Unit 9-1

Unit 9 The p-Block Elements

Section 9.1 The Halogens

（1）Characteristic properties of the halogens

The Group VII elements, the halogens, are reactive non-metals. They have the electronic structure
ns2 np5 for their valence shells. Halogens exist as diatomic molecules, X2. The first element in the
group, fluorine, is anomalous, just as lithium and beryllium are in Group I and II respectively. Astatine
at the bottom, is radioactive, as are francium and radium in the s-block. Not much is known about this
element except that it seems to be typical of its group as far as its chemical properties are concerned.

Element atomic electronic colour and atomic ionic radius electronegativity electron
number configuration state radius nm X- nm affinity kJmol-1
Fluorine 9 [He]2s22p5 pale yellow g. 0.072 0.136 4.0 -348
2 5
Chlorine 17 [Ne]3s 3p yellow green g. 0.099 0.181 3.0 -364
10 2 5
Bromine 35 [Ar]3d 4s 4p red brown l. 0.114 0.195 2.8 -342
Iodine 53 [Kr] violet black s. 0.133 0.216 2.5 -314
Astatine 85 [Xe] 0.140 ? 2.2 ?

1. High electronegativity and electron affinity

All halogens have high electronegativities and highly negative values of electron affinity, indicating
that they have a high tendency to attract an additional electron to complete the octet, which has extra
stability.

2. Ionic and covalent bonding in oxidation state -1

When halogens react with other elements, they can complete their octet by either gaining an
additional electron to form the halide ion, or by sharing their p electron to form a covalent bond,
depending on the electronegativity of the atom with which the halogen is bonded.
Ionic bonding
All the Group VII elements form ionic halides with electropositive metals, i.e. the alkali and alkaline
earth metals. The halogen atom, X, achieves a noble gas configuration by gaining one electron to form a
halide ion, X-, with oxidation state -1.
Covalent bonding
All the halogen atoms may achieve a noble gas electronic configuration by forming a single covalent
bond with non-metals, e.g. in the hydrogen halides, HX :
Except for fluorine, the halogens can also show covalencies of 3,5 and 7, by promoting electrons
from p orbitals into empty d orbitals in the valence shell. Iodine, for example, shows covalencies 1,3,5
and 7:
5s 5p 5p 5p 5d 5d 5d 5d 5d covalency example
1 ICl
3 ICl3
5 IF5
7 IF7
Why can fluorine atoms form only a single covalent bond whereas all the other halogens have
maximum covalencies greater then one ?
Fluorine cannot expand its octet as there are no low lying empty d-orbitals available and the energy
required to promote electrons into the third quantum shell is prohibitively high. Since it is the most
electronegative of all elements and only one of its unpaired p-orbital is available for completion of
the octet, its only possible oxidation states are limited to -1 with other atom and 0 with itself in F2 .
 Unit 9-2
（2）Variation in properties of the halogens and their compounds

1. Variations in melting and boiling points, electronegativities and electron affinities

Element atomic radius melting point boiling point electronegativity electron affinity
nm K K kJmol-1
Fluorine 0.072 53 85 4.0 -348
Chlorine 0.099 172 239 3.0 -364
Bromine 0.114 266 331 2.8 -342
Iodine 0.133 387 456 2.5 -314

(a) Describe and explain the trends in melting points and boiling points of the halogen group.
Melting points and boiling points increase down the group due to the increase in van der Waals
forces. Van der Waals forces increase as the number of electrons of a molecule increases. The
greater the number of electrons, the greater the possibility that temporary dipoles will be large, and
the stronger the attractive forces. Moreover, as the molecular size increases so the possible area of
contact between molecules increases, with a consequent increase in the attractive power of van der
Waals forces.

(b) Describe and explain the trends in electronegativity of the halogen group.
Electronegativity decreases as the group is descended. This is because the outer electrons become
progressively better shielded from the nucleus as the atomic size increases. Thus, electrons in a
covalent bond are attracted less and less to the halogen as its atomic number increases.

(c) Describe and explain the trends in electron affinity from chlorine to iodine.
Electron affinity is defined as : X(g) + e- → X-(g) E.A. = ∆H0
Electron affinity decreases numerically with increasing atomic number. This is because the outer
electrons become more shielded from the nucleus as the atomic size increases, so the tendency to
attract another electron decreases as the group is descended.

(d) Suggest a reason why the electron affinity of fluorine is anomalous.

The low value of fluorine is probably due to the repulsion between the incoming electron and the
electrons in the outer shell. This incoming electron must get closer to the shell electrons in the case
of F because of its very small size, compared to the other halogens.

(e) Consider the bond dissociation enthalpies of the halogens shown in table :
Element F-F Cl-Cl Br-Br I-I
Bond length nm 0.148 0.198 0.228 0.266
-1
Bond dissociation enthalpy kJ mol 158 242 193 151

(1) Explain the trend from chlorine to iodine.

Bond dissociation enthalpy decreases in the order Cl2, Br2, I2, owing to the increasing length of
the halogen-halogen bond. The increasing bond length is due to the increasing atomic size of
the halogen with increasing atomic number.

(2) Suggest a reason for the low bond dissociation enthalpy of fluorine.
This is probably due to the repulsion of non-bonding pairs of electrons on each fluorine atom at
each end of the F-F bond. The fluorine atoms are so small that the repulsion between these
non-bonding electrons are much greater than in the case of other halogens, because of their
closer proximity.
 Unit 9-3
2. Relative oxidizing power of halogens
When the halogens combine with metals or non-metals, they normally act as oxidizing agents :
1 X2(standard) + e → X-(aq)

The half-reaction can be separated into three stages as shown in figure :

1 X2(standard) + e X-(aq)

X(g) + e X-(g)

F Cl Br I
∆H at
0
/ kJ mol-1
79 121 97 76
Electron affinity /kJ mol-1 -348 -364 -342 -314
∆H0hyd / kJ mol-1 -457 -381 -351 -307
∆H0 / kJ mol-1 -726 -624 -596 -545
E0 /V +2.87 +1.36 +1.07 +0.54

Fluorine is the most reactive halogen and the most powerful oxidizing.
Order of oxidizing power : F2 > Cl2 > Br2 > I2

The high reactivity of fluorine is explained partly in terms of its low bond dissociation enthalpy,
which means that little energy is required to break the F-F bond in the initial stages of a reaction.
Another factor is the tendency to form strong bonds with other elements. Thus, fluorine tends to bring
out the highest oxidation states of other elements.

Reactions with iron (II) ion

The reaction between fluorine and aqueous solution of Fe2+ is unsuitable to carry out because water
is oxidized to oxygen and HF gas :
2 F2(g) + 2 H2O(l) → 4 HF(aq) + O2(g) (Traces of H2O2 and ozone are also formed.)

Chlorine and bromine will both oxidize Fe2+(aq) to Fe3+(aq) :

Cl2(aq) + 2 Fe2+(aq) → 2 Cl-(aq) + 2 Fe3+(aq)
Br2(aq) + 2 Fe2+(aq) → 2 Br-(aq) + 2 Fe3+(aq)

Iodine, however, is such a weak oxidizing agent that it cannot remove electrons from iron (II) ions to
form iron (III) ions. These observations are exactly as we might have predicted since E0 for
Fe3+(aq), Fe2+(aq) / Pt is + 0.77 V.

Reaction with sodium and phosphorus

Reactant Fluorine Chlorine Bromine Iodine
Sodium Reacts explosively Continues to burn Continues to burn Continues to burn
to form NaF in chlorine to form in vapour to form in vapour to form
NaCl NaBr NaI
Red phosphorus Ignites On heating forms Reacts Solid spontaneously
spontaneously to PCl3 and PCl5 spontaneously to forms PI3
form PF5 form PBr3
Examples: 2 Na(s) + F2(g) →
P4(s) + 6 Cl2(g) →
P4(s) + 10 Cl2(g) →
 Unit 9-4
3. Disproportionation of the halogens in alkalis
Disproportionation is a redox reaction in which one particular reactant is simultaneously oxidized
and reduced.

Fluorine
Fluorine , being the strongest oxidizing agent, will oxidize the hydroxide ions :

OF2 is unstable and at 70℃, it decomposes to liberate oxygen gas :

2 F2(g) + 4 OH-(aq) → 4 F-(aq) + O2(g) + 2 H2O(l)
70℃

Chlorine, Bromine and iodine undergo very similar reactions with alkalis.
Chlorine
With cold, dilute alkali at 15℃, chlorine disproportionates to form a mixture of chloride and
chlorate(I) ions :

At 70℃, chlorate (I) further disproportionates to form chloride and chlorate (V) ions :

Therefore, sodium chlorate (V) is obtained by passing chlorine gas into hot concentrated solution of
sodium hydroxide :

Bromine
As the decomposition of bromate (I) is rapid at 15℃, it may be made only at temperature about 0
℃ :
Br2(l) + 2 OH-(aq) → Br-(aq) + BrO-(aq) + H2O(l)
0℃
At 15℃, bromate (V) and bromide is formed by the disproportionation of bromine with alkalis :

Iodine
With iodine, decomposition of Iodate (I) occurs rapidly even at 0℃, so iodate (V) and iodide being
formed immediately upon dissolving iodine in alkali :

Stability of halate(I) ion : ClO- > BrO- > IO-

(a) The disproportionation reactions of bromine and iodine with alkalis are reversible. Bromine or
iodine can be regenerated by the reaction of the corresponding halate (V) and halide ions in acidic
medium. Write the ionic equations involved.

(b) Sodium chlorate (III) and sodium chlorate (V) are formed when chlorine dioxide is dissolved in
sodium hydroxide solution. Deduce the ionic equation for the disproportionation reaction.

(c) Potassium iodate (VII) is sufficiently powerful to oxidize Mn2+(aq) to MnO4-(aq) in acidic medium.
The resulting solution turns dark blue with the addition of starch solution. Deduce the ionic
equation.
4. Comparative study of the reactions of halide ions
 Unit 9-5
Reactions with halogens

Chlorine water Bromine water Iodine solution

Initial colour almost none orange brown
1. Colour after shaking with KI solution brown brown
I-(aq) Colour after shaking Upper layer yellow yellow
with CCl3CH3(l) lower layer violet violet
Conclusion I- oxidized I- oxidized
2. Colour after shaking with KBr solution orange unchanged
Br-(aq) Colour after shaking Upper layer almost none yellow
with CCl3CH3(l) lower layer orange brown violet
Conclusion Br- oxidized no reaction
3. Colour after shaking with KCl solution unchanged unchanged
Cl-(aq) Colour after shaking Upper layer almost none yellow
with CCl3CH3(l) lower layer orange brown violet
Conclusion no reaction no reaction
Write ionic equations for the reactions taking place.
Cl2(aq) + 2 Br-(aq) → 2 Cl-(aq) + Br2(aq) EOcell =
Cl2(aq) + 2 I-(aq) → 2 Cl-(aq) + I2(aq) EOcell =
Br2(aq) + 2 I-(aq) → 2 Br-(aq) + I2(aq) EOcell =

Reactions with silver ions

Reagent F-(aq) Cl-(aq) Br-(aq) I-(aq)

AgNO3(aq) acidified no reaction white precipitate pale yellow yellow precipitate
with HNO3(aq) of AgCl precipitate of AgBr of AgI
Solubility of AgX(s) soluble soluble slightly soluble insoluble
in excess NH3(aq)
Effect of sunlight no effect white AgCl turns pale yellow AgBr no effect
on AgX(s) purple-grey turns green-yellow

Except fluoride, an aqueous solution of halide precipitates the corresponding silver ion from silver
nitrate acidified with dilute nitric acid. Excess nitric acid must be present to prevent the precipitation of
other insoluble silver compounds such as sulphite and carbonate.
Ag+(aq) + X-(aq) → AgX(s) X = Cl, Br and I

If excess ammonia solution is added, silver chloride dissolves readily due to the formation of a
soluble and colourless complex, diamminesilver (I) ion :

Silver bromide is slightly soluble in excess ammonia solution :

The darkening effect of light on the silver chloride and silver bromide precipitates is because the
light converts some of the silver halide to small particles of metallic silver, which darkens the
precipitates.
For example, eye-glasses that darken in the sunlight contain small amounts of white, finely dispersed
silver chloride, AgCl. Exposure to sunlight converts some of the Ag+ ions to metallic silver, which is
dark. The reaction is reversible: in a dark room, AgCl is reformed and the glass becomes clear again.

Reactions with phosphoric (V) acid and sulphuric (VI) acid

 Unit 9-6

Reagent added Fluoride Chloride Bromide Iodide

1. Action of Steamy fumes Steamy fumes Steamy fumes Steamy fumes
conc. H3PO4(aq) on warming. on warming. on warming. on warming.
Suspected product HF(g) HCl(g) HBr(g) HI(g)
Confirmatory test White smoke with White smoke with White smoke with White smoke with
ammonia. ammonia. ammonia. ammonia.

2. Action of Steamy fumes on Steamy fumes in Steamy fumes in Steamy violet

conc. H2SO4(l) heating. cold. No green gas cold. Brown gas on fumes in cold. More
even on heating. warming. on warming. Bad
egg smell.
Suspected product HF(g) HCl(g) HBr(g) and Br2(g) HI(g) , I2(g) and H2S(g)
Confirmatory test White smoke with White smoke with White smoke with Violet colour in
ammonia. ammonia. Blue ammonia. CCl3CH3(l)
litmus turns red but Orange-brown
not bleached. colour in
CCl3CH3(l)

(a) List the hydrogen halides in order of decreasing ease of oxidation by concentrated sulphuric acid.
Explain the sequence using bond energy terms.
HI, HBr, HCl, HF (HI most readily oxidized).
The oxidation of a hydrogen halide by sulphuric acid can be represented by the equation :
2 H-X(g) + H2SO4(l) → X-X + SO2(g) + 2H2O(l) (except HF and HCl)

In energy terms, the difference between one halide and another lies in the differences in E(H-X)
and E(X-X). Since two H-X bonds have to be broken for each X-X bond formed, differences in
E(H-X) are more important. The group trend in E(H-X) is very pronounced; the H-I bond is the
weakest and HI is therefore most readily oxidized.

(b) Outline the laboratory preparation of each of the four hydrogen halides, HF, HCl, HBr and HI.
Preparation of HF and HCl : Both of these gases may be prepared by heating a halide salt with
concentrated sulphuric (VI) acid.
CaF2(s) + H2SO4(l) → CaSO4(s) + 2 HF(g)
NaCl(s) + H2SO4(l) → NaHSO4(s) + HCl(g)
HCl may be collected by downward delivery. HF is usually made in small quantities only and not
collected since it attacks glassware.
Preparation of HBr and HI : Both of these gases are prepared by heating the appropriate halide salt
with a non-oxidizing, non-volatile acid such as phosphoric (V) acid.
NaBr(s) + H3PO4(l) →
NaI(s) + H3PO4(l) →
Both gases may be collected by downward delivery.

(c) Explain the observations and write the equations for the reaction between conc.H2SO4(l). and
(i) bromide
Brown fumes are formed.

(ii)iodide
Violet fumes are seen and smell of bad eggs is noticed.
5. Acidic properties of hydrogen halide and the anomalous behaviour of hydrogen fluoride
 Unit 9-7

Hydrogen fluoride Hydrogen chloride Hydrogen Hydrogen iodide

bromide
Boiling point / ℃ 20 -85 -69 -35
Bond dissociation +567 +431 +366 +298
enthalpy / kJ mol-1
Acid dissociation 7 x 10-4 107 >107 >107
constant /mol dm-3

All the hydrogen halides are extremely soluble in water. The resulting solutions are strongly acidic
(except HF(aq) ) because of the reaction with water to form hydroxonium ion,
HX(g) + H2O(l) → X-(aq) + H3O+(aq)

(a) With the aid of a labelled diagram, explain why HF is a liquid at s.t.p. whereas all the other
hydrogen halides are gases.

Measurement of molar mass show that HF is associated in the liquid state, i.e. it exists as (HF)n,
where n is at least 2. This association is due to the presence of hydrogen bonds which operate
between the HF molecules.

Therefore, more energy is required to separate individual HF molecules than other hydrogen halides
molecules, and hence boiling point of HF is the greatest amongst hydrogen halides.

(b) Why is hydrofluoric acid ,HF(aq) ,a weak acid in dilute solution whereas the others are strong ?
HF(aq) + H2O(l) = F-(aq) + H3O+(aq) Ka = 7 x 10-4 mol dm-3

Hydrofluoric acid is a weak acid (only about 10% of the HF molecules ionize in 0.1 M solution) for
the following reasons :
(i) The H-F bond is very strong.
(ii) Hydrogen bonds between HF molecules make ionization more difficult.
The other hydrogen halides have weaker hydrogen-halide bonds and do not form hydrogen bonds.

(c) Amongst the three strong acids, hydrochloric acid, hydrobromic acid and hydroiodic acid, there are
small differences in acid strength. State and explain the trend which exist.

Acid strength decreases slightly in the order HI(aq) > HBr(aq) > HCl(aq) . This is mainly due to the
increase in bond enthalpy in passing from HI to HCl.

(d) Comment on the following statement.

Hydrofluoric acid forms two salts with potassium hydroxide : potassium fluoride (KF) and
potassium hydrogen difluoride (KHF2).

HF is a weak acid, i.e. it is only partially ionize into F- and H3O+. Some of the F- ions react with
HF molecules to form HF2- ions :

The HF2- ion is hydrogen bonded :

Thus, hydrofluoric acid contains two anions, F- and HF2-, and when it reacts with KOH, two salts are
formed, i.e. KF and KHF2 .
 Unit 9-8
6. Laboratory preparation of chlorine and hydrogen chloride gases

Laboratory preparation of chlorine gas :

Laboratory preparation of hydrogen chloride gas :

Section 9.2 Group IV Elements

 Unit 9-9

（1）Characteristic properties of the Group IV elements

The similarity between elements in the same family which was so obvious in Group I, II and VII is
much less apparent in Group IV. Here there is a considerable change in the character of the elements as
atomic number rises.

1. Variation in melting point and boiling point

The following table shows a list of physical properties for the elements in Group IV :

Element atomic Electronic Atomic radius Melting point Boiling point Conductivity
number configuration / nm / oC / oC
2 2
Carbon 6 [He]2s 2p 0.077 3730(d.) 4830(d.) fairly good(g.)
non-cond.(d.)
2 2
Silicon 14 [Ne]3s 3p 0.117 1410 2680 semi-cond.

Germanium 32 [Ar]3d104s24p2 0.122 937 2830 semi-cond.

Tin 50 [Kr] 0.141 232 2270 good

Lead 82 [Xe] 0.154 327 1730 good

d. = diamond g. = graphite

These changes in property are related to the increasing metallic character and the decreasing
non-metallic character as atomic number rises.

Element Electronegativity First ionization Type of structure

enthalpy / kJ mol-1
＊

C 2.5 1086 Giant covalent

Si 1.8 787 Giant covalent (similar to diamond)
Ge 1.8 760 Giant covalent (similar to diamond)
Sn 1.8 707 Giant metallic
Pb 1.8 715 Giant metallic

The structural changes from giant covalent structures in carbon and silicon to giant metallic
structures in tin and lead help to explain the changes in physical properties.

Giant covalent structures :

 Unit 9-10
In diamond, every carbon atom can be imagined to be at the center of a regular tetrahedron
surrounded by four carbon atoms whose centers are at the corners of the tetrahedron. Within the
structure, every carbon atom forms four covalent bonds by sharing electrons with each of its four nearest
neighbours. Silicon and germanium crystallize in the same giant covalent structure as diamond.

In graphite, the carbon atoms are arranged in flat, parallel layers. Each layer contains millions of
hexagonally arranged carbon atoms. Each carbon atom is covalently bonded to three other atoms in its
layer. These are formed by three of the four valence electrons of carbon, whilst the fourth electron is
delocalised over the whole layer. This delocalisation of electrons similar to that in metals results in
graphite conducting electricity and in its shiny appearance.

In the giant covalent structures of diamond, graphite, silicon and germanium, atoms are linked by
localized electrons in strong covalent bonds throughout the whole three-dimensional lattice. It is
therefore very difficult to distort a covalently bonded crystal, because this would involve breaking many
covalent bonds. Consequently, diamond, graphite, silicon and germanium have very high melting points
and very high boiling points.

Giant metallic structures :

Tin and lead have distorted close-packed metal structures. As the atoms get larger and the atomic
radius increases, the metallic bonding becomes weaker. As a result the attraction of mobile valence
electrons for the cationic lattice gets less. Hence there is a decrease in melting point and boiling point
from tin to lead.

＊ The first ionization enthalpy decreases considerably from carbon to silicon. After that, it falls
relatively little. The reason for this is that, after silicon, there is a large increase in nuclear charge.
This is associated with the filling of 'd' and 'f' sub-shells and it counterbalances the increase in atomic
radius.

2. Dissimilarity in properties of elements as illustrated by the composition of oxides and chlorides

 Unit 9-11
The most striking feature of the compounds of Group IV elements is the existence of two oxidation
states, +2 and +4. All the Group IV elements have four electrons in their outermost shell (ns2 np2), so it
is not surprising that they show a well-defined oxidation state of +4. However, none of the elements
forms an M4+ cation in its solid compounds. This is due to the high ionization enthalpies involved in
removing four successive electrons from an atom. Consequently, the bonding in the tetravalent
compounds is predominantly covalent.

Compounds of tin and lead in which the Group IV element has an oxidation state +2 are normally
regarded as ionic. In these compounds, the Sn2+ and Pb2+ ions are believed to form by loss of the two 'p'
electrons in the outer shell. The two 's' electrons remain relatively stable and unreactive in the filled 's'
sub-shell. This is sometimes referred to as the inert pair effect.

Composition of oxides of Group IV elements :

Oxides in the +4 oxidation state :

Oxide CO2 SiO2 GeO2 SnO2 PbO2

Structure simple giant covalent intermediate between giant covalent and ionic
molecular
Boiling point - 78 2590 1200 1900 decomposes on
/ oC heating
Thermal stable even high temperatures decomposes to
stability PbO

Oxides in the +2 oxidation state :

Oxide CO SiO GeO SnO PbO

Structure simple molecular predominantly ionic

Boiling point - 191 / / / 1470

/ oC
Thermal readily oxidized to dioxide stable
stability

It is interesting to consider the relative stabilities of the +2 and +4 oxidation states for the oxides of
different elements.

In carbon and silicon oxides, the +4 state is very stable relative to +2. The +2 state is rare and
easily oxidized to +4. Thus, CO reacts very exothermically to form CO2. SiO is too unstable to exsist
under normal conditions, although it has been obtained at 2000 oC.

Germanium forms oxides in both +4 and +2 states. However, GeO2 is rather stable than GeO.
GeO is readily converted to GeO2.

In tin compounds, the +4 state is only slightly more stable than the +2 state.

In lead compounds, the +2 state is more stable. PbO2 is a strong oxidizing agent, whilst PbO is
relatively stable. Thus, PbO2 can oxidize hydrochloric acid to chlorine :

Composition of chlorides of Group IV elements :

 Unit 9-12
All the elements of Group IV form tetrachlorides of formula ECl4. All tetrachlorides are volatile
covalent compounds.

Tetrachloride CCl4 SiCl4 GeCl4 SnCl4 PbCl4

Structure Simple molecular

Molecular shape : tetrahedral

Volatility Low melting point and boiling point.

All are volatile liquids at room temperature.

Thermal As the E-Cl bonds become longer and weaker down the group, the tetrachlorides
stability become less stable. Thus, CCl4, SiCl4 and GeCl4 are stable even at high temperatures.

SnCl4 decomposes on heating to form SnCl2 and Cl2.

PbCl4 decomposes readily to form PbCl2 and Cl2.

Dichloride CCl2 SiCl2 GeCl2 SnCl2 PbCl2

Structure Too unstable to exist Unstable Predominantly Predominantly

ionic; ionic;
in solution, in solution,
Sn2+ is formed. Pb2+ is formed.

（2）Silicon and silicates

 Unit 9-13
1. Uses of silicon
Occurrence :
As a tetravalent metalloid, silicon is less reactive than its chemical analog carbon. It is the second
most abundant element in the Earth's crust, making up 25.7% of it by weight. It occurs in feldspar, mica,
quartz and sand, mainly in the form of silicon dioxide (also known as silica) and silicates (compounds
containing silicon, oxygen and metals).
Major uses of silicon :
Semiconductor - Semiconductor is a special class of materials which have an electrical resistivity
between those of electrical conductors and electrical insulators. The semiconductors which are
pure elements and compounds are described as intrinsic semiconductors. Silicon is the intrinsic
semiconductor which is used for the production of the integrated circuits known as silicon chips.
Ultrapure silicon can be doped with other elements to adjust its electrical response by controlling the
number and charge (positive or negative) of current carriers. Such semiconductor is called
extrinsic semiconductor. There are two types of extrinsic semiconductors : n-type and p-type.
In n-type semiconductors, the dopants are Group V elements, such as phosphorus and antimony,
which have five electrons in the outer shell. When a dopant atom replaces an atom of silicon in the
structure, the fifth electron is supplied to the material, creating a negative charge.
In p-type semiconductors, the dopants are Group III elements, such as boron and alumjinium,
which have three electrons in the outer shell. When a dopant atom replaces a silicon atom, it forms
three electron-pair bonds with silicon atoms, but the fourth bond is incomplete : it has only one
electron. The vacancy is called an electron hole and is positively charge.
Transistors, solar cells and other semiconductor devices which are used in electronics and other
high-tech applications are often composed of the semiconductors of silicon.

Steel - Silicon is an important constituent of some steels.

Bronze - Most bronze produced is an alloy of copper and silicon.

Photonics - Silicon can be used in lasers to produce coherent light with a wavelength of 456 nm.

LCDs and solar cells - Hydrogenated amorphous silicon has shown promise in the production of
low-cost, large-area electronics in applications such as LCDs. It has also shown promise for
large-area, low-cost solar cells.

Glass - Silica from sand is a principal component of glass. Glass can be made into a great variety
of shapes and with a many different physical properties. Silica is used as a base material to make
window glass, containers, and insulators, and many other useful objects.

Construction - Silica is a major ingredient in bricks because of its low chemical activity.

Abrasives - Silicon carbide is one of the most important abrasives.

2. Bonding and structures of silicates

 Unit 9-14
Silicon and oxygen make up most of the Earth’s crust. They form the basis of a class of minerals
called silicates. All silicates and analogues are derived from the silicate ions, SiO42-. The silicon
atoms can be replaced by other metals to form analogous compounds, notably the aluminosilicates in
which aluminium atoms partially replace the silicon atoms.

(a) The builiding block of the silicate minerals

All silicate minerals are buil up from the basic unit of silicate(IV) ion, SiO42-, which hs the following
structural representations :

The Si atoms is covalently bonded to 4 oxygen atoms. Each oxygen atom possesses a formal
negative charge. Hence each tetrahedral unit has a formal charge of –4. when linked together, the
extended units are also negative charged. Presence of other metallic ions such ad Ca2+ or Mg2+ are
necessary for electrical neutrality.

The covalent Si-O bond, having a bond enthapy of 466 kJ mol-1, is particularly strong compared with
the C-C bond which has a bond enthalpy of 347 kJ mol-1. The linkage –Si-O-Si-O- is very stable and
instead of existing as discrete units of SiO42- ions, the silicates tend to form infinite chains, sheets or
networks.

(b) The silicate structures

Structure Figure Corners shared at Repeat unit Example

each tetrahedron
Tetrahedra A 0 SiO44- Olivines,
(Mg/Fe)2SiO4
Pairs of B 1 Si2O76- Thortveitite,
tetrahedra Sc2(Si2O7)
Closed rings C 2 SiO32- Beryl,
Be3Al2(Si6O18)
Infinite single D 2 SiO32- / Si2O64- Pyroxenes,
chains CaMg(Si2O6)
Infinite double E 2.5 Si4O116- Amphibole (asbestos),
Chains Ca2Mg5(Si4O11)2(OH)2
Infinite sheets F 3 Si2O52- Talc,
Mg3(Si4O10)(OH)2
Infinite G 4 SiO2 Quartz,
three-dimensional (SiO2)n
network
(i) Tetradedra / pairs of tetrahedra
SiO44- Si2O76-
 Unit 9-15

The cations are arranged around the tetrahedral units on a regular crystalline lattice.
(ii) Closed rings

(iii) Infinite single chains

(iv) Infinite double chains

Asbestos is a generic term for a group of naturally occurring hydrated silicates that can be processed
mechanically into long fibres. Asbestos refers to two kinds of minerals : amphiboles and chrysotile.
Amphibole, Ca2Mg5(Si4O11)2(OH)2, possesses the infinite double chain structure of Fig. E.
Chrysotile, Mg3Si2O5(OH)4, accounts for almost 90% of worldwide asbestos production. It has a
sheet structure of Fig. F.
Both chain and sheet structures are held together by the electrostatic attraction between the cations
and the negative silicates structures. Crystal cleavage is expected to occur along the chain direction
because the non-directional ionic links are comparatively weaker than the strong Si-O covalent bonds.
Hence asbestos minerals are fibrous.
(v) Infinite sheets
 Unit 9-16

Talc, Mg3(Si4O10)(OH)2 has structure consisting of layers and parallel infinite sheets. All of the
strong bonding interactions among the atoms occur within the layers. Two parallel infinite sheets have
the unshared oxygen atoms of the tetrahedral pointing towards each other. In the middle of this
sandwich are the magnesium and hydroxide ions, which serve to bind the two silicate sheets together.
Only weak van der Waals forces hold the sandwiches (layers) together. Thus layers can slip easily
across one another and accounts for the ease for it to be pulverized to make talcum powder, a soft and
fine powder t make one's skin feel smooth and dry.

(vi) Infinite three-dimensional network

The mineral Quartz is one form of silica. In quartz, all the four vertices of each tetrahedron are
linked to other tetrahedral. The quartz network carries no charge and there are no cations in its structure.
The three dimensional network silicates such as quartz are much harder than their linear or layer
counterparts. As the silica structure consists of a giant network of strong covalent bonds. Melting
points of quartz and silica (sand) are very high.

Example
Predict the structure of each of the following silicate minerals :
(a) Andradite, Ca3Fe2(SiO4)3

(b) Vlasovite, Na2ZnSi4O10

(c) Hardystonite, Ca2ZnSi2O7

(d) Chrysotile, Mg3Si2O5(OH)4

(c) The aluminosilicates
 Unit 9-17
Very often the silicon atoms are replaced by aluminium atoms to form the silicate analogue, the
aluminosilicates. When an aluminium atom replaces a silicon atom, it contributes only three electrons to
the bonding framework in place of the four electrons of silicon atoms. The additional required electron
is supplied by the ionization of a metal atom such as sodium or potassium.

(i) Infinite sheets

Mica belongs to a family in which one of the four silicon atoms in the structural unit of talc is
replaced by an aluminium atom and inserting a potassium atom to supply the fourth electron needed for
electrical neutrality. Mica has a composition of KMg3(AlSi3O10)(OH)2. Micas are harder than talc
and their layers slide less readily over one another. Like talc, crystals of mica cleave easily into sheets.
The cations occupy sites between the infinite sheets. The van der Waals attraction between sheets is
increased by the presence of extra ionic charge and accounts for the overall hardness of mica over talc.

(ii) Infinite three dimensional network

The feldspars, in which albite NaAlSi3O8 is an example, are the most abundant aluminosilicate
minerals in the Earth's surface. The silicon atoms and aluminium atoms occupy the centers of
interlinked tetrahedral of SiO44- and AlO45-. These tetrahedral connect at each corner to other tetrahedral
forming an intricate, three dimensional, negatively charged framework. The sodium cations sit within
the voids in this structure.

Example
Predict the structure of each of the following aluminosilicate minerals. In each case, the aluminium
atoms grouped with the silicon and oxygen in the formula substitute for Si in the tetrahedral sites.

(a) Biktatite, Li(AlSi2O6)

(b) Muscovite, KAl2(AlSi3O10)(OH)2

(c) Cordierite, Al3Mg2(AlSi5O18)

3. Daily life importance of the silicate minerals

(a) Silicates
 Unit 9-18

(i) Asbestos (Infinite double chains or infinite sheets)

Asbestos is an excellent thermal insulator that is non-combustible, acid-resistant, and

strong. In the past, it was used extensively in construction work to make cement floor
tiles, roof covers and ducts.
It can also be woven into fabric to make fire-resistant blankets.
Its use has been decreased greatly in recent years because inhalation of small asbestos
fibres during mining and manufacturing or during the removal of grayed and crumbled
building materials can cause the lung disease called asbestosis.

(ii) Talc (Infinite sheets)

The common use of talc crystals is to make talcum powder which is a soft and fine powder
to make one's skin feel smooth and dry.
Its resistance to heat and electricity makes it ideal for surfacing benches and switchboards.
It is also an important filler for paint and rubber.

(iii) Quartz (Infinite three dimensional network)

The hardness of quartz is widely made use of in construction work as sandstones.

Quartz / silica tubing are used for high temperature heating.
Quartz possesses piezoelectric property which enables it to make crystal oscillators used in
watches and electronic circuits and also as pressure sensor in electronic balances.
Quartz is also widely used in jewelry and ornamental decorations.

(b) Aluminosilicates

(i) Feldspar (Infinite three dimensional network)

In glassmaking, feldspar provides alumina for improving hardness, durability, and

resistance to chemical corrosion.
In ceramic, feldspar is used as flux, lowering the vitrifying temperature of a ceramic body
during firing and forming a glassy phase.

(ii) Mica (Infinite sheets)

Mica possesses excellent electrical insulation and is widely used in electronic products
such as capacitors, washers for transistors and radar high tension coils.
It also has excellent heat insulation and is used in soldering irons and jet engines.