ion, 13.7, is this must be compensated by the formation of strong WC
isoelectronic with CO2 . bonds. Similar considerations apply to interstitial nitrides
(see Section 14.6).
–N C N– Transition metals with rmetal < 130 pm (e.g. Cr, Fe, Co, Ni)
(13.7) form carbides with a range of stoichiometries (e.g. Cr3 C2 ,
1300 K Fe3 C) which possess complicated structures involving CC
CaC2 þ N2  CaNCN þ C
"
ð13:28Þ bonding. In Cr3 C2 (formed by reaction 13.32), the Cr atoms
 Black plate (358,1)

358 Chapter 13 . The group 14 elements

form a lattice of edge-sharing trigonal prisms each occupied Germides, stannides and plumbides
by a C atom such that carbon chains run through the structure
with CC distances comparable to single bonds. Germanium, tin and lead do not form solid state binary
compounds with metals. In contrast, the formation of Zintl
1870 K; in
presence of H2
phases and Zintl ions (see Section 8.6), which contain clusters
3Cr2 O3 þ 13C  2Cr3 C2 þ 9CO
"
ð13:32Þ of group 14 metal atoms, is characteristic of these elements. As
we have already seen, anionic units containing silicon are
Carbides of this type are hydrolysed by water or dilute acid
known, in addition to the formation of metal silicides with
to give mixtures of hydrocarbons and H2 .
extended solid state structures. The synthesis of [Sn5 ]2 (equa-
tion 8.35) typifies the preparations of other Zintl ions and the
Silicides
use of the encapsulating ligand crypt-222 to bind an alkali
The structures of the metal silicides (prepared by direct metal counter-ion (see Figure 10.8) has played a crucial role
combination of the elements at high temperatures) are in the development of Zintl ion chemistry. Thus, salts such
diverse, and a full discussion of the structures is beyond as [K(crypt-222)]2 [Sn5 ] and [Na(crypt-222)]4 [Sn9 ] can be
the scope of this book.† Some examples of their solid state isolated. Modern technology allows low-temperature X-ray
structural types are: diffraction studies of sensitive (e.g. thermally unstable)
compounds. It is now‡ therefore possible to investigate salts
. isolated Si atoms (e.g. Mg2 Si, Ca2 Si);
such as [Li(NH3 )4 ]4 [Pb9 ]:NH3 and [Li(NH3 )4 ]4 [Sn9 ]:NH3
. Si2 -units (e.g. U3 Si2 );
which are formed by the direct reaction of an excess of Pb
. Si4 -units (e.g. NaSi, KSi, CsSi)
or Sn in solutions of lithium in liquid NH3 .
. Sin -chains (e.g. CaSi);
Diamagnetic Zintl ions include [M4 ]4 (M ¼ Ge, Sn, Pb),
. planar or puckered hexagonal networks of Si atoms (e.g.
[M5 ]2 (M ¼ Sn, Pb), [M9 ]4 (M ¼ Ge, Sn, Pb), [Ge9 ]2 ,
b-USi2 , CaSi2 );
[Ge10 ]2 , [Sn8 Tl]3 , [Sn9 Tl]3 and [Pb2 Sb2 ]2 . Paramagnetic
. three-dimensional network of Si atoms (e.g. SrSi2 , a-
ions are exemplified by [Sn9 ]3 and [Ge9 ]3 . The structure of
USi2 ).
[Sn5 ]2 was shown in Figure 8.3. Figure 13.12 shows the
The Si4 -units present in the alkali metal silicides are structures of [Sn9 ]4 and [Ge9 ]3 , and illustrates some of
noteworthy. The [Si4 ]4 anion is isoelectronic with P4 and the main deltahedral families of the group 14 Zintl ions.
the solid state structures of several group 1 metal silicides Bonding in these ions is delocalized, and for the diamagnetic
contain tetrahedral Si4 -units, but these are not isolated clusters, Wade’s rules (see Section 12.11) can be used to
anions. The structure of Cs4 Si4 comes close to featuring rationalize the observed structures. Wade’s rules were devel-
discrete, tetrahedral [Si4 ]4 ions, but significant cation–anion oped for borane clusters. A {BH}-unit contributes two elec-
interactions exist. The silicide K3 LiSi4 possesses tetrahedral trons to cluster bonding and, similarly, a group 14 atom
Si4 -units linked by Liþ ions to give infinite chains, and in contributes two electrons to cluster bonding if a lone pair
K7 LiSi8 , pairs of Si4 -units are connected as shown in structure of electrons is localized outside the cage. Thus, in bonding
13.8 with additional interactions involving Kþ ions. terms, an Si, Ge, Sn or Pb atom can mimic a {BH}-unit.
More strictly, an atom of each group 14 element is isolobal
7–
Si with a {BH}-unit (see Section 23.5).

Si Si
Worked example 13.4 Structures of Zintl ions
Si
Rationalize the structure of [Sn9 ]4 shown in Figure 13.12a.
Li
There are nine Sn atoms and each provides two valence
Si
electrons, assuming that each atom carries a lone pair of
Si Si
electrons.
There are four electrons from the 4 charge.
Si
Total number of cage-bonding electrons available
(13.8)
¼ ð9  2Þ þ 4 ¼ 22 electrons
Silicides are hard materials, but their melting points are ¼ 11 pairs
generally lower than those of the metal carbides. Treatment
of Mg2 Si with dilute acids gives mixtures of silanes (see
Section 13.6). The properties of some silicides make them
†
useful as refractory materials (e.g. Fe3 Si and CrSi2 ); Fe3 Si For further details, see: A.F. Wells (1984) Structural Inorganic
Chemistry, 5th edn, Clarendon Press, Oxford, p. 987.
is used in magnetic tapes and disks to increase their ‡
N. Korber and A. Fleischmann (2001) Journal of the Chemical Society,
thermal stability. Dalton Transactions, p. 383.
 Black plate (359,1)

Chapter 13 . Carbides, silicides, germides, stannides and plumbides 359

Fig. 13.12 The structures, established by X-ray diffraction, of (a) [Sn9 ]4 , determined for the salt [Na(crypt-222)]4 [Sn9 ]
[J.D. Corbett et al. (1977) J. Am. Chem. Soc., vol. 99, p. 3313], and (b) [Ge9 ]3 , determined for the compound
[K(crypt-222)]3 [Ge9 ] PPh3 [C. Belin et al. (1991) New J. Chem., vol. 15, p. 931]; for discussion of cryptand ligands including
crypt-222, see Section 10.8. (c) Schematic representations of structure types for selected Zintl ions. See also Figure 13.13.

Thus, [Sn9 ]4 has 11 pairs of electrons with which to bond trigonal prismatic structures (Figure 13.12b). When
nine Sn atoms. Cs2 K[Ge9 ] is added to a mixture of 1,2-ethanediamine and
This means that there are (n þ 2) pairs of electrons for n crypt-222, coupling of the [Ge9 ]3 radicals occurs to give
vertices, and so [Sn9 ]4 is a nido-cage, based on a 10-vertex Cs4 [K(crypt-222)]2 [(Ge9 )2 ]; formally, the coupling involves
deltahedron (see Figure 12.24) with one vertex vacant. the oxidation of one lone pair on each [Ge9 ]3 cage. The
This corresponds to the observed structure of a monocapped structure of the [(Ge9 )2 ]6 ion (Figure 13.13a) consists of
square-antiprism. two monocapped square-antiprismatic clusters (each with
delocalized bonding) connected by a localized, two-centre
Self-study exercises two-electron GeGe bond. Wade’s rules can be applied to
each cage in [(Ge9 )2 ]6 as follows:
1. By referring to Figures 12.24 and 13.12c, rationalize the struc-
tures of: . eight of the Ge atoms each carries a lone pair of electrons
(a) [Ge4 ]4 ; (b) [Sn5 ]2 ; (c) [Ge9 ]2 ; (d) [Ge10 ]2 . and provides two electrons for cluster bonding;
. the Ge atom involved in the inter-cage GeGe bond
2. Rationalize why [Sn5 ]2 and [Pb5 ]2 are isostructural.
contributes three electrons to cluster bonding (one elec-
3. Rationalize why [Pb5 ]2 adopts the same cluster structure as tron is used for the external GeGe bond);
C2 B3 H5 . [Hint: Look back to worked example 12.10] . the 6 charge provides three electrons to each cage;
. total electron count per cage ¼ 16 þ 3 þ 3 ¼ 22 electrons;
. 11 pairs of electrons are available to bond nine Ge atoms,
Reaction conditions are critical to the selective formation of and so each cage is classed as a nido-cluster, consistent
a Zintl ion. The alloy KSn2 reacts with crypt-222 (see with the observed monocapped square-antiprism
Section 10.8) in 1,2-diaminoethane to give [K(crypt- (Figure 13.13a).
222)]3 [Sn9 ] containing the paramagnetic [Sn9 ]3 ion.
However, reaction times must be less than two days, since The Zintl ions shown in Figure 13.12 are closo- or nido-
longer periods favour the formation of [K(crypt-222)]4 [Sn9 ] clusters. The compounds Rb4 Li2 Sn8 and K4 Li2 Sn8 , which
containing the diamagnetic [Sn9 ]4 ion. The paramagnetic contain arachno-[Sn8 ]6 (Figure 13.13b), have been prepared
clusters [Sn9 ]3 and [Ge9 ]3 both adopt distorted tricapped by the direct fusion of tin metal with the respective alkali
 Black plate (360,1)

360 Chapter 13 . The group 14 elements

Fig. 13.13 (a) The structure (X-ray diffraction) of the [(Ge9 )2 ]6 ion in Cs4 [K(crypt-222)]2 [(Ge9 )2 ]
6en (en ¼ 1,2-
ethanediamine) [L. Xu et al. (1999) J. Am. Chem. Soc., vol. 121, p. 9245]. (b) The arachno-[Sn8 ]6 cluster in Rb4 Li2 Sn8 .
(c) The solid state structure of Rb4 Li2 Sn8 shows that Liþ ions cap the open cage to give [Li2 Sn8 ]4 (see text). (d) The open
[Sn12 ]12 cluster in the compound CaNa10 Sn12 ; the cage encapsulates a Ca2þ ion.

metals. X-ray diffraction studies on Rb4 Li2 Sn8 show that the In the discussion of Wade’s rules in Section 12.11 and, in
arachno-[Sn8 ]6 cluster is stabilized by interactions with Liþ particular, in Box 12.9, we described the involvement of
ions which effectively close up the open cage as shown in radial and tangential orbitals in cluster bonding in boranes.
Figure 13.13c. In addition, each Liþ ion interacts with an Outward-pointing radial orbitals on each B atom are
SnSn edge of an adjacent cluster and as a result, a involved in the formation of the external (exo) BH -
network of interconnected cages is formed, with Rbþ ions bonds. Similarly, in most Zintl ions, the lone pair of electrons
in cavities between the Zintl ions. The combination of that is localized on each atom is accommodated in an
small and large cations is an important factor in the stabili- outward-pointing orbital. In the oxidative coupling of two
zation of this system. The same strategy has been used to [Ge9 ]3 cages to give [(Ge9 )2 ]6 (Figure 13.13a), the localized
stabilize another open-cage Zintl ion, [Sn12 ]12 (Figure single bond that joins the cages and which formally arises
13.13d), which is formed by fusing together stoichiometric from the oxidation of a lone pair per cluster is radially
amounts of Na, Ca and Sn. The product is CaNa10 Sn12 , oriented with respect to each cluster. However, in
and in the solid state, the Ca2þ ion provides a stabilizing [(Ge9 )3 ]6 (Figure 13.14), the intercluster bonds are not
effect by being sited at the centre of the [Sn12 ]12 cluster. A radially related to each cluster, but lie parallel to the prism
related system in which Sr2þ replaces Ca2þ has also been edges. In addition, the GeGe bond lengths for the
prepared.
As more Zintl ions are isolated, challenges to the rationa-
lization of the bonding within Wade’s rules are encountered.
For example, the oxidation of [Ge9 ]4 using PPh3 , AsPh3 , As
or Sb gives [(Ge9 )3 ]6 (equations 13.33 and 13.34). The
[(Ge9 )3 ]6 anion (Figure 13.14) consists of three tricapped
trigonal prismatic cages, each with two elongated prism
edges.
3Rb4 ½Ge9  þ 3EPh3  Rb6 ½ðGe9 Þ3  þ 3Rb½EPh2  þ 3RbPh
"

ðE ¼ P; AsÞ ð13:33Þ
Fig. 13.14 The structure (X-ray diffraction) of the
3½Ge9 4 þ 14E  ½ðGe9 Þ3 6 þ 2½E7 3
"
ðE ¼ As; SbÞ [(Ge9 )3 ]6 ion in [Rb(crypt-222)]6 [(Ge9 )3 ]:3en
(en ¼ 1,2-ethanediamine) [A. Ugrinov et al. (2002) J. Am.
ð13:34Þ Chem. Soc., vol. 124, p. 10990].
 Black plate (361,1)

Chapter 13 . Halides and complex halides 361

intercluster bonds are significantly longer in [(Ge9 )3 ]6 than

that in [(Ge9 )2 ]6 . This suggests that the bonds that connect
the cages in [(Ge9 )3 ]6 are of bond orders less than 1 and that C H F2 C F HF
the bonding is not localized. It is, therefore, not possible to
apply Wade’s rules to each cage in this tricluster system.

r H o ¼ 480 kJ mol1 ð13:37Þ
The preparation of a fully fluorinated organic compound
tends therefore to be carried out in an inert solvent (the
13.8 Halides and complex halides vaporization of which consumes the heat liberated) in a
reactor packed with gold- or silver-plated copper turnings
(which similarly absorb heat but may also play a catalytic
Carbon halides
role). Other methods include use of CoF3 or AgF2 as fluor-
Selected physical properties of the tetrahalides of C and Si inating agents, or electrolysis in liquid HF (see Section 8.7).
are listed in Table 13.3. The carbon tetrahalides differ mark- Fluorocarbons (see also Section 16.3) have boiling points
edly from those of the later group 14 elements: they are inert close to those of the corresponding hydrocarbons but have
towards water and dilute alkali and do not form complexes higher viscosities. They are inert towards concentrated
with metal halides. The distinction has been attributed to alkalis and acids, and dissolve only in non-polar organic
the absence of d orbitals in the valence shell of a C atom; solvents. Their main applications are as high-temperature
look back at the electronic versus steric debate, outlined in lubricants. Freons are chlorofluorocarbons (CFCs) or
Section 13.3. However, one must be cautious. In the case chlorofluorohydrocarbons, made by partial replacement of
of CX4 being inert towards attack by water, the ‘lack of chlorine as in, for example, the first step of scheme 13.38.
C d orbitals’ presupposes that the reaction would proceed Although CFCs have been used extensively in aerosol
through a 5-coordinate intermediate (i.e. as is proposed for propellants, air-conditioners, foams for furnishings, refriger-
hydrolysis of silicon halides). Of course, it is impossible to ants and solvents, concern over their role in the depletion of
establish the mechanism of a reaction that does not occur! the ozone layer has resulted in rapid phasing out of their use
Certainly, CF4 and CCl4 are thermodynamically unstable as is described in Box 13.7.
with respect to hydrolysis; compare the value of
r Go for HF 970 K
equation 13.35 with that of 290 kJ mol1 for the hydrolysis CHCl3  CHF2 Cl  C2 F4 þ HCl
" "
ð13:38Þ
SbCl5 ; SbF3
of SiCl4 .
Two important polymers are manufactured from chloro-
CCl4 ðlÞ þ 2H2 OðlÞ  CO2 ðgÞ þ 4HClðaqÞ
"

fluoro-compounds. The monomer for the commercially

r Go ¼ 380 kJ mol1 ð13:35Þ named Teflon or PTFE is C2 F4 (tetrafluoroethene) which is
prepared by reaction 13.38; polymerization occurs in the
Carbon tetrafluoride is extremely inert and may be prepared
presence of water with an organic peroxide catalyst. Teflon
by the reaction of SiC and F2 , with the second product, SiF4 ,
is an inert white solid, stable up to 570 K; it has widespread
being removed by passage through aqueous NaOH. Equa-
domestic applications, e.g. non-stick coatings for kitchen-
tion 13.36 shows a convenient laboratory-scale synthesis of
ware. The monomer CF2 ¼CFCl is used to manufacture
CF4 from graphite-free calcium cyanamide (see structure
the commercial polymer Kel-F. Both Teflon and Kel-F are
13.7); trace amounts of CsF are added to prevent the forma-
used in laboratory equipment such as sealing tape and
tion of NF3 .
washers, parts in gas cylinder valves and regulators, coatings
CsF; 298 K; 12 h for stirrer bars, and sleeves for glass joints operating under
CaNCN þ 3F2  CF4 þ CaF2 þ N2
"
ð13:36Þ
vacuum.
Uncontrolled fluorination of an organic compound Carbon tetrachloride (Table 13.3) is produced by chlori-
usually leads to decomposition because large amounts of nation of CH4 at 520–670 K or by the reaction sequence
heat are evolved (equation 13.37). 13.39, in which the CS2 is recycled.

Table 13.3 Selected physical properties of the carbon and silicon tetrahalides.

Property CF4 CCl4 CBr4 CI4 SiF4 SiCl4 SiBr4 SiI4

Melting point / K 89 250 363 444 (dec) 183 203 278.5 393.5
Boiling point / K 145 350 462.5 – 187 331 427 560.5
Appearance at 298 K Colourless Colourless Colourless Dark red Colourless Colourless, Colourless, Colourless
gas liquid solid solid gas, fumes fuming fuming solid
in air liquid liquid
 Black plate (362,1)

362 Chapter 13 . The group 14 elements

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.7 CFCs and the Montreal Protocol

The ozone layer is a stratum in the atmosphere 15–30 km are still ozone-depleting (they are classified as ‘Class II’
above the Earth’s surface, and it protects life on the Earth ozone-depleters) and will be phased out by 2020.
from UV radiation originating from the Sun because O3 Hydrofluorocarbons appear to have little or no ozone-
absorbs strongly in the ultraviolet region of the spectrum. depleting effect and can also be used in refrigerants and
An effect of UV radiation on humans is skin cancer. Chloro- aerosol propellants.
fluorocarbons (CFCs) are atmospheric pollutants which
contribute towards the depletion of the ozone layer. In
1987, the ‘Montreal Protocol for the Protection of the
Ozone Layer’ was established and legislation was
implemented to phase out the use of CFCs: an almost
complete phase-out of CFCs was required by 1996 for
industrial nations, with developing nations following this
ban by 2010. Taking the 1986 European consumption of
CFCs as a standard (100%), the graph opposite illustrates
how the usage of these chemicals (e.g. aerosol propellants,
refrigerants) was reduced between 1986 and 1993. The
phasing out of CFCs has affected the manufacture of
asthma inhalers, large numbers of which used to use a
CFC-based propellant. These inhalers are being replaced
by new models with hydrofluoroalkane (HFA) propellants. [Data from Chemistry & Industry, 1994, p. 323.]
CFCs are not the only ozone-depleting chemicals. Other
‘Class I’ ozone-depleters include CH2 ClBr, CBr2 F2 , CF3 Br,
Further information
CCl4 , CHCl3 and CH3 Br. In the past, methyl bromide has
had widespread agricultural applications for pest control For up-to-date information from the Environmental
(see Box 16.3). Alternative pesticides for, for example, soil Protection Agency, see: http://www.epa.gov/ozone/title6/
treatment continue to be developed in order to comply phaseout/mdi/
with the Montreal Protocol which bans CH3 Br by 2005 For information on the Montreal Protocol Unit within the
(2015 in developing countries). United Nations Development Programme, see: http://
As an interim measure, hydrochlorofluorocarbons www.undp.org/seed/eap/montreal/
(HCFCs) can be used in refrigerants in place of CFCs. For relevant information from the European Environment
While less harmful to the environment than CFCs, HCFCs Agency, see: http://themes.eea.eu.int/

9
Fe catalyst > used in World War I chemical warfare. It is manufactured
CS2 þ 3Cl2







CCl4 þ S2 Cl2 >
"
= by reaction 13.42, and is used industrially in the production
CS2 þ 2S2 Cl2

CCl4 þ 6S ð13:39Þ
"
>
> of diisocyanates (for polyurethane polymers), polycarbonates
;
6S þ 3C

3CS2
"
and 1-naphthyl-N-methylcarbamate, 13.10 (for insecticides).
In the past, CCl4 has been widely used as a solvent and for activated carbon catalyst
CO þ Cl2
















COCl2 "
ð13:42Þ
the chlorination of inorganic compounds. However, its high
toxicity and the fact that photochemical or thermal decompo- O
sition results in the formation of CCl3
and Cl
radicals has led
C
to its manufacture and use being controlled by environmental O NHMe
legislation. Reactions 13.40 and 13.41 give preparations of
Cl NH2
CBr4 and CI4 (Table 13.3). Both compounds are toxic and
are easily decomposed to their elements; CI4 decomposes O C O C
slowly in the presence of H2 O, giving CHI3 and I2 . Cl NH2
3CCl4 þ 4AlBr3

3CBr4 þ 4AlCl3
"
ð13:40Þ (13.9) (13.10) (13.11)

AlCl3 Fluorination of COCl2 using SbF3 yields COClF and COF2

CCl4 þ 4C2 H5 I



CI4 þ 4C2 H5 Cl
"
ð13:41Þ
which, like COCl2 , are unstable to water, and react with NH3
Carbonyl chloride ( phosgene), 13.9, is a highly toxic, (to give urea, 13.11) and alcohols (to give esters). Reaction of
colourless gas (bp 281 K) with a choking smell, and was COCl2 with SbF5 yields the linear cation [ClCO]þ . Its
 Black plate (363,1)

Chapter 13 . Halides and complex halides 363

presence in the condensed phase has been established by partially hydrolysed (compare equations 13.44 and 13.45).
vibrational spectroscopic studies. Reaction between COF2 Controlled hydrolysis of SiCl4 results in the formation of
and SbF5 , however, gives an adduct F2 CO SbF5 rather (Cl3 Si)2 O, through the intermediate SiCl3 OH.
than [FCO]þ [SbF6 ] .
2SiF4 þ 4H2 O  SiO2 þ 2½H3 Oþ þ ½SiF6 2 þ 2HF
"

Silicon halides ð13:44Þ

Many fluorides and chlorides of Si are known, but we SiCl4 þ 2H2 O  SiO2 þ 4HCl
"
ð13:45Þ
confine our discussion to SiF4 and SiCl4 (Table 13.3) and The reaction between equimolar amounts of neat SiCl4 and
some of their derivatives. Silicon and Cl2 react to give SiCl4 , SiBr4 at 298 K leads to an equilibration mixture of SiCl4 ,
and SiF4 can be obtained by fluorination of SiCl4 using SiBrCl3 , SiBr2 Cl2 , SiBr3 Cl and SiBr4 (see end-of-chapter
SbF3 , or by reaction 13.43; compare with equations 12.28 problem 2.28) which can be separated by fractional distilla-
and 14.78. tion. The Lewis base N-methylimidazole (MeIm) reacts with
SiO2 þ 2H2 SO4 þ 2CaF2  SiF4 þ 2CaSO4 þ 2H2 O
"
SiCl4 and SiBr2 Cl2 to give trans-[SiCl2 (MeIm)4 ]2þ (Figure
13.15a) as the chloride and bromide salts respectively. This
ð13:43Þ
provides a means of stabilizing an [SiCl2 ]2þ cation.
Both SiF4 and SiCl4 are molecular with tetrahedral struc- The formation of [SiF6 ]2 , the hexafluorosilicate ion
tures. They react readily with water, but the former is only (Figure 13.15b), illustrates the ability of Si to act as an F

Fig. 13.15 Solid state structures (X-ray diffraction) of (a) trans-[SiCl2 (MeIm)4 ]2þ from the salt [SiCl2 (MeIm)4 ]Cl2 :3CHCl3
(MeIm ¼ N-methylimidazole) [K. Hensen et al. (2000) J. Chem. Soc., Dalton Trans., p. 473], (b) octahedral [SiF6 ]2 ,
determined for the salt [C(NH2 )3 ]2 [SiF6 ] [A. Waskowska (1997) Acta Crystallogr., Sect. C, vol. 53, p. 128] and (c) trigonal
bipyramidal [SiF5 ] , determined for the compound [Et4 N][SiF5 ] [D. Schomburg et al. (1984) Inorg. Chem., vol. 23, p. 1378].
Colour code: Si, pink; F, green; N, blue; C, grey; Cl, green; H, white.
 Black plate (364,1)

364 Chapter 13 . The group 14 elements

acceptor and increase its coordination number beyond 4. PbX2 halides are more stable than PbX4 . Tin tetrafluoride
Hexafluorosilicates are best prepared by reactions of SiF4 (which forms hygroscopic crystals, see Section 11.5) is
with metal fluorides in aqueous HF; the Kþ and Ba2þ salts prepared from SnCl4 and HF. At 298 K, SnF4 is a white
are sparingly soluble. In aqueous solution, fluorosilicic acid solid and has a sheet structure, 13.12, with octahedral Sn
is a strong acid, but pure H2 SiF6 has not been isolated. atoms. At 978 K, SnF4 sublimes to give a vapour containing
The [SiF5 ] ion (Figure 13.15c) is formed in the reaction of tetrahedral molecules. SnF4 is thermally stable, but PbF4
SiO2 with aqueous HF, and may be isolated as a tetra- (which has the same solid state structure as SnF4 ) decom-
alkylammonium ion. Silicon tetrachloride does not react poses into PbF2 and F2 when heated, and must be prepared
with alkali metal chlorides, although lattice energy con- by the action of F2 or halogen fluorides (see Section 16.7) on
siderations suggest that it might be possible to stabilize the Pb compounds.
[SiCl6 ]2 ion using a very large quaternary ammonium
cation.
Sn
Halides of germanium, tin and lead
Sn Sn
There are many similarities between the tetrahalides of Ge Sn
and Si, and GeX4 (X ¼ F, Cl, Br or I) is prepared by direct
combination of the elements. At 298 K, GeF4 is a colourless
gas, GeCl4 , a colourless liquid, and GeI4 a red-orange solid
=F
(mp 417 K); GeBr4 melts at 299 K. Each hydrolyses, liber-
ating HX. Unlike SiCl4 , GeCl4 accepts Cl (e.g. reaction (13.12)
13.46). F F
F 205 pm
in SOCl2 Sn Sn
GeCl4 þ 2½Et4 NCl  ½Et4 N2 ½GeCl6 
"
ð13:46Þ
F F
The Si(II) halides SiF2 and SiCl2 can be obtained only as
218 pm
unstable species (by action of SiF4 or SiCl4 on Si at Sn Sn

1500 K) which polymerize to cyclic products. In contrast, F
Ge forms stable dihalides; GeF2 , GeCl2 and GeBr2 are F F
produced when Ge is heated with GeX4 , but the products (13.13)
disproportionate on heating (equation 13.47). Tin(II) fluoride is water-soluble and can be prepared in


aqueous media. In contrast, PbF2 is only sparingly soluble.
2GeX2  GeX4 þ Ge
"
ð13:47Þ One form of PbF2 adopts a CaF2 lattice (see Figure
5.18a), while the solid state structure of SnF2 consists of
Reaction between GeF2 and F gives [GeF3 ] . Several puckered Sn4 F8 rings, 13.13, with each Sn being trigonal
compounds of type MGeCl3 exist where Mþ may be an pyramidal consistent with the presence of a lone pair. In
alkali metal ion or a quaternary ammonium or phosphonium structures 13.12 and 13.13, the SnF bridge bonds are
ion (e.g. equations 13.48–13.50). Crystal structure deter- longer than the terminal bonds, a feature that is common
minations for [BzEt3 N][GeCl3 ] (Bz ¼ benzyl) and in this type of structure. Many tin fluoride compounds
[Ph4 P][GeCl3 ] confirm the presence of well-separated show a tendency to form FSnF bridges in the solid
trigonal pyramidal [GeCl3 ] ions. In contrast, CsGeCl3 state, as we illustrate later.
adopts a perovskite-type structure (Figure 5.23) which is Tin(IV) chloride, bromide and iodide are made by
distorted at 298 K and non-distorted above 328 K. combining the respective elements and resemble their Si
CsGeCl3 belongs to a group of semiconducting compounds and Ge analogues. The compounds hydrolyse, liberating
CsEX3 (E ¼ Ge, Sn, Pb; X ¼ Cl, Br, I). HX, but hydrates such as SnCl4 4H2 O can also be isolated.
CsCl; conc HCl The reaction of Sn and HCl gives SnCl2 , a white solid
GeðOHÞ2  CsGeCl3 "
ð13:48Þ which is partially hydrolysed by water. The hydrate
SnCl2 2H2 O is commercially available and is used as a
GeCl2 ð1;4-dioxaneÞ þ Ph4 PCl
reducing agent. In the solid state, SnCl2 has a puckered-
 ½Ph4 P½GeCl3  þ 1;4-dioxane
"
ð13:49Þ layer structure, but discrete, bent molecules are present in
the gas phase.
in 6M HCl
Ge þ RbCl  RbGeCl3 "
ð13:50Þ The Sn(IV) halides are Lewis acids, their ability to accept
halide ions (e.g. reaction 13.51) following the order
The preference for the þ2 over þ4 oxidation state
SnF4 > SnCl4 > SnBr4 > SnI4 .
increases down the group, the change being due to the
thermodynamic 6s inert pair effect (Box 12.3). Whereas in presence of HClðaqÞ
members of the GeX4 family are more stable than GeX2 , 2KCl þ SnCl4  K2 ½SnCl6  "
ð13:51Þ
 Black plate (365,1)

Chapter 13 . Oxides, oxoacids and hydroxides 365

stoichiometry, reaction conditions and counter-ion. In these

iodoplumbates, the Pb(II) centres are in either octahedral or
square-based pyramidal environments (Figure 13.17).

Worked example 13.5 Group 14 halides: structure and

energetics

Fig. 13.16 The structures of (a) [SnCl2 F] and (b) SnF4 sublimes at 978 K. Describe the changes that take place
[Sn2 F5 ] from the solid state structure (X-ray during sublimation and the processes that contribute to the
diffraction) of [Co(en)3 ][SnCl2 F][Sn2 F5 ]Cl (en, see Table 6.7); enthalpy of sublimation.
each Sn atom is in a trigonal pyramidal environment [I.E.
Rakov et al. (1995) Koord. Khim., vol. 21, p. 16]. Colour code:
Sublimation refers to the process:
Sn, brown; F, small green; Cl, large green.
SnF4 ðsÞ  SnF4 ðgÞ
"

Similarly, SnCl2 accepts Cl to give trigonal pyramidal In the solid state, SnF4 has a sheet structure (see structure
[SnCl3 ] , but the existence of discrete anions in the solid 13.12) in which each Sn is octahedrally sited. In the gas
state is cation-dependent (see earlier discussion of CsGeCl3 ). phase, SnF4 exists as discrete, tetrahedral molecules. During
The [SnF5 ] ion can be formed from SnF4 , but in the solid sublimation, the SnF4 units must be released from the solid
state, it is polymeric with bridging F atoms and octahedral state structure, and this involves breaking SnFSn bridges
Sn centres. The bridging F atoms are mutually cis to one and converting them into terminal SnF bonds. Each Sn
another. Bridge formation is similarly observed in Naþ salts atom goes from an octahedral to tetrahedral environment.
of [Sn2 F5 ] and [Sn3 F10 ]4 , formed by reacting NaF and Enthalpy changes that take place are:
SnF2 in aqueous solution. Figure 13.16 shows the structures
. enthalpy change associated with SnF bond cleavage
of the [SnCl2 F] and [Sn2 F5 ] ions.
(endothermic process);
Lead tetrachloride is obtained as an oily liquid by the
. enthalpy change associated with the conversion of half an
reaction of cold concentrated H2 SO4 on [NH4 ]2 [PbCl6 ]; the
SnFSn bridge interaction to a terminal SnF bond
latter is made by passing Cl2 through a saturated solution
(two of these per molecule);
of PbCl2 in aqueous NH4 Cl. The ease with which
. enthalpy change associated with a change in hybridi-
[PbCl6 ]2 is obtained is a striking example of stabilization
zation of the Sn atom as it changes from octahedral to
of a higher oxidation state by complexation (see Section
tetrahedral, and an associated change in the SnF
7.3); in contrast, PbCl4 is hydrolysed by water and decom-
bond strength for the terminal SnF bonds.
poses to PbCl2 and Cl2 when gently heated. The Pb(II)
halides are considerably more stable than their Pb(IV)
analogues and are crystalline solids at 298 K; they can be Self-study exercises
precipitated by mixing aqueous solutions of soluble halide 1. Above 328 K, CsGeCl3 adopts a perovskite structure; at 298 K,
and soluble Pb(II) salts (e.g. equation 13.52). Note that few the structure is distorted, but remains based on perovskite.
Pb(II) salts are very soluble in water. Does solid CsGeCl3 contain discrete [GeCl3 ] ions? Explain
PbðNO3 Þ2 ðaqÞ þ 2NaClðaqÞ  PbCl2 ðsÞ þ 2NaNO3 ðaqÞ
"
your answer.
[Ans. Refer to Figure 5.23 and related discussion]
ð13:52Þ
2. Explain why PbX2 halides are more stable than PbX4 halides.
Lead(II) chloride is much more soluble in hydrochloric acid [Ans. The answer is in Box 12.3]
than in water owing to the formation of [PbCl4 ]2 . In the
solid state, PbCl2 has a complicated structure with 9-coordi- 3. In reactions 13.46 and 13.49, which reactants are Lewis acids
and which are Lewis bases? Give an explanation for your
nate Pb centres, but PbF2 has the fluorite structure
answer. What is the general name for the products?
(Figure 5.18a). The yellow diiodide adopts the CdI2 lattice [Ans. Acid ¼ electron acceptor; base ¼ electron donor; adduct]
(Figure 5.22). Discrete iodoplumbate anions such as
[Pb3 I10 ]4 (Figure 13.17a), [Pb7 I22 ]8 , [Pb10 I28 ]8 and
[Pb5 I16 ]6 (Figure 13.17b) as well as related polymeric
iodoplumbates† can be formed by reacting PbI2 and NaI in
the presence of large cations such as [R3 N(CH2 )4 NR3 ]2þ 13.9 Oxides, oxoacids and hydroxides
(R ¼ Me, n Bu) or [P(CH2 Ph)4 ]þ . The reactions can be
driven towards a particular product by varying the reactant
Oxides and oxoacids of carbon
†
See for example: H. Krautscheid, C. Lode, F. Vielsack and H. Vollmer Unlike the later elements in group 14, carbon forms stable,
(2001) Journal of the Chemical Society, Dalton Transactions, p. 1099. volatile monomeric oxides: CO and CO2 . A comment on
 Black plate (366,1)

366 Chapter 13 . The group 14 elements

Fig. 13.17 The structures (X-ray diffraction) of (a) the [Pb3 I10 ]4 ion in the [n Bu3 N(CH2 )4 Nn Bu3 ]2þ salt [H. Krautscheid et al.
(1999) J. Chem. Soc., Dalton Trans., p. 2731] and (b) the [Pb5 I16 ]6 ion in the salt [n BuN(CH2 CH2 )3 Nn Bu]3 [Pb5 I16 ]:4DMF
[H. Krautscheid et al. (2000) Z. Anorg. Allg. Chem., vol. 626, p. 3]. Colour code: Pb, blue; I, yellow.

the difference between CO2 and SiO2 can be made in the light are formed respectively. Carbon monoxide combines with
of the thermochemical data in Table 13.2: the C¼O bond F2 , Cl2 and Br2 (as in equation 13.42), sulfur and selenium.
enthalpy term is more than twice that for the CO bond, The high toxicity of CO arises from the formation of a
while the Si¼O bond enthalpy term is less than twice that stable complex with haemoglobin (see Section 28.3) with
of the SiO bond. In rationalizing these differences, there the consequent inhibition of O2 transport in the body. The
is some justification for saying that the C¼O bond is oxidation of CO to CO2 is the basis of quantitative analysis
strengthened relative to Si¼O by ( p–p)
contributions, for CO (equation 13.54) with the I2 formed being removed
and, in the past, it has been argued that the SiO bond is and titrated against thiosulfate. CO is similarly oxidized by
strengthened relative to the CO bond by ( p–d)
-bonding a mixture of MnO2 , CuO and Ag2 O at ambient temperatures
(but see comments at the end of Section 13.6). Irrespective and this reaction is used in respirators.
of the interpretation of the enthalpy terms however, the
I2 O5 þ 5CO  I2 þ 5CO2
"
ð13:54Þ
data indicate that (ignoring enthalpy and entropy changes
associated with vaporization) SiO2 is stable with respect to The thermodynamics of the oxidation of carbon is of
conversion into molecular O¼Si¼O, while CO2 is stable immense importance in metallurgy as we have already
with respect to the formation of a macromolecular species discussed in Section 7.8.
containing 4-coordinate C and CO single bonds. Selected physical properties of CO and CO2 are given in
However, an extended solid phase of CO2 has recently Table 13.4; bonding models are described in Sections 1.7
been prepared by laser-heating a molecular phase at and 4.7. The bond in CO is the strongest known in a stable
1800 K and under 40 GPa pressure; the vibrational spectrum molecule and confirms the efficiency of ( p–p)
-bonding
of the new phase indicates that it is structurally similar to between C and O. However, considerations of the bonding
quartz (see below).† provide no simple explanation as to why the dipole
Carbon monoxide is a colourless gas, formed when C moment of CO is so low.
burns in a restricted supply of O2 . Small-scale preparations In an excess of O2 , C burns to give CO2 . Solid CO2 is
involve the dehydration of methanoic acid (equation called dry ice and readily sublimes (Table 13.4) but may be
13.53). CO is manufactured by reduction of CO2 using
coke heated above 1070 K or by the water–gas shift reaction
(see Section 9.4). Industrially, CO is very important and we Table 13.4 Selected properties of CO and CO2 .
consider some relevant catalytic processes in Chapter 26.
conc H2 SO4
Property CO CO2
HCO2 H  CO þ H2 O
"
ð13:53Þ
Melting point / K 68 –
Carbon monoxide is almost insoluble in water under normal Boiling point / K 82 195 (sublimes)
conditions and does not react with aqueous NaOH, but at
f H o (298 K) / kJ mol1 110.5 393.5
high pressures and temperatures, HCO2 H and Na[HCO2 ]
f Go (298 K) / kJ mol1 137 394
Bond energy / kJ mol1 1075 806
CO bond distance / pm 112.8 116.0
†
Quartz-like CO2 , see: V. Iota, C.S. Yoo and H. Cynn (1999) Science, Dipole moment / D 0.11 0
vol. 283, p. 1510.
 Black plate (367,1)

Chapter 13 . Oxides, oxoacids and hydroxides 367

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.8 ‘Greenhouse’ gases

Carbon dioxide normally comprises
0.04% by volume of returned according to the carbon cycle:
the Earth’s atmosphere, from which it is removed and

The balance is a delicate one, and the increase in combustion Industrialized countries that signed the 1997 Kyoto
of fossil fuels and decomposition of limestone for cement Protocol are committed to reducing their ‘greenhouse’
manufacture in recent years have given rise to fears that a gas emissions. Taking 1990 emission levels as a baseline,
consequent increase in the CO2 content of the atmosphere a target of
5% reduction must be achieved by 2008–
will lead to an ‘enhanced greenhouse effect’, raising the 2012. This target is an average over all participating
temperature of the atmosphere. This arises because the countries.
sunlight that reaches the Earth’s surface has its maximum
energy in the visible region of the spectrum where the atmos-
Further reading
phere is transparent. However, the energy maximum of the
Earth’s thermal radiation is in the infrared, where CO2 N. Doak (2002) Chemistry & Industry, Issue 23, p. 14 –
absorbs strongly (see Figure 3.11). Even a small increase in ‘Greenhouse gases are down’.
the CO2 component of the atmosphere might have serious G.D. Farquhar (1997) Science, vol. 278, p. 1411 – ‘Carbon
effects because of its effects on the extent of the polar ice dioxide and vegetation’.
caps and glaciers, and because of the sensitivity of reaction J.G. Ferry (1997) Science, vol. 278, p. 1413 – ‘Methane:
rates to even small temperature changes. The danger is Small molecule, big impact’.
enhanced by the cutting down and burning of tropical rain A. Kendall, A. McDonald and A. Williams (1997) Chemistry
forests which would otherwise reduce the CO2 content of & Industry, p. 342 – ‘The power of biomass’.
the atmosphere by photosynthesis. J.D. Mahlman (1997) Science, vol. 278, p.1416 – ‘Uncertain-
The second major ‘greenhouse’ gas is CH4 which is ties in projections of human-caused climate warming’.
produced by the anaerobic decomposition of organic A. Moss (1992) Chemistry & Industry, p. 334 – ‘Methane
material; the old name of ‘marsh gas’ came about because from ruminants in relation to global warming’.
bubbles of CH4 escape from marshes. Flooded areas such For information from the European Environment Agency,
as rice paddy fields produce large amounts of CH4 , and see: http://www.eea.eu.int/
ruminants (e.g. cows, sheep and goats) also expel sizeable The Carbon Dioxide Information Analysis Center (CDIAC)
quantities of CH4 . Although the latter is a natural process, provides up-to-date information on trends in ‘greenhouse’
recent increases in the numbers of domestic animals gas emissions and global change: http://cdiac.esd.ornl.gov/
around the world are naturally leading to increased release home.html
of CH4 into the atmosphere. See also Box 15.6: Volcanic emissions

kept in insulated containers for laboratory use in, e.g. low- CaCO3 þ 2HCl  CaCl2 þ CO2 þ H2 O
"
ð13:55Þ
temperature baths (Table 13.5). Supercritical CO2 has
become a much studied and versatile solvent (see Section Carbon dioxide is the world’s major environmental source of
8.13). Small-scale laboratory syntheses of gaseous CO2 acid and its low solubility in water is of immense biochemical
usually involve reactions such as 13.55; for the industrial and geochemical significance. In an aqueous solution of
production of CO2 , see Figure 10.5 and Section 9.4. carbon dioxide, most of the solute is present as molecular
 Black plate (368,1)

368 Chapter 13 . The group 14 elements

Table 13.5 Selected low-temperature baths involving dry ice.‡ remains a fact that, under ambient conditions, H2 CO3 is
not a readily studied species.†
Bath components Temperature / K O–

Dry ice þ ethane-1,2-diol 258 O C

Dry ice þ heptan-3-one 235
Dry ice þ acetonitrile 231 O–
Dry ice þ ethanol 201 (13.14)
Dry ice þ acetone 195
Dry ice þ diethyl ether 173 The carbonate ion is planar and possesses D3h symmetry
with all CO bonds of length 129 pm. A delocalized
‡
To construct a bath, add small pieces of solid CO2 to the solvent. Initial bonding picture involving ( p–p)
-interactions is appropriate,
sublimation of the CO2 ceases as the bath temperature decreases to the and VB theory describes the ion in terms of three resonance
point where solid dry ice persists. The bath temperature is maintained by
occasionally adding small pieces of dry ice. See also Table 14.1. structures of which one is 13.14. The CO bond distance in
[CO3 ]2 is longer than in CO2 (Table 13.4) and is consistent
with a formal bond order of 1.33. Most metal carbonates,
other than those of the group 1 metals (see Section 10.7),
CO2 rather than as H2 CO3 , as can be seen from the value of
are sparingly soluble in water. A general method of
K
1:7  103 for the equilibrium:
preparing peroxo salts can be used to convert K2 CO3 to
CO2 ðaqÞ þ H2 OðlÞ Ð H2 CO3 ðaqÞ K2 C2 O6 ; the electrolysis of aqueous K2 CO3 at 253 K using
Aqueous solutions of CO2 are only weakly acidic, but it does a high current density produces a salt believed to contain
not follow that H2 CO3 (carbonic acid) is a very weak acid. the peroxocarbonate ion, 13.15. An alternative route
The value of pKa (1) for H2 CO3 is usually quoted as 6.37. involves the reaction of CO2 with KOH in 86% aqueous
This evaluation, however, assumes that all the acid is H2 O2 at 263 K. The colour of the product is variable and
present in solution as H2 CO3 or [HCO3 ] when, in fact, a probably depends upon the presence of impurities such as
large proportion is present as dissolved CO2 . By taking KO3 . The electrolytic method gives a blue material whereas
this into account, one arrives at a ‘true’ pKa (1) for H2 CO3 the product from the second route is orange. Peroxocarbo-
of
3.6. Moreover, something that is of great biological nates are also believed to be intermediates in the reactions
and industrial importance is the fact that combination of of CO2 with superoxides (see Section 10.6).
CO2 with water is a relatively slow process. This can be –O

shown by titrating a saturated solution of CO2 against

C O O 115 pm
aqueous NaOH using phenolphthalein as indicator. Neutral-
O C C C O
ization of CO2 occurs by two routes. For pH<8, the main 125 pm
O O C
pathway is by direct hydration (equation 13.56), which
shows pseudo-first order kinetics. At pH>10, the main O–
pathway is by attack of hydroxide ion (equation 13.57). (13.15) (13.16)
The overall rate of process 13.57 (which is first order in A third oxide of carbon is the suboxide C3 O2 which is made
both CO2 and [OH] ) is greater than that of process 13.56. by dehydrating malonic acid, CH2 (CO2 H)2 , using P2 O5 at


CO2 þ H2 O  H2 CO3
"
slow 430 K. At room temperature, C3 O2 is a gas (bp 279 K), but
H2 CO3 þ ½OH  ½HCO3  þ H2 O
"
very fast it polymerizes above 288 K to form a red-brown paramag-
ð13:56Þ netic material. The structure of C3 O2 is usually described
 
as ‘quasi-linear’ because IR spectroscopic and electron
CO2 þ ½OH  ½HCO3  "
slow diffraction data for the gaseous molecule show that the
½HCO3  þ ½OH  ½CO3 2 þ H2 O
"
very fast energy barrier to bending at the central C atom is only
ð13:57Þ 0.37 kJ mol1 , i.e. very close to the vibrational ground
Until 1993, there was no evidence that free carbonic acid had state. The melting point of C3 O2 is 160 K. An X-ray diffrac-
been isolated, although an unstable ether adduct is formed tion study of crystals grown just below this temperature
when dry HCl reacts with NaHCO3 suspended in Me2 O at confirms that the molecules are essentially linear in the
243 K, and there is mass spectrometric evidence for H2 CO3 solid state (structure 13.16). However, the data are best
being a product of the thermal decomposition of interpreted in terms of disordered (see Section 18.3), bent
[NH4 ][HCO3 ]. However, IR spectroscopic data now indicate molecules with a CCC bond angle close to 1708, consis-
that H2 CO3 can be isolated using a cryogenic method in tent with a ‘quasi-linear’ description. The species
which glassy MeOH solution layers of KHCO3 (or
Cs2 CO3 ) and HCl are quenched on top of each other at †
See: R. Ludwig and A. Kornath (2000) Angewandte Chemie Inter-
78 K and the reaction mixture warmed to 300 K. In the national Edition, vol. 39, p. 1421 and references therein – ‘In spite of
absence of water, H2 CO3 can be sublimed unchanged. It the chemist’s belief: carbonic acid is surprisingly stable’.
 Black plate (369,1)

Chapter 13 . Oxides, oxoacids and hydroxides 369

[OCNCO]þ , [NCNCN] and [N5 ]þ are isoelectronic with 1143 K 1742 K 1983 K
β-quartz β-tridymite β-cristobalite liquid
C3 O2 , but they are not isostructural with the ‘quasi-linear’ slow slow slow

C3 O2 . Unambiguously non-linear structures are observed 846 K fast

393–
fast
473–
fast
433 K 548 K
for [OCNCO]þ (\CNC ¼ 1318 in [OCNCO]þ [Sb3 F16 ] ),
the dicyanamide ion [NCNCN] (\CNC ¼ 1248 in α-quartz α-tridymite α-cristobalite
Cs[NCNCN]), and [N5 ]þ (see Section 14.5).
Fig. 13.18 Transition temperatures between polymorphs of
SiO2 .

Worked example 13.6 Lewis structures

range, but possesses a low-temperature (a) and high-
(a) Draw a Lewis structure for linear C3 O2 . (b) Consider temperature (b) modification (Figure 13.18). The structure
possible Lewis structures for linear and non-linear (bent at of b-cristobalite and its relationship to that of diamond
the central atom) [OCNCO]þ and [NCNCN] . Comment on was shown in Figure 5.19. The different polymorphs of
these structures in view of the following X-ray diffraction silica resemble b-cristobalite in having tetrahedral SiO4 -
crystallographic data: units, but each is made unique by exhibiting a different
arrangement of these building blocks. a-Quartz has an
½OCNCOþ ½Sb3 F16  \CNC ¼ 131o , interlinked helical chain structure and is optically active
\OCN ¼ 173o , CO ¼ 112 pm, CN ¼ 125 pm because the chain has a handedness. It is also piezoelectric
and is therefore used in crystal oscillators and filters for
Cs½NCNCN \CNC ¼ 124o , \NCN ¼ 172o , frequency control and in electromechanical devices such as
av: CNterm ¼ 115 pm, av: CNcentre ¼ 128 pm microphones and loudspeakers.
(a) A Lewis structure for C3 O2 is: O
=
O C C C O Si
O
O
O
(b) Possible Lewis structures can be drawn by considering
(13.17)
isoelectronic relationships between C and Nþ , O and N ,
and N and Oþ . A piezoelectric crystal is one that generates an electric field (i.e.
Therefore starting from linear C3 O2 , Lewis structures for develops charges on opposite crystal faces when subjected to
linear [OCNCO]þ and [NCNCN] are: mechanical stress) or that undergoes some change to atomic
positions when an electric field is applied to it; such crystals
O C N C O N C N C N must lack a centre of symmetry (e.g. contain tetrahedral
arrangements of atoms). Their ability to transform electrical
However, the observed bond angles at the central atom show oscillations into mechanical vibration, and vice versa, is the
that the ions are non-linear in the solid state salts studied. basis of their use in, e.g., crystal oscillators.
For each ion, if a negative charge is localized on the
central N atom, then a Lewis structure consistent with a Transitions from one polymorph to another involve initial
non-linear structure can be drawn: SiO bond cleavage and require higher temperatures than
the changes between a- and b-forms of one polymorph.
N N When liquid silica cools, it forms a non-crystalline glass
C C C C consisting of an infinite lattice assembled from SiO4 tetra-
O O N N
hedra connected in a random manner. Only a few oxides
form glasses (e.g. B2 O3 , SiO2 , GeO2 , P2 O5 and As2 O5 )
The observed bond lengths in salts of [OCNCO]þ and since the criteria for a random assembly are:
[NCNCN] are consistent with the above Lewis structures.
. the coordination number of the non-oxygen element must
be 3 or 4 (a coordination number of 2 gives a chain and
greater than 4 gives too rigid a structure);
Silica, silicates and aluminosilicates . only one O atom must be shared between any two non-
oxygen atoms (greater sharing leads to too rigid an
Silica, SiO2 , is an involatile solid and occurs in many
assembly).
different forms, nearly all of which possess lattice structures
constructed of tetrahedral SiO4 building blocks, often When silica glass is heated to
1750 K, it becomes plastic
represented as in structure 13.17. Each unit is connected to and can be worked in an oxy-hydrogen flame. Silica glass
the next by sharing an oxygen atom to give SiOSi apparatus is highly insensitive to thermal shock owing to
bridges. At atmospheric pressure, three polymorphs of the low coefficient of thermal expansion of silica. Borosilicate
silica exist; each is stable within a characteristic temperature glass (Pyrex) contains 10–15% B2 O3 and has a lower melting
 Black plate (370,1)

370 Chapter 13 . The group 14 elements

point than silica glass. Soda glass contains added alkali

which converts some of the SiOSi bridges in the silica
network into terminal Si¼O groups, reducing the melting
point below that of borosilicate glass.
In all forms of silica mentioned so far, the SiO bond length
is
160 pm and the SiOSi bond angle
1448, values close
to those in (H3 Si)2 O (Figure 13.11). By heating silica under
very high pressure, a rutile form (see Figure 5.21) containing
6-coordinate Si is formed in which the SiO bond length is
179 pm (compare with the sum of rcov (Si) ¼ 118 pm and
rcov (O) ¼ 73 pm). This form of silica is more dense and less
reactive than ordinary forms. Silica is not attacked by acids
other than HF, with which it forms [SiF6 ]2 . Fusion of SiO2
with alkali leads to the formation of silicates.
Although esters of type Si(OR)4 (equation 13.58) are
known, no well-defined ‘silicic acid’ (H4 SiO4 ) has been
established. Fig. 13.19 Ionic radii of selected ions involved in silicates.
These data can be used to rationalize cation replacements in
SiCl4 þ 4ROH  SiðORÞ4 þ 4HCl
"
ð13:58Þ silicates.
Normal silica is only very slowly attacked by alkali, but
silicates are readily formed by fusion of SiO2 and metal
hydroxides, oxides or carbonates. The range of known sili- SiOSi bond angle of
1408. Figure 13.19 compares the
cates is large and they, and the aluminosilicates (see later), ionic radii of ions commonly present in silicates; the value
are extremely important, both in nature and for commercial for the ‘Si4þ ’ ion is an estimate. Since the Al3þ and Si4þ
and industrial purposes. ions are similar sizes, replacement is common and leads to
Sodium silicates of variable composition are made by the formation of aluminosilicates. If Al3þ replaces Si4þ ,
heating sand (which is impure quartz containing, e.g., however, an extra singly charged cation must be present to
iron(III) oxide) with Na2 CO3 at
1600 K. If the sodium maintain electrical neutrality. Thus, in the feldspar ortho-
content is high (Na :Si
3.2–4 :1), the silicates are water- clase, KAlSi3 O8 , the anion [AlSi3 O8 ] is readily recognized
soluble and the resulting alkaline solution (water glass) as being related to SiO2 (i.e. [AlSi3 O8 ] is isoelectronic
contains ions such as [SiO(OH)3 ] and [SiO2 (OH)2 ]2 ; with Si4 O8 ) and [AlSi3 O8 ] possesses the structure of
water glass is used commercially in detergents where it quartz with one-quarter of the Si replaced by aluminium;
controls the pH and degrades fats by hydrolysis. If the Na the Kþ ions occupy cavities in the relatively open lattice.
content is low, the silicate ions consist of large polymeric Double replacements are also common, e.g. {Naþ þ Si4þ }
species and their Naþ salts are insoluble in water. Equilibrium replaced by {Ca2þ þ Al3þ } (look at the radii comparisons
between the different species is attained rapidly at pH>10, in Figure 13.19).
and more slowly in less alkaline solutions. The overwhelming majority of silicates have structures
The Earth’s crust is largely composed of silica and silicate based on SiO4 tetrahedra (13.17) which, by sharing O atoms,
minerals, which form the principal constituents of all rocks assemble into small groups such as 13.18, cyclic motifs, infinite
and of the sands, clays and soils that result from degradation chains, infinite layers or infinite three-dimensional networks.
of rocks. Most inorganic building materials are based on Sharing an atom only involves corners of tetrahedra; sharing
silicate minerals and include natural silicates such as sand- an edge would bring two O2 ions too close together.
stone, granite and slate, as well as manufactured materials –O
such as cement, concrete and ordinary glass. The latter is –O O–
manufactured by fusing together limestone, sand and Si
Na2 CO3 . Clays are used in the ceramics industry and mica
= O
as an electrical insulator. Fibrous asbestos once had exten-
sive use in heat- and fire-resistant materials, but the health
risks associated with the inhalation of asbestos fibres are Si
–O O–
now well established and alternative heat- and fire-proofing O–
materials are replacing asbestos (see Box 13.9). We discuss
(13.18)
uses of zeolites later in the section.
It is universal practice to describe silicates in terms of a Of the metal ions most commonly occurring in silicates,
purely ionic model. However, although we might write the coordination numbers with respect to O2 ions are: 4
Si4þ , the 4þ charge is unlikely on ionization energy for Be2þ , 4 or 6 for Al3þ , 6 for Mg2þ , Fe3þ or Ti4þ , 6 or 8
grounds and is incompatible with the commonly observed for Naþ , and 8 for Ca2þ .
 Black plate (371,1)

Chapter 13 . Oxides, oxoacids and hydroxides 371

APPLICATIONS

Box 13.9 The rise and fall of fibrous asbestos

In the commercial market, the term asbestos covers fibrous friction products including brake linings. The dramatic
forms of the minerals actinolite, amosite, anthophyllite, downturn in the use of asbestos is associated with its severe
chrysotile, crocidolite and tremolite. The ability of the health risks: the respiratory disease asbestosis is caused by
fibres to be woven along with their heat resistance and high the inhalation of asbestos fibres by workers constantly
tensile strength led to widespread applications of asbestos exposed to them. Strict legislation controls the use of
in fire-proofing materials, brake linings, prefabricated asbestos, and demolition or renovation of old buildings
boards for construction, roofing tiles and insulation. As the often reveals large amounts of asbestos, which can be
graph below shows, world production of asbestos was at a cleared only under qualified specialists. The decline in the
peak in the mid-1970s and has since declined. Most of the production and use of asbestos is set to continue as further
asbestos mined nowadays is chrysotile, and continuing restrictive legislation is passed.
applications are largely in roofing materials, gaskets and

[Data: US Geological Survey]

Further reading B. Fubini and C. Otero Areán (1999) Chemical Society

Reviews, vol. 28, p. 373 – ‘Chemical aspects of the toxicity
I. Fenoglio, M. Tomatis and B. Fubini (2001) Chemical of inhaled mineral dusts’.
Communications, p. 2182 – ‘Spontaneous polymerisation For information from the Environmental Protection Agency
on amphibole asbestos: relevance to asbestos removal’. on asbestos, see: http://www.epa.gov/asbestos/

Figure 13.20 illustrates the structures of some silicate If the SiO4 tetrahedra sharing two corners form an infinite
anions; [Si2 O7 ]6 is shown in structure 13.18. The simplest chain, the Si :O ratio is 1 :3 (Figure 13.20). Such chains are
silicates contain the [SiO4 ]4 ion and include Mg2 SiO4 present in CaSiO3 (b-wollastonite) and CaMg(SiO3 )2
(olivine) and the synthetic b-Ca2 SiO4 (which is an important (diopside, a member of the pyroxene group of minerals
constituent of cement, setting to a hard mass when finely which possess [SiO3 ]n 2n chains). Although infinite chains
ground and mixed with water). The mineral thortveitite, are present in these minerals, the relative orientations of the
Sc2 Si2 O7 (a major source of scandium), contains discrete chains are different. Asbestos consists of a group of fibrous
[Si2 O7 ]6 ions. The cyclic ions [Si3 O9 ]6 and [Si6 O18 ]12 minerals, some of which (e.g. Ca2 Mg5 (Si4 O11 )2 (OH)2 , tremo-
occur in Ca3 Si3 O9 (a-wollastonite) and Be3 Al2 Si6 O18 lite) contain the double-chain silicate [Si4 O11 ]n 6n shown in
(beryl) respectively, while [Si4 O12 ]8 is present in the Figures 13.20 and 13.22. More extended cross-linking of
synthetic salt K8 Si4 O12 . Short-chain silicates are not chains produces layer structures of composition [Si2 O5 ]2 ;
common, although [Si3 O10 ]8 occurs in a few rare minerals. ring sizes within the layers may vary. Such sheets occur
Cage structures have been observed in some synthetic in micas and are responsible for the characteristic cleavage
silicates and two examples are shown in Figure 13.21. of these minerals into thin sheets. Talc, characterized by
 Black plate (372,1)

372 Chapter 13 . The group 14 elements

–O
O–

–
O O– O–
–O Si
–
O O
O O–
Si –
O O–
Si Si
O– O O
Si – O–
O O
O O O
Si Si Si
–O
–
O –
O O–
Si Si O–
O– – Si Si O O –O
O O–
O Si O O
–O O– –
O Si O–
–O O–
–
O O–

[SiO4]4– [Si3O9]6– [Si4O12]8– [Si6O18]12–

[SiO3]n2n–

[Si4O11]n6n–

Fig. 13.20 Schematic representations of the structures of selected silicates. Conformational details of the rings are omitted. In the
polymeric structures, each tetrahedron represents an SiO4 -unit as shown in structure 13.17. (See also Figure 13.22.)

its softness, has the composition Mg3 (Si2 O5 )2 (OH)2 ; include orthoclase, celsian, albite and anorthite. In feldspars,
Mg2þ ions are sandwiched between composite layers the holes in the structure that accommodate the cations are
each containing [Si2 O5 ]2 sheets and [OH] ions, and the quite small. In zeolites, the cavities are much larger and
assembly can be represented by the sequence can accommodate not only cations but also molecules such
 
{Si2 O2 2þ 2
5 }{OH }{Mg }3 {OH }{Si2 O5 }. This is electrically as H2 O, CO2 , MeOH and hydrocarbons. Commercially
neutral, allowing talc to cleave readily in a direction parallel and industrially, zeolites (both natural and synthetic) are
to the sandwich. A consequence of this cleavage is that talc extremely important. The Al : Si ratio varies widely among
is used as a dry lubricant, e.g. in personal care preparations. zeolites; Al-rich systems are hydrophilic and their ability to
Infinite sharing of all four oxygen atoms of the SiO4 take up H2 O leads to their use as laboratory drying agents
tetrahedra gives a composition SiO2 (see earlier) but partial (molecular sieves). Different zeolites contain different-sized
replacement of Si by Al leads to anions [AlSin O2n þ 2 ] , cavities and channels, permitting a choice of zeolite to
[Al2 Sin O2n þ 2 ]2 etc. Minerals belonging to this group effect selective molecular adsorption. Silicon-rich zeolites
include orthoclase (KAlSi3 O8 ), albite (NaAlSi3 O8 ), anorthite are hydrophobic. Catalytic uses of zeolites (see Sections
(CaAl2 Si2 O8 ) and celsian (BaAl2 Si2 O8 ). Feldspars are 26.6 and 26.7) are widespread, e.g. the synthetic zeolite
aluminosilicate salts of Kþ , Naþ , Ca2þ or Ba2þ and consti- ZSM-5 with composition Nan [Aln Si96  n O192 ]
16H2 O
tute an important class of rock-forming minerals; they (n < 27) catalyses benzene alkylation, xylene isomerization
 Black plate (373,1)

Chapter 13 . Oxides, oxoacids and hydroxides 373

Fig. 13.21 The structures, elucidated by X-ray diffraction, of (a) [Si8 O20 ]8 , determined for the salt [Me4 N]8 [Si8 O20 ] 65H2 O
[M. Wiebcke et al. (1993) Microporous Materials, vol. 2, p. 55], and (b) [Si12 O30 ]12 , determined for the salt
K12 [a-cyclodextrin]2 [Si12 O30 ] 36H2 O [K. Benner et al. (1997) Angew. Chem., Int. Ed. Engl., vol. 36, p. 743]. The silicon atoms in
(a) and (b) define a cube and hexagonal prism respectively. Colour code: Si, purple; O, red.

and conversion of methanol to hydrocarbons (for motor Oxides, hydroxides and oxoacids of
fuels). Figure 13.23 illustrates the cavities present in zeolite germanium, tin and lead
H-ZSM-5.† Electrical neutrality upon Al-for-Si replacement
can also be achieved by converting O to a terminal OH The dioxides of Ge, Sn and Pb are involatile solids. Germa-
group. These groups are strongly acidic, which means that nium dioxide closely resembles SiO2 , and exists in both
such zeolites are excellent ion-exchange (see Section 10.6) quartz and rutile forms. It dissolves in concentrated HCl
materials and have applications in, for example, water puri- forming [GeCl6 ]2 and in alkalis to give germanates. While
fication and washing powders (see Section 11.7). these are not as important as silicates, we should note that
many silicates do possess germanate analogues, but there
Zeolites are crystalline, hydrated aluminosilicates that are germanates that, at present, have no silicate counterparts
possess framework structures containing regular channels (e.g. the product of reaction 13.59).
and/or cavities; the cavities contain H2 O molecules and
molten
cations (usually group 1 or 2 metal ions). 5GeO2 þ 2Li2 O  Li4 ½Ge5 O12 
"
ð13:59Þ
Relatively few open-framework germanates (i.e. with
structures related to those of zeolites) are known, although
this is a developing area.‡ Although Si and Ge are both
group 14 elements, the structural building-blocks in silicates
are more restricted than those in germanates. Whereas
silicates are composed of tetrahedral SiO4 -units (Figures
13.20–13.23), the larger size of Ge allows it to reside in
GeO4 (tetrahedral), GeO5 (square-based pyramidal or

†
Zeolites are generally known by acronyms that reflect the research or
Fig. 13.22 Part of one of the double chains of general industrial companies of origin, e.g. ZSM stands for Zeolite Socony
formula [Si4 O11 ]n 6n present in the mineral tremolite. Mobil.
Compare this representation with that in Figure 13.20. Each ‡
See for example: M. O’Keefe and O.M. Yaghi (1999) Chemistry – A
red sphere represents an O atom, and each tetrahedral O4 -unit European Journal, vol. 5, p. 2796; L. Beitone, T. Loiseau and G. Férey
surrounds an Si atom. (2002), Inorganic Chemistry, vol. 41, p. 3962 and references therein.
 Black plate (374,1)

374 Chapter 13 . The group 14 elements

(a) (b)

Fig. 13.23 The structure of H-ZSM-5 zeolite (Al0:08 Si23:92 O48 ) is typical of a zeolite in possessing cavities which can
accommodate guest molecules. (a) and (b) show two orthogonal views of the host lattice; the structure was determined by
X-ray diffraction for the zeolite hosting 1,4-dichlorobenzene [H. van Koningsveld et al. (1996) Acta Crystallogr., Sect. B, vol. 52,
p. 140]. Colour code: (Si, Al), purple; O, red.

APPLICATIONS

Box 13.10 Kaolin, smectite and hormite clays: from ceramics to natural absorbers

Crystalline clays (aluminosilicate minerals) are categorized paper manufacture within the US and 24% was exported
according to structure. Clays in the kaolin or china clay for the same end-use. Worldwide, 41 Mt of kaolin-type
group (e.g. kaolinite, Al2 Si2 O5 (OH)4 ) possess sheet struc- clays were produced in 2001, the major producers being the
tures with alternating layers of linked SiO4 tetrahedra and US, Uzbekistan and the Czech Republic.
AlO6 octahedra. Smectite clays (e.g. sodium montmorillonite, Smectite clays tend to be referred to as bentonite, the name
Na[Al5 MgSi12 O30 (OH)6 ]) also have layer structures, with deriving from the rock in which the clays occur; 4.3 Mt of
cations (e.g. Naþ , Ca2þ , Mg2þ ) situated between the bentonite was mined in the US in 2001, and this represented
aluminosilicate layers. Interactions between the layers are 41% of the total world production. Fuller’s earth is a general
weak, and water molecules readily penetrate the channels term used commercially to describe hormite clays; 2.9 Mt was
causing the lattice to expand; the volume of montmorillonite produced in 2001 in the US (74% of world production).
increases several times over as water is absorbed. Hormite Applications of smectite and hormite clays stem from their
clays (e.g. palygorskite) possess structures in which chains ability to absorb water, swelling as they do so. Drilling
of SiO4 tetrahedra are connected by octahedral AlO6 or fluids rely on the outstanding, reversible behaviour of
MgO6 units; these clays exhibit outstanding adsorbent and sodium montmorillonite as it takes in water: the property
absorbent properties. of thixotropy. When static, or at low drill speeds, an
Within industry and commerce, terms other than the aqueous suspension of the clay is highly viscous owing to
mineral classifications are common. Ball clay is a type of the absorption of water by lattice and the realignment of
kaolin particularly suited to the manufacture of ceramics: the charged aluminosilicate layers. At high drill speeds,
in 2001, 35% of the ball clay produced in the US was used electrostatic interactions between the layers are destroyed
for tile manufacture, 22% for sanitary ware, 14% for and the drill-fluid viscosity decreases. Fuller’s earth clays
pottery and various ceramics, 6% for refractory materials, are remarkably effective absorbents and two major
7% for other uses, and the remainder was exported. applications are in pet litter, and in granules which can be
Kaolinite (which is white and soft) is of great importance applied to minor oil spillages (e.g. at fuel stations).
in the paper industry for coatings and as a filler; of the
8.1 Mt produced in the US in 2001, 36% was consumed in [Statistical data: US Geological Survey]
 Black plate (375,1)

Chapter 13 . Oxides, oxoacids and hydroxides 375

is synthesized by a hydrothermal method (such methods

are used for both germanate and zeolite syntheses) using
the amine N(CH2 CH2 NH2 )3 to direct the assembly of the
three-dimensional network. In the solid state structure, the
protonated amine is hydrogen-bonded to the germanate
framework through NH



O interactions.

A hydrothermal method of synthesis refers to a heterogeneous

reaction carried out in a closed system in an aqueous solvent
with T > 298 K and P > 1 bar. Such reaction conditions
permit the dissolution of reactants and the isolation of
products that are poorly soluble under ambient conditions.

Germanium monoxide is prepared by dehydration of the

yellow hydrate, obtained by reaction of GeCl2 with
aqueous NH3 , or by heating Ge(OH)2 , obtained from
GeCl2 and water. The monoxide, which is amphoteric, is
not as well characterized as GeO2 , and disproportionates
Fig. 13.24 A ‘stick’ representation of part of the inorganic
at high temperature (equation 13.60).
framework of the germanate
[Ge10 O21 (OH)][N(CH2 CH2 NH3 )3 ]. The [N(CH2 CH2 NH3 )3 ]3þ 970 K
cations are not shown but reside in the largest of the cavities 2GeO  GeO2 þ Ge
"
ð13:60Þ
in the network. The structure was determined by X-ray
diffraction [L. Beitone et al. (2002) Inorg. Chem., vol. 41, Solid SnO2 and PbO2 adopt a rutile-type structure (Figure
p. 3962]. Colour code: Ge, grey; O, red. 5.21). SnO2 occurs naturally as cassiterite but can easily be
prepared by oxidation of Sn. In contrast, the formation of
trigonal bipyramidal) and GeO6 (octahedral) environments. PbO2 requires the action of powerful oxidizing agents such
Figure 13.24 shows part of the three-dimensional network of as alkaline hypochlorite on Pb(II) compounds. On heating,
the germanate [Ge10 O21 (OH)][N(CH2 CH2 NH3 )3 ] which PbO2 decomposes to PbO via a series of other oxides (equa-
contains 4-, 5- and 6-coordinate Ge atoms. The germanate tion 13.61). In the last step in the pathway, the reaction

APPLICATIONS

Box 13.11 Sensing gases

Detecting the presence of toxic gases can be carried out by Tin(IV) oxide sensors play a major role in the commercial
IR spectroscopic means, but such techniques do not lend market and can be used to detect all the following gases, but
themselves to a domestic market. Capitalizing on the n- other sensor materials include:
type semiconducting properties of SnO2 has led to its use
. ZnO, Ga2 O3 and TiO2 /V2 O5 for CH4 detection;
in gas sensors, and sensors that detect gases such as CO,
. La2 CuO4 , Cr2 O3 /MgO and Bi2 Fe4 O9 for C2 H5 OH
hydrocarbons or solvent (alcohols, ketones, esters, etc.)
vapour detection;
vapours are commercially available and are now in
. ZnO, Ga2 O3 , ZrO2 and WO3 for H2 detection;
common use in underground car parking garages, auto-
. ZnO, TiO2 (doped with Al and In) and WO3 for NOx ;
matic ventilation systems, fire alarms and gas-leak detectors.
. ZnO, Ga2 O3 , Co3 O4 and TiO2 (doped with Pt) for CO
The presence of even small amounts of the target gases
detection;
results in a significant increase in the electrical conductivity
. ZrO2 for O2 detection.
of SnO2 , and this change is used to provide a measure of the
gas concentration, triggering a signal or alarm if a pre-set
threshold level is detected. The increase in electrical conduc-
Further reading
tivity arises as follows. Adsorption of oxygen on to an SnO2
surface draws electrons from the conduction band. The W. Göpel and G. Reinhardt (1996) in Sensors Update, eds
operating temperature of an SnO2 sensor is 450–750 K H. Baltes, W. Göpel and J. Hesse, VCH, Weinheim, vol. 1,
and in the presence of a reducing gas such as CO or hydro- p. 47 – ‘Metal oxides sensors’.
carbon, the SnO2 surface loses oxygen and at the same time, J. Riegel, H. Neumann and H.-W. Wiedenmann (2002) Solid
electrons return to the conduction band of the bulk solid State Ionics, vol. 152–153, p. 783 – ‘Exhaust gas sensors for
resulting in an increase in the electrical conductivity. automotive emission control’.
Doping the SnO2 with Pd or Pt increases the sensitivity of For more information on semiconductors: see Sections 5.8
a detector. and 5.9.
 Black plate (376,1)

376 Chapter 13 . The group 14 elements

13.10 Silicones

Although silicones are organometallic compounds, they

are conveniently described in this chapter because of their
structural similarities to silicates. Hydrolysis of Men SiCl4  n
(n ¼ 1–3) might be expected to give the derivatives
Men Si(OH)4  n (n ¼ 1–3). By analogy with carbon analo-
gues, we might expect Me3 SiOH to be stable (except with
respect to dehydration at higher temperatures), but
Me2 Si(OH)2 and MeSi(OH)3 undergo dehydration to
Me2 Si¼O and MeSiO2 H respectively. However, at the
Fig. 13.25 Two views (a) from the side and (b) from beginning of Section 13.9, we indicated that an Si¼O bond
above of a part of one layer of the SnO and red PbO is energetically less favourable than two SiO bonds. As a
lattices. Colour code: Sn, Pb, brown; O, red. consequence, hydrolysis of Men SiCl4  n (n ¼ 1–3) yields
silicones which are oligomeric products (e.g. reaction 13.65)
conditions favour the decomposition of Pb3 O4 , the O2
containing the tetrahedral groups 13.19–13.21 in which
formed being removed. This is in contrast to the conditions
each O atom represents part of an SiOSi bridge. Diols
used to make Pb3 O4 from PbO (see the end of Section 13.9).
can condense to give chains (13.22) or rings (e.g. 13.23).
566 K 624 K 647 K 878 K Hydrolysis of MeSiCl3 produces a cross-linked polymer.
PbO2  Pb12 O19  Pb12 O17  Pb3 O4  PbO
" " " "

ð13:61Þ 2Me3 SiOH  Me3 SiOSiMe3 þ H2 O

"
ð13:65Þ
When freshly prepared, SnO2 is soluble in many acids (equa-
tion 13.62) but it exhibits amphoteric behaviour and also Me O
reacts with alkalis; reaction 13.63 occurs in strongly alkaline
media to give a stannate. Si Si
Me Me
þ 2
O O
SnO2 þ 6HCl  2½H3 O þ ½SnCl6 
"
ð13:62Þ Me Me
SnO2 þ 2KOH þ 2H2 O  K2 ½SnðOHÞ6 
"
ð13:63Þ (13.19) (13.20)

In contrast, PbO2 shows acidic (but no basic) properties,

forming [Pb(OH)6 ]2 when treated with alkali. Crystalline O
salts such as K2 [Sn(OH)6 ] and K2 [Pb(OH)6 ] can be isolated.
The monoxides SnO and PbO (red form, litharge) possess Si
O
layer structures in which each metal centre is at the apex of O
Me
a square-based pyramidal array (Figure 13.25). Each metal
(13.21)
centre bears a lone pair of electrons occupying an orbital
pointing towards the space between the layers, and electronic O O O
effects contribute to the preference for this asymmetric Si Si Si
structure. Litharge is the more important form of PbO, but
a yellow form also exists. While PbO can be prepared by Me Me Me Me Me Me
heating the metal in air above 820 K, SnO is sensitive to (13.22)
oxidation and is best prepared by thermal decomposition of
tin(II) oxalate; PbO can also be made by dehydrating Me Me
Pb(OH)2 . Both SnO and PbO are amphoteric, but the oxo-
anions formed from them, like those from GeO, are not well Si
characterized. Of the group 14 elements, only lead forms a O O
mixed oxidation state oxide; Pb3 O4 (red lead) is obtained by
heating PbO in an excess of air at 720–770 K, and is better Me Si Si
Me
formulated as 2PbO PbO2 . In the solid state, two Pb environ- O
Me Me
ments are present. Nitric acid reacts with Pb3 O4 (according to (13.23)
equation 13.64), while treatment with glacial acetic acid yields
Silicone polymers have a range of structures and applica-
a mixture of Pb(CH3 CO2 )2 and Pb(CH3 CO2 )4 , the latter
tions (see Box 13.12), and, in their manufacture, control of
compound being an important reagent in organic chemistry;
the polymerization is essential. The methylsilicon chlorides
the two acetate salts can be separated by crystallization.
are co-hydrolysed, or the initial products of hydrolysis are
Pb3 O4 þ 4HNO3  PbO2 þ 2PbðNO3 Þ2 þ 2H2 O
"
ð13:64Þ equilibrated by heating with H2 SO4 which catalyses the
 Black plate (377,1)

Chapter 13 . Sulfides 377

APPLICATIONS

Box 13.12 Diverse applications of silicones

Silicone products have many commercial roles. At one end of waterproofing materials, synthetic rubbers and hydraulic
the market, they are crucial ingredients in personal care fluids. Silicones tend to be viscous oils which are immiscible
products: silicones are the components of shampoos and with water, but for use in shampoos, silicones may be
conditioners that improve the softness and silkiness of dispersed in water to give emulsions.
hair, and are also used in shaving foams, toothpastes, anti- Silicones have a wide range of advantageous chemical and
perspirants, cosmetics, hair-styling gels and bath oils. At physical properties. For example, they are resistant to attack
the other end of the spectrum, silicones find very different by acids and bases, are not readily combustible, and remain
applications in silicone greases, sealants, varnishes, unchanged on exposure to UV radiation.

conversion of cyclic oligomers into chain polymers, bringing solvent which is used in the production of rayon and cello-
about redistribution of the terminal OSiMe3 groups. For phane. Carbon disulfide is insoluble in water, but is, by a
example, equilibration of HOSiMe2 (OSiMe2 )n OSiMe2 OH narrow margin, thermodynamically unstable with respect to
with Me3 SiOSiMe3 leads to the polymer hydrolysis to CO2 and H2 S. However, this reaction has a
Me3 Si(OSiMe2 )n OSiMe3 . Cross-linking, achieved by co- high kinetic barrier and is very slow. Unlike CO2 , CS2
hydrolysis of Me2 SiCl2 and MeSiCl3 , leads, after heating at polymerizes under high pressure to give a black solid with
520 K, to silicone resins that are hard and inert; tailoring the chain structure 13.24. When shaken with solutions of
the product so that it possesses a smaller degree of cross- group 1 metal sulfides, CS2 dissolves readily to give trithio-
linking results in the formation of silicone rubbers. carbonates, M2 CS3 , which contain the [CS3 ]2 ion 13.25,
the sulfur analogue of [CO3 ]2 . Salts are readily isolated,
e.g. Na2 CS3 forms yellow needles (mp 353 K). The free acid
H2 CS3 separates as an oil when salts are treated with hydro-
13.11 Sulfides chloric acid (equation 13.66), and behaves as a weak acid in
aqueous solution: pKa ð1Þ ¼ 2:68, pKa ð2Þ ¼ 8:18.
The disulfides of C, Si, Ge and Sn show the gradation in 273 K
properties that might be expected to accompany the increas- BaCS3 þ 2HCl  BaCl2 þ H2 CS3
"
ð13:66Þ
ingly metallic character of the elements. Pertinent properties S S S–
of these sulfides are given in Table 13.6. Lead(IV) is too
powerful an oxidizing agent to coexist with S2 , and PbS2 C C S C
is not known. S S
S–
Carbon disulfide is made by heating charcoal with sulfur at
(13.24) (13.25)
1200 K, or by passing CH4 and sulfur vapour over Al2 O3 at
950 K. It is highly toxic (by inhalation and absorption The action of an electric discharge on CS2 results in the
through the skin) and extremely flammable, but is an excellent formation of C3 S2 , 13.26 (compare with 13.16), a red

Table 13.6 Selected properties of ES2 (E ¼ C, Si, Ge, Sn).

Property CS2 SiS2 GeS2 SnS2

Melting point / K 162 1363 (sublimes) 870 (sublimes) 873 (dec.)

Boiling point / K 319 – – –
Appearance at 298 K Volatile liquid, White needle-like crystals White powder or Golden-yellow
foul odour crystals crystals
Structure at 298 K Linear molecule Solid state, chain‡ Three-dimensional CdI2 -type lattice
S¼C¼S S
lattice with Ge3 S3 and (see Figure 5.22)
S
S S larger rings with
Si Si Si Si shared vertices.‡
S S
S S

‡
At high pressures and temperatures, SiS2 and GeS2 adopt a b-cristobalite lattice (see Figure 5.19c).
 Black plate (378,1)

378 Chapter 13 . The group 14 elements

S C C C S S–
(13.26)
Ge
liquid which decomposes at room temperature, producing a S S
black polymer (C3 S2 )x . When heated, C3 S2 explodes. In S
contrast to CO, CS is a short-lived radical species which –S Ge Ge
S S–
decomposes at 113 K; it has, however, been observed in the Ge
upper atmosphere. S S
Several salts of the [C2 S4 ]2 anion are known (made by, –S

for example, reaction 13.67), although the free acid (an (13.28)
analogue of oxalic acid) has not been isolated.
S S– S–
½CH3 CS2  þ 2½Sx 2 –S
S–
2  2 Sn Sn Sn Sn
 ½C2 S4 
"
þ ½HS þ H2 S þ ½S2x  4  ð13:67Þ –S
S– –S S–
S
S S– S–
In [Et4 N]2 [C2 S4 ], the anion has D2d symmetry, i.e. the
(13.29) (13.30)
dihedral angle between the planes containing the two
CS2 -units is 908 (structure 13.27), whereas in
[Ph4 P]2 [C2 S4 ] 6H2 O, this angle is 79.58. It is interesting to Tin(IV) forms a number of thiostannates containing discrete
compare these structural data with those for salts of the anions, e.g. Na4 SnS4 contains the tetrahedral [SnS4 ]4 ion,
related oxalate ion, [C2 O4 ]2 . The solid state structures of and Na4 Sn2 S6 and Na6 Sn2 S7 contain anions 13.29 and
anhydrous alkali metal oxalates respond to an increase in 13.30 respectively.
the size of the metal ion. In Li2 C2 O4 , Na2 C2 O4 , K2 C2 O4 The monosulfides of Ge, Sn and Pb are all obtained by
and in one polymorph of Rb2 C2 O4 , the [C2 O4 ]2 ion is precipitation from aqueous media. Both GeS and SnS
planar. In the second polymorph of Rb2 C2 O4 and in crystallize with layer structures similar to that of black phos-
Cs2 C2 O4 , the [C2 O4 ]2 ion adopts a staggered conformation phorus (see Section 14.4). Lead(II) sulfide occurs naturally as
(as in 13.27). Oxalate salts in general tend to exhibit planar galena and adopts an NaCl lattice. Its formation as a black
anions in the solid state. The CC bond length (157 pm) is precipitate (Ksp
1030 ) is observed in the qualitative test
consistent with a single bond and indicates that the planar for H2 S (equation 13.70). The colour and very low solubility
structure is not a consequence of
-delocalization but is, of PbS suggest that it is not a purely ionic compound.
instead, a result of intermolecular interactions in the PbðNO3 Þ2 þ H2 S  "
PbS þ 2HNO3 ð13:70Þ
crystal lattice. black ppt

Pure PbS is a p-type semiconductor when S-rich, and an n-

type when Pb-rich (the non-stoichiometric nature of solids
is discussed in Section 27.2). It exhibits photoconductivity
and has applications in photoconductive cells, transistors
and photographic exposure meters.

If a material is a photoconductor, it absorbs light with the

result that electrons from the valence band are excited into
(13.27)
the conducting band; thus, the electrical conductivity
increases on exposure to light.
Silicon disulfide is prepared by heating Si in sulfur vapour.
Both the structure of this compound (Table 13.6) and the
chemistry of SiS2 show no parallels with SiO2 ; SiS2 is
instantly hydrolysed (equation 13.68). Worked example 13.7 Tin and lead sulfides

SiS2 þ 2H2 O  SiO2 þ 2H2 S

"
ð13:68Þ Calculate the solubility of PbS given that Ksp ¼ 1030 . Is
your answer consistent with the fact that PbS is shown as a
The disulfides of Ge and Sn (Table 13.6) are precipitated precipitate in reaction 13.70?
when H2 S is passed into acidic solutions of Ge(IV) and
Sn(IV) compounds. Some sulfides have cluster structures, Ksp refers to the equilibrium:
e.g. [Ge4 S10 ]4 (13.28), prepared by reaction 13.69.
PbSðsÞ Ð Pb2þ ðaqÞ þ S2 ðaqÞ
þ
Aqueous solution in presence of Cs
4GeS2 þ 2S2  ½Ge4 S10 4 "
½Pb2þ ½S2 
Ksp ¼ 1030 ¼ ¼ ½Pb2þ ½S2 
ð13:69Þ ½PbS
 Black plate (379,1)

Chapter 13 . Cyanogen, silicon nitride and tin nitride 379

½Pb2þ  ¼ ½S2  enough for them to be well-established and much studied

species.
Therefore, making this substitution in the equation for Ksp
Cyanogen, C2 N2 , is a toxic, extremely flammable gas
gives:
(mp 245 K, bp 252 K) which is liable to react explosively
½Pb2þ 2 ¼ 1030 with some powerful oxidants. Although
f H o (C2 N2 ,
298 K) ¼ þ297 kJ mol1 , pure C2 N2 can be stored for long
½Pb2þ  ¼ 1015 mol dm3
periods without decomposition. Reactions 13.71 and 13.72
Thus, the extremely low solubility means that PbS will give two syntheses of C2 N2 ; reaction 13.72 illustrates the
appear as a precipitate in reaction 13.70. pseudo-halide like nature of [CN] which is oxidized by
Cu(II) in an analogous fashion to the oxidation of I to I2 .
Self-study exercises Cyanogen is manufactured by air-oxidation of HCN over a
silver catalyst.
1. Describe the coordination environment of each Pb2þ and S2
570 K
ion in galena. [Ans. NaCl structure; see Figure 5.15] HgðCNÞ2 þ HgCl2  C2 N2 þ Hg2 Cl2
"
ð13:71Þ
13 3
2. The solubility of SnS in water is 10 mol dm . Calculate a aqueous
value for Ksp . [Ans. 1026 ] solution;

2CuSO4 þ 4NaCN  C2 N2 þ 2CuCN þ 2Na2 SO4
"

3. Lead-deficient and lead-rich PbS are p- and n-type semi- ð13:72Þ

conductors respectively. Explain the difference between these
two types of semiconductors. 116 pm
[Ans. see Figure 5.13 and accompanying discussion] N C C N
137 pm

(13.31)

Cyanogen has the linear structure 13.31 and the short CC
13.12 Cyanogen, silicon nitride and tin distance indicates considerable electron delocalization. It
nitride burns in air with a very hot, violet flame (equation 13.73),
and resembles the halogens in that it is hydrolysed by
alkali (equation 13.74) and undergoes thermal dissociation
In discussing bonds formed between the group 14 elements
to CN
at high temperatures.
and nitrogen, two compounds of particular importance
emerge: cyanogen, C2 N2 , and silicon nitride. Tin(IV) C2 N2 þ 2O2  2CO2 þ N2
"
ð13:73Þ
nitride has recently been prepared.
C2 N2 þ 2½OH  ½OCN þ ½CN þ H2 O
"
ð13:74Þ
Cyanogen and its derivatives
NH2
The CN
radical is a pseudo-halogen, i.e. its chemistry
resembles that of a halogen atom, X; it forms C2 N2 , HCN 115 pm N
N
and [CN] , analogues of X2 , HX and X . Although C2 N2 H C N
106.5 pm
and HCN are thermodynamically unstable with respect to N N
H
decomposition into their elements, hydrolysis by H2 O, and
oxidation by O2 , they and [CN] are kinetically stable (13.32) (13.33)

RESOURCES, ENVIRONMENTAL AND BIOLOGICAL

Box 13.13 Hydrogen cyanide in plant material

A number of plants and their fruits, e.g. apricot and plum sweet or bitter variety; bitter cassava contains larger
kernels, grape and apple seeds, are natural sources of quantities of cyanoglucosides which liberate HCN when
HCN. The origin of the HCN is a cyanoglucoside, amygdalin the roots are crushed or chewed. In order to render the
(a sugar derivative) which is present in the fruit stones root crop safe as a foodstuff, bitter cassava must be subjected
and seeds; hydrolysis of amygdalin releases HCN. Cassava to careful treatment of shredding, pressure and heat. A
is an important root crop grown in tropical regions as a beneficial side-effect is the natural defence that cassava has
source of starch, and, for example, it is used for the against, for example, insect pests.
production of tapioca. Cassava plants may be either a
 Black plate (380,1)

380 Chapter 13 . The group 14 elements

Hydrogen cyanide, HCN, 13.32, is an extremely toxic and

2K½OCN  2KCN þ O2
"
ð13:80Þ
flammable, colourless volatile liquid (mp 260 K, bp 299 K)
with a high dielectric constant due to strong hydrogen O C N– –O C N
bonding; it has a characteristic smell of bitter almonds.
The pure liquid polymerizes to HC(NH2 )(CN)2 and (13.34)
(H2 N)(NC)C¼C(CN)(NH2 ) mixed with higher molecular 121 pm
mass polymers, and in the absence of a stabilizer such as O C N
H3 PO4 , polymerization may be explosive. In the presence 117 pm 99 pm
of traces of H2 O and NH3 , HCN forms adenine, 13.33, H
and on reduction, gives MeNH2 . It is thought that HCN 128º
was one of the small molecules in the early atmosphere of
the Earth, and played an important role in the formation (13.35)
of many biologically important compounds. Hydrogen
Two acids can be derived from 13.34: HOCN (cyanic acid
cyanide is prepared on a small scale by adding acid to
or hydrogen cyanate) and HNCO (isocyanic acid, 13.35). It
NaCN, and industrially by reactions 13.75 and 13.76.
has been established that HOCN and HNCO are not in
Pt=Rh; equilibrium with each other. Isocyanic acid (pKa ¼ 3:66) is
12501550 K; 2 bar
2CH4 þ 2NH3 þ 3O2  2HCN þ 6H2 O "
obtained by heating urea (equation 13.81) but rapidly
ð13:75Þ trimerizes, although heating the trimer regenerates the
Pt; 14501550 K monomer.
CH4 þ NH3  HCN þ 3H2
"
ð13:76Þ
H
Many organic syntheses involve HCN, and it is of great O N O
NH2 C C
industrial importance, a large fraction going into the produc- ∆ Trimerization
O C OCNH
tion of 1,4-dicyanobutane (adiponitrile) for nylon manufac- – NH3 HN NH
NH2 ∆ C
ture, and cyanoethene (acrylonitrile) for production of
acrylic fibres. O
In aqueous solution, HCN behaves as a weak acid keto-Tautomer of
(pKa ¼ 9:31) and is slowly hydrolysed (equation 13.77). An cyanuric acid
older name for hydrocyanic acid is prussic acid.
(13.81)
HCN þ 2H2 O  ½NH4 þ þ ½HCO2 
"
ð13:77Þ

aqueous solution
The fulminate ion, [CNO] , is an isomer of the cyanate ion.
2HCN þ Na2 CO3  2NaCN þ H2 O þ CO2
" Fulminate salts can be reduced to cyanides but cannot be
ð13:78Þ prepared by oxidation of them. The free acid readily
polymerizes but is stable for short periods in Et2 O at
The neutralization of aqueous HCN by Na2 CO3 , NaHCO3 low temperature. Metal fulminates are highly explosive;
or Na[HCO2 ] generates NaCN, the most important salt of mercury(II) fulminate may be prepared by reaction 13.82
the acid. It is manufactured by reaction 13.78, and has wide- and is a dangerous detonator.
spread uses in organic chemistry (e.g. for the formation of
CC bonds); it is also used in the extraction of Ag and 2Na½CH2 NO2  þ HgCl2  HgðCNOÞ2 þ 2H2 O þ 2NaCl
"

Au. (For discussion of the extraction of Ag and Au, and ð13:82Þ

treatment of [CN] waste, see equation 22.4 and Box
22.2). At 298 K, NaCN and KCN adopt the NaCl lattice, Cl N Cl
C C
each [CN] ion freely rotating (or having random orienta- 116 pm
tions) about a fixed point in the lattice and having an Cl C N N N
163 pm C
effective ionic radius of
190 pm. At lower temperatures,
transitions to structures of lower symmetry occur, e.g. Cl
NaCN undergoes a cubic to hexagonal transition below
(13.36) (13.37)
283 K. Crystals of NaCN and KCN are deliquescent, and
both salts are soluble in water and are highly toxic. Fusion Cyanogen chloride, 13.36 (mp 266 K, bp 286 K), is prepared
of KCN and sulfur gives potassium thiocyanate, KSCN. by the reaction of Cl2 with NaCN or HCN, and readily
Mild oxidizing agents convert [CN] to cyanogen (equa- trimerizes to 13.37, which has applications in the manu-
tion 13.72) but with more powerful oxidants such as PbO facture of dyestuffs and herbicides.
or neutral [MnO4 ] , cyanate ion, 13.34, is formed (reaction
13.79). Potassium cyanate reverts to the cyanide on heating Silicon nitride
(equation 13.80).
The wide applications of silicon nitride, Si3 N4 , as a ceramic
PbO þ KCN  Pb þ K½OCN
"
ð13:79Þ and refractory material and in the form of whiskers (see
 Black plate (381,1)

Chapter 13 . Aqueous solution chemistry and salts of oxoacids of germanium, tin and lead 381

Section 27.6) justify its inclusion here. It is a white, are therefore usually acidified and complex ions are then
chemically inert amorphous powder, which can be formed likely to be present, e.g. if SnCl2 is dissolved in dilute hydro-
by reaction 13.83, or by combining Si and N2 above 1650 K. chloric acid, [SnCl3 ] forms. In alkaline solutions, the domi-
4HCl

nant species is [Sn(OH)3 ] . Extensive hydrolysis of Sn(IV)
SiCl4 þ 4NH3  SiðNH2 Þ4  SiðNHÞ2  Si3 N4
" " "
species in aqueous solution also occurs unless sufficient
ð13:83Þ acid is present to complex the Sn(IV); thus, in aqueous
The two main polymorphs, a- and b-Si3 N4 , possess similar HCl, Sn(IV) is present as [SnCl6 ]2 . In alkaline solution at
infinite chain lattices in which Si and N are in tetrahedral high pH, [Sn(OH)6 ]2 is the main species and salts of this
and approximately trigonal planar environments, respec- octahedral ion, e.g. K2 [Sn(OH)6 ], can be isolated.
tively. Recently, a denser, harder polymorph, g-Si3 N4 , has In comparison with their Sn(II) analogues, Pb(II) salts are
been obtained by high-pressure and -temperature (15 GPa, much more stable in aqueous solution with respect to
>2000 K) fabrication. This polymorph has the spinel struc- hydrolysis and oxidation. The most important soluble oxo-
ture (see Box 12.6): the N atoms form a cubic close- salts are Pb(NO3 )2 and Pb(CH3 CO2 )2 . The fact that many
packed structure in which two-thirds of the Si atoms water-insoluble Pb(II) salts dissolve in a mixture of
occupy octahedral holes and one-third occupy tetrahedral [NH4 ][CH3 CO2 ] and CH3 CO2 H reveals that Pb(II) is
holes. The oxide spinels that we discussed in Box 12.6 strongly complexed by acetate. Most Pb(II) oxo-salts are,
contained metal ions in the þ2 and þ3 oxidation states, i.e. like the halides, sparingly soluble in water; PbSO4
(AII )(BIII )2 O4 . In g-Si3 N4 , all the Si atoms are in a single (Ksp ¼ 1:8  108 ) dissolves in concentrated H2 SO4 .
(þ4) oxidation state. Another new refractory material is The Pb4þ ion does not exist in aqueous solution, and the
Si2 N2 O, made from Si and SiO2 under N2 /Ar atmosphere value of E o ðPb4þ =Pb2þ Þ given in Table 13.1 is for the half-
at 1700 K; it possesses puckered hexagonal nets of alter- reaction 13.85 which forms part of the familiar lead–acid
nating Si and N atoms, the sheets being linked by battery (see equations 13.3 and 13.4). For half-reaction
SiOSi bonds. 13.85, the fourth-power dependence of the half-cell potential
upon [Hþ ] immediately explains why the relative stabilities of
Tin(IV) nitride Pb(II) and Pb(IV) depend upon the pH of the solution (see
Section 7.2).
Tin(IV) nitride, Sn3 N4 , was first isolated in 1999 from the
PbO2 ðsÞ þ 4Hþ ðaqÞ þ 2e Ð Pb2þ ðaqÞ þ 2H2 OðlÞ
reaction of SnI4 with KNH2 in liquid NH3 at 243 K followed
by annealing the solid product at 573 K. Sn3 N4 adopts a Eo ¼ þ1:45 V ð13:85Þ
spinel-type structure, related to that of g-Si3 N4 described
Thus, for example, PbO2 oxidizes concentrated HCl to Cl2 ,
above. Tin(IV) nitride is the first nitride spinel that is
but Cl2 oxidizes Pb(II) in alkaline solution to PbO2 . It may
stable under ambient conditions.
be noted that thermodynamically, PbO2 should oxidize
water at pH ¼ 0, and the usefulness of the lead–acid battery
depends on there being a high overpotential for O2 evolution.
13.13 Aqueous solution chemistry and Yellow crystals of Pb(SO4 )2 may be obtained by electro-
lysis of fairly concentrated H2 SO4 using a Pb anode;
salts of oxoacids of germanium, however, in cold water, it is hydrolysed to PbO2 , as are
tin and lead Pb(IV) acetate and [NH4 ]2 [PbCl6 ] (see Section 13.8). The
complex ion [Pb(OH)6 ]2 forms when PbO2 dissolves in
When GeO2 is dissolved in basic aqueous solution, the concentrated KOH solution, but on dilution of the solution,
solution species formed is [Ge(OH)6 ]2 . With hydrochloric PbO2 is reprecipitated.
acid, GeO2 forms [GeCl6 ]2 . Although GeO2 is reduced by
H3 PO2 in aqueous HCl solution and forms the insoluble
Ge(OH)2 when the solution pH is increased, it is possible
to retain Ge(II) in aqueous solution under controlled Glossary
conditions. Thus, 6 M aqueous HCl solutions that contain
0.2–0.4 mol dm3 of Ge(II) generated in situ (equation
13.84) are stable for several weeks. The following terms were introduced in this chapter.
Do you know what they mean?
GeIV þ H2 O þ H3 PO2  H3 PO3 þ GeII þ 2Hþ
"
ð13:84Þ q catenation
Table 13.1 lists standard reduction potentials for the M4þ / q metastable
2þ
M and M2þ /M (M ¼ Sn, Pb) couples. The value of q Zintl ion
E ðSn4þ =Sn2þ Þ ¼ þ0:15 V shows that Sn(II) salts in
o
q pyrophoric
aqueous solution are readily oxidized by O2 . In addition, q piezoelectric
hydrolysis of Sn2þ to species such as [Sn2 O(OH)4 ]2 and q hydrothermal
[Sn3 (OH)4 ]2þ is extensive. Aqueous solutions of Sn(II) salts q photoconductor