THE GROUP14 ELEMENTS (CARBON GROUP)

Carbon is the first member of group 14 or IVA of the periodic table. It consists of five elements
carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). Carbon and silicon are nonmetals,
germanium is metalloid and tin and lead are metals.

Electronic configuration
Elements Electronic configuration ( ns 2 np 2 )
6C 1s 2 , 2 s 2 2 p 2 or [He ] 2 s 2 2 p 2

14 Si 1 s 2 , 2 s 2 2 p 6 ,3 s 2 3 p 2 or [ Ne ] 3 s 2 3 p 2

32 Ge 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 2 or [ Ar ] 3 d 10 4 s 2 4 p 2

50 Sn 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 6 4 d 10 ,5 s 2 5 p 2 or [Kr ] 4 d 10 5 s 2 5 p 2

82 Pb 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 6 4 d 10 4 f 14 ,5 s 2 5 p 6 5 d 10 ,6 s 2 6 p 2 or [ Xe ] 4 f 14 5 d 10 6 s 2 6 p 2

Physical properties
(1) Non-metallic nature : The non-metallic nature decreases along the group.
C Si Ge Sn Pb
Non-metal metalloid metal metal or semi metal

(2) Abundance: Carbon and silicon are most abundant elements in earth’s crust whereas
germanium occurs only as traces. Tin and lead also occur in small amounts. Only carbon occurs in
free state as coal, diamond and graphite and in combined state as carbonates, CO2 petroleum and
natural gas Silicon is the second most abundant element after oxygen in earth’s crust in form of
silicates and silica. Germanium found in traces in coal and in certain deposits. It is important
constituent for making conductors and transistors The important ore of tin is tin stone (SnO 2) or
cassiterite. Lead is found is form of galena (PbS), anglesite (PbSO4) and cerussite (PbCO3) The
abundance ratio in earth’s crust is given below,
Element C Si Gs Sn Pb
Abundance in earth’s crust (ppm) 320 277200 7 40 16

(3) Density: The density of these elements increases down the group as reported below
Element C Si Ge Sn Pb
Density (g/ml) 3.51 (for diamond) 2.34 5.32 7.26 11.34
2.22 (for graphite)

(4) Melting point and boiling points

(i) The m.pt and b.pt. of this group members decrease down the group.
Element C Si Ge Sn Pb
m.pt(K) 4373 1693 1218 505 600
b.pt.(K) – 3550 3123 2896 2024
(ii) The m.pt and b.pt of group 14 elements are however, higher than their corresponding group 13
elements. This is due to the formation of four covalent bonds on account of four electrons in their
valence shells which results in strong binding forces in between their atoms in solid as well as in
liquid state.

(5) Atomic radii and atomic volume

(i) Both atomic radii and atomic volume increases gradually on moving down the group due to the
effect of extra shell being added from member to member.
C Si Ge Sn Pb
Atomic radius (pm) 0.77 111 122 141 144
Atomic volume (ml) 3.4 11.4 13.6 16.3 18.27
(ii) The atomic radii of group 14 elements are less than their corresponding group 13 elements due
to increase in nuclear charge in the same period.
(iii) Some of the ionic radii involving six co-ordination of these group elements are given below,
C Si Ge Sn Pb
2+
Ionic radius (M ) in pm – – 73 118 119
++
Ionic radius (M ) in pm – 40 53 69 78

(6) Electronegativity : The electronegativity decreases from C to Si and then becomes constant.
C Si Ge Sn Pb
Electronegativity on pauling scale 2.5 1.8 1.8 1.7 1.6

The electronegativity from silicon onwards is almost constant or shows a comparatively smaller
decreases due to screening effects of d10 electrons in elements from Ge onwards.
(7) Ionisation energy
(i) The ionisation energy decreases regularly down the group; Pb however shows a higher value
than Sn due to poor shielding of inner f-orbitals as a result of which effective nuclear charge
experienced by outer shell electrons becomes more in Pb.

Ionisation energy (kJ mol-1) C Si Ge Sn Pb

IE1 1086 786 761 708 715
IE2 2352 1577 1537 1411 1450
IE3 4620 3284 3300 2942 3081
IE4 6220 4354 4409 3929 4082
(ii) The first ionisation energies of group 14 elements are higher than their corresponding group 13
elements because of smaller size.
(iii) The electropositive character of these elements increases down the group because of decreases
in ionisation energy.

(8) Oxidation state

(i) Presence of four electrons in outermost shell of these elements reveals that the members of
this family can gain four electrons forming M4+ or M4- ions to show ionic nature or exhibit
tetravalent covalent nature by sharing of four electron pairs in order to attain stable
configuration.
 (ii) The formation of M4+ or M4- ions require huge amount of energy which is normally not
available during normal course of reactions, therefore, these elements usually do not form
M4+ or M4- ions, but they usually form compounds with covalence of four.
(iii) Ge, Sn and Pb also exhibit +2 oxidation state due to inert pair effect.
(iv) Sn2+ and Pb2+ show ionic nature.
(v) The tendency to form +2 ionic state increases on moving down the group due to inert pair
effect.

(9) Catenation
(i) The tendency of formation of long open or closed atom chains by the combination of same
atoms in themselves is known as catenation.
(ii) The catenation is maximum in carbon and decreases down the group.
(iii) This is due to high bond energy of catenation.
-1
Bond Bond energy in kJ mol
C-C 348
Si-Si 180
Ge-Ge 167
Sn-Sn 155
Pb-Pb No catenation

(iv) Only carbon atoms also form double or triple bonds involving p-p multiple bond within
itself.
> C = C<; – C  C –
(v) Carbon also possesses the tendency to form closed chain compounds with O,S and N atoms as
well as forming p-p multiple bonds with other elements particularly nitrogen and oxygen
e.g. C =O; C=N; CN; C=S are the functional groups present in numerous molecules due to
this reason.
(vi) Carbon can form chain containing any number of carbon atoms Si and Ge cannot extend the
chain beyond 6 atoms, while Sn and Pb do not form chains containing more than one or two
atoms.
(vii) The reason for greater tendency of carbon for catenation than other elements in the group
may further be explained by the fact that the C-C bond energy is approximately of the same
magnitude as the energies of the bond between C and other elements. On the other hand, the
Si-Si bond is weaker than the bond between silicon and other elements.
Bond Bond energy (k J/mol) Bond Bond energy (kJ/mol)
C-C 348 Si-Si 180
C-O 315 Si-O 372
C-H 414 Si-H 339
C-Cl 326 Si-Cl 360
C-F 439 Si-F 536

(10) Allotropy
(i) The phenomenon of existence of a chemical element in two or more forms differing in
physical properties but having almost same chemical nature is known as allotropy. If an
element or compound exists in two or more forms, it is also known as polymorphism e.g. zinc
blende and wurtzite are polymorphs of ZnS. This phenomenon is due to the difference either
 in the number of atoms in the molecules [as in the case of oxygen (O2) and ozone (O3)] or
arrangement of atoms in the molecules in crystal structure (as in the case of various forms of
carbon).
(ii) All the elements of group 14 except lead exhibit allotropy.
(iii) Crystalline carbon occurs mainly into two allotropic forms (i) graphite and (ii) diamond (a
third allotropic form called fullerenes e.g. C60 and C70 were recently discovered by Prof.
Richard E. Smalley and his coworkes), amorphous carbon exists in different forms viz coal,
coke, carbon black, lamp black, bone charcoal. Amorphous carbon is usually considered to
contain microcrystals of graphite.
Carbon

Crystalline Amorphous (microcrystalline)

Diamond Graphite Coal Charcoal Lamp black

The phenomenon of the existence of an element in different forms, which have different physical
properties but similar chemical properties, is known as allotropy. Such different forms of an
element are called its allotropes or allotropic forms. Carbon shows allotropy. The various
allotropic forms of carbon can be broadly classified into two classes.

(a) Crystalline form

Diamond and graphite are the two crystalline forms of carbon. Graphite is thermodynamically
more stable than diamond. Its free energy of formation is 1.9 kJ mol1 lower than that of the
diamond under standard conditions. Thus thermodynamically, diamonds should get transformed
into graphite on their own. But it does not happen at least on our lifetime scale. This is because,
this conversion is not favoured by kinetic factors, for example the activation energy for this
reaction is very high.

Structure of diamond
In diamond, the carbon atoms are arranged tetrahedrally (sp 3 hybridisation of C): each C atom is
linked to its neighbours by four single covalent bonds. This leads to a threedimensional network
of covalent bonds. It is because of this, that diamond is very hard and has high melting and boiling
points. Since, all the valence electrons of carbon are used up in forming the covalent bonds, hence
diamond does not conduct electricity.

Structure of graphite
In graphite, the carbon atoms are arranged in regular hexagons in flat parallel layers.
Each carbon in these layers is bonded to three other by sp2 covalent bonds. This gives some double
bond character to graphite. Each layer is bonded to the adjacent layers by weak Vander Waal’s
forces. As a result, each layer can slide over the other easily. It is because of this structure that
graphite is soft and slippery and can act as a lubricant. The presence of double bond character (the
presence of delocalised electrons) makes graphite a good conductor of electricity.

Difference between diamond and graphite

Diamond Graphite

Crystalline, transparent with extra brilliance. Crystalline, opaque and shiny substance
Hardest form Soft having soapy touch
Bad conductor of electricity Good conductor of electricity
3 3
High Density (3.51 g /cm ) heavy Low Density (2.25 g/cm ), lighter than diamond
Colourless Greyish white
Tetrahedral shaped Two dhnensional layer structure having regular hexagonal sheets.
3 2
sp hybridisation sp hybridization
Less stable, more energy More stable, less energy
CD  CG ; = – 0.5 k.cal CGCD at high temperature and high P
Used in cutting glass and jewellery; an abrasive Used as lubricating agent, electrodes, in pencils, crucibles
(due to high m.pt)

(b) Amorphous form:

Coal, coke, charcoal (or wood charcoal), animal charcoal (or bone black), lamp black, carbon
black, gas carbon and petroleum coke are the amorphous form of carbon.

Chemical properties

(1) Hydrides : All the elements of group 14 combine with hydrogen directly or indirectly to
form the covalent hydrides, MH 4 (M = C, Si, Ge, Sn or Pb). The number of hydrides and
the ease of preparation decrease on going from carbon to lead.
The hydrides of silicon are called silanes having the general formula Si n H 2n 2 . The
hydrides of germanium are called germanes while those of tin are called the stannanes. Only
lead forms an unstable hydride of the formula, PbH 4 called the plumbane.
Three hydrides of germanium, i.e., GeH 4 ,Ge 2 H 6 and Ge 3 H 8 and only two hydrides of tin
i.e., SnH 4 and Sn 2 H 6 are well known.
(2) Oxides : Carbon forms five oxides CO ,CO 2 ,C 3O 2 (carbon suboxide), C 5O 2 and C12O 9 ,C 3O 2
is the anhydride of malonic acid and CO 2 is the anhydride of H 2CO 3 (carbonic acid) CO 2
is a non-polar linear molecule due to maximum tendency of C to form p–p multiple bond
with oxygen. Si forms SiO 2 . Pb forms a number of oxides. PbO can be obtained by heating
Pb(NO 3 )2 , 2 Pb( NO 3 ) 2  2 PbO  4 NO 2  O 2 .
Heat
The red form of PbO is called
litharge and the yellow form is massicot. Pb3O 4 (Red lead, or Sindur) is prepared by
o
470 C
heating litharge in air at 470C, 6PbO  O 2   2Pb3O 4 , Pb3O 4 is a mixed oxide of
PbO 2 .2PbO. Pb2O 3 is called lead sesquioxide. GeO 2 , SnO 2 etc. are also network solids.
Note : SiO 2 ,GeO 2 ,SnO 2 and PbO 2 are all solids. CO 2 and SiO 2 is acidic, GeO 2 is
weakly acidic while SnO 2 and PbO 2 are amphoteric in nature. All the elements of group
14 except silicon from monoxides e.g., CO ,GeO ,SnO and PbO. Out of these monoxides
only CO is neutral, while all other monoxides are basic.
(3) Halides : Elements of group 14 react with halogens directly to form tetrahedral and covalent
halides except C where its halide is produced by the action of halogens on hydrocarbons.
PbBr4 and PbI 4 do not exist because Pb 4 is a strong oxidant and Br  and I  are strong
reductants. Hence Pb 4 ion is difficult to survive in presence of strong reductants Br  and
I  and is immediately reduced to Pb 2  .
ANOMALOUS BEHAVIOUR OF CARBON
Carbon is found to differ in many properties from the rest of the members of group 14. This is
because of the following : (i) Its smallest size (ii) Its high electronegativity (iii) Its property to
catenate (iv) Absence of d-orbitals in it.
Some of the properties in which it differs from other members are,
(1) The melting and boiling points of carbon are very high as compared to the rest to the members
of the family.
(2) Carbon in its diamond form is one of the hardest substance known.
(3) It has maximum tendency to show catenation.
(4) Carbon has high tendency to form P – P multiple bonds with other elements like nitrogen,
oxygen, sulphur etc. Other members of the family form P  – d bonds and that also to a
lesser extent.
(5) CO 2 is a gas while the dioxides of all other members are solids.
(6) Carbon shows a maximum covalency of four while other members of the family may expand
their covalency to six e.g., [SiCl 6 ]2 ,[PbCl 6 ]2 etc.
(7) Carbon is not affected by alkalies whereas other members react on fusion. For example, silicon
form silicates, Si  2 NaOH  1 / 2 O 2  Na 2 SiO 3  H 2 .
Sodium silicate

COMPOUNDS OF CARBON
Carbon monoxide

Structure of CO
Electronic structure of carbon monoxide may be represented as follows
 +
:C:::O: or C O
Preparation:
(i) By the reduction of carbon dioxide with carbon.
heat
CO2 + C 2CO
(ii) By the reduction of carbon dioxide with zinc or iron.
heat
CO2 + Zn  ZnO + CO
(iii) By the reduction of oxides of heavy metal with carbon. For example,
heat
ZnO + C  Zn + CO

(iv) By heating oxalic acid with sulphuric acid.

COOH H2SO4
CO + CO2
H2O
COOH
(v) By heating formic acid with sulphuric acid. In this reaction, sulphuric acid acts as a dehydrating
H SO , 400 K
agent. HCOOH 2 4  CO
H2O

Reactions
(i) With hydrogen
Carbon monoxide reacts with hydrogen when heated to 420670 K under 300 atm pressure and in
the presence of a catalyst (ZnO + Cu) to form methyl alcohol.
 ZnO  Cu
CO + H2 CH3 OH
420  670 K, 300 atm methyl alcohol

(ii) With chlorine

Carbon monoxide reacts with chlorine to give phosgene.
CO + Cl2  
sunlight
COCl2
phosgene (or carbonyl chloride)
CARBON DIOXIDE (CO2)
Preparation
(i) Carbon dioxide may be prepared by the complete combustion of carbon, hydrocarbons, carbon
monoxide etc.
2CO + O2(g)  2CO2(g) + Heat
CH4 + 2O2(g)  CO2(g) + 2H2O
heat
CaCO3 CaO + H2O + CO2(g)

(ii) By the action of acids on carbonates

In laboratory, carbon dioxide gas is prepared by the action of dil. HCl on marble chips (CaCO 3)
CaCO3(s) + 2HCl(dil.)  CaCl2(aq) + CO2(g) + H2O
(a) With Mg: CO2 + 2Mg  2MgO + C
(b) With Na: CO2 + 4Na  2Na2O + C

Chemical Properties:

(i) Acidic nature

CO2 dissolves in water to give carbonic acid. Therefore, carbon dioxide is called carbonic
anhydride.
CO2 + H2O H2CO3
carbon dioxide carbonic acid
Carbonic acid is a very weak dibasic acid. It ionises in aqueous solutions as,
H2CO3(aq) H+ + HCO3 (aq) K1 = 4.2  107
HCO3 (aq) H+ + CO 32 (aq) K2 = 4.8  1011
Carbonic acid being a dibasic acid forms two sets of salts, the hydrogen carbonates, HCO3 and
carbonates, CO 32 .

(ii) With lime water

When CO2 is bubbled through limewater, it turns milky due to the formation of CaCO 3. When
more CO2 is bubbled, solution becomes clear due to the formation of Ca(HCO 3)2. On boiling the
clear solution, milkiness reappears due to the formation of CaCO 3 once again.
 CO  CO
Ca(OH)2  
2
 CaCO3  
2
 Ca(HCO3)2 
heat
CaCO3
H2O H2O  CO 2
H 2 O

The reaction forms the basis of lime water test for the detection of CO 32 and HCO3 ions in any
salt/salt mixture.

Carbonic Acid
OH
O=C
OH

Carbonic acid (H2CO3) has never been isolated, but it gives rise to two series of salts, hydrogen
carbonates and carbonates.
 NaOH NaHCO3
Sodium bicarbonate
H O
H2CO3 2 (acid salt)
2NaOH

2H2O
Na2CO3
Sodium carbonate
(normal salt)

Carbonates (CO32-) and Bicarbonates (HCO3-)

Carbonic acid is dibasic acid and gives rise to two series of salts, carbonates (normal salts)
and bicarbonates (acid salts) due to successive removal of the replaceable hydrogens
from H2CO3.

H2CO3 + NaOH  NaHCO3 + H2O

These can also be prepared using the following methods

With NaOH

2NaOH + CO2  Na2CO3

Sodium carbonate

Na2CO3 + H2O + CO2  2NaHCO3

Sodium bicarbonate

By precipitation:
Heavy metal carbonates are precipitated from their salt solutions with washing soda.
BaCl2 + Na2CO3  BaCO3 + 2NaCl
While carbonates of many metals are known, bicarbonates of only alkali metals exist in the solid
state.

Haldies and Carbon

Carbon combines with all the halogens to form tetrahalides, viz, CF4, CCl4, CBr4 and Cl4, mixed
tetrahalides like CFCl3, CF2Cl2 and CCl3Br and trihalides of the formula CHX3, viz, CHCl3
(chloroform) and CHI3 (iodoform).

General characteristics
(i) The thermal stability of tetrahalides of carbon follows the order,
(ii) The tetrahalides especially those containing both fluorine and chlorine are chemically inert,
noninflammable gases or liquids.
CF4 > CCl4 > CBr4 > CI4
(iii) Freon (CF2Cl2) is used as a refrigerant.

Carbides and Sulphides

Carbides
Carbides are the binary compounds containing carbon and another less electronegative element or
of similar electronegativity. Compounds of carbon and a less electronegative element are called
carbides. This excludes compounds with N, P, O, S and the halogens from this section.

Preparation of carbides
(a) Aluminium carbide is obtained by heating aluminium with carbon in an electric furnance.
 4Al + 3C     Al4C3
electric furnace

(b) Silicon carbide is obtained by heating (sand) with carbon in an electric furnance.
SiO2 + 2C  
2300 K
SiC + 2CO(g)
(c) Calcium carbide is obtained by heating lime (CaO) with coke in a electric furnance.
CaO + 3C     CaC2 +
electric furnace
CO
2300 K

Kinds of Carbides
These are of three kinds
(1) Salt like carbides
Based on the product obtained on hydrolysis, they are further subdivided into three types.
(a) Methanide (b) Allylide (c) Acetylide
Both Be2C and Al4C3 are called methanides because they react with H2O, yielding methane.

Carbides with a C2 unit are well known. They are formed mainly by the elements in group I
I II
(M2 C 2 ) ; group II (M C2); the coinage metals (Cu, Ag, Au); Zn and Cd and some of the
lanthanides (LnC2 and Ln4(C2)3). These are all colourless ionic compounds and contain the carbide
ion (CC)2. By far the most important compound is CaC2. This is made commercially by
strongly heating lime and coke:
CaO + 3C  CaC2 + CO ; H = +466 kJ mol1
The reaction is endothermic and a temperature of 2200°C is required. These carbides react
exothermically with water, liberating ethyne (formerly called acetylene). So, they are called
acetylides.
CaC2 + 2H2O  Ca(OH)2 + HCCH
The acetylides have a NaCl type of lattice, with Ca2+ replacing Na+ and C 22 replacing Cl. In
CaC2, SrC2 and BaC2 the elongated shape of the (CC)2 ion causes tetragonal distortion of the
unit cell, that is it elongates the unit cell in one direction. One of the two carbides of magnesium
Mg2C3 contains a C3 unit and on hydrolysis with water it yields propyne CH 3CCH. So, Mg2C3 is
called allylide.
(2) Covalent carbides
These are extremely hard and chemically inert. SiC and B4C are the most important covalent
carbides. Silicon carbide is hard, infusible and chemically inert. It is widely used as an abrasive
called carborundum and about 300000 tonnes are produced annually by heating quartz or sand
with an excess of coke in an electric furnace at 20002500°C.
SiO2 + 2C  Si + 2CO
Si + C  SiC
SiC is very unreactive. It is unaffected by acids (except H 3PO4), but it does react with NaOH and
air and with Cl2 at 100°C.
SiC + 2NaOH + 2O2  Na2SiO3 + CO2 + H2O
SiC + 2Cl2  SiCl4
SiC is often dark purple, black or dark green due to traces of Fe and other impurities,
but pure samples are pale yellow to colourless. SiC has a three dimensional structure of Si and C
atoms, each atom tetrahedrally surrounded by four of the other kind .
(3) Metallic / interstitial carbides
These are formed by bigger transition elements eg.Ti and V. These are formed mostly by transition
elements and some of the lanthanides and actinides. The Cr, Mn, Fe, Co and Ni groups form a
large number of carbides with a wide range of stoichiometries. They are typically infusible or are
very high melting and are very hard. For example, TaC has a melting point of 3900°C, and is very
hard and WC is also very hard. Both are used to make cutting tools. Interstitial carbides retain
many of the properties of metals. They conduct electricity by metallic conduction and have a lustre
like a metal.

Uses of Carbides
Aluminium carbide (Al4C3) is used for the manufacture of methane. Magnesium carbide (Mg 2C3)
is used for preparing alkyne.
Al4C3 + 12H2O  4Al(OH)3 + 3CH4
Mg2C3 + 4H2O  2Mg(OH)2 + CH3CCH

Sulphides
CS2 is prepared from natural gas by the following reaction.

CH4(g) + 4S  

600 C
CS2 + 2H2S
Al2O3 / SiO 2

PREPARATION OF SILICON AND ITS REACTIONS

(1) Occurrence : Silicon is the second most abundant element ( 27.7%) in earth’s crust next to
oxygen .It does not occur in free state. It occurs mainly in the form of Silica and silicates.
Silicates are formed in rocks and clay as silicates of Mg, Al, K or Fe. e.g. Feldspar ;
K 2 Al 2 O 3 . 6 SiO 2 , Kaolinite; Al 2 O 3 . 2 SiO 2 . 2 H 2 O .
(2) Preparation : Elemental silicon is obtained by reduction of silica with high purity coke in an
electric furnace using excess of silica e.g. SiO 2  2C  Si  2CO
Very high purity silicon required for making semiconductors is obtained by reduction of highly
purified SiCl 4 form ( SiHCl 3 ) with hydrogen followed by purification by zone refining eg.
SiCl 4  2 H 2  Si  4 HCl ; SiHCl 3  H 2  Si  3 HCl
(3) Properties : Silicon exists in three isotopes 14 Si 29 (most common), 14 Si 30 with air at high
temperature SiO 2 form, Si + O 2  Si O 2 .
With steam, Si reacts when heated to redness to liberate hydrogen,
Si + 2 H 2 O   Si O 2 + 2 H 2 .
Redness

With halogens, Si reacts at elevated temperature forming SiX 4 except fluorine which reacts at
room temperature.
Silicon combines with C at 2500K forming Silicon Carbide (SiC) known as carborundum (an
extremely hard substance), Si + C   SiC.
2500 K

It reacts with metals like Ca, Mg etc in an electric arc furnace to form Silicides ( Ca 2 Si , Mg 2 Si etc.)
Silicon dissolves in hot aqueous alkalies liberating hydrogen,
Si + 4NaOH  Na 4 SiO 4  2H 2 
Heat

It also dissolves in fused Na 2 CO 3 displacing carbon Na 2 SiO 3  C .

(4) Uses of silicon : It is added to steel as ferrosilicon ( an alloy of Fe and Si) to make it acid
resistant. It is used in the pure form as a starting material for production of silicon polymers
(Silicones).
COMPOUNDS OF SILICON

Carborundum (Silicon Carbide), SiC

It is obtained when a mixture of sand, carbon, common salt and saw dust is strongly heated in an
electric furnace.
SiO2 + 3C  SiC + 2CO
Salt is added to act as flux and saw dust makes the mass porous. Two carbon rods connected by a
thin carbon core act as electrodes in the furnace. Carborundum is
formed round the central core of carbon. It is crushed, washed with H 2SO4, NaOH, H2O and then
dried.
Properties
(i) Pure carborundum is colourless, but commercial samples posses yellow, green or blue colour.
(ii) It is very hard mass. However, its hardness is less than diamond.
(iii) It is chemically inert and resists the attack of almost all the reagents except fused caustic soda.
The fused alkali dissolves it in presence of air.
4NaOH + SiC + 2O2  Na2SiO3 + Na2CO3 + 2H2O
Its structure is similar to diamond.
Uses
It is used as an abrasive instead of emery. It is used to make grinder, knife sharpeners, etc. Two
oxides of silicon SiO and SiO2 have been reported. SiO is thought to be formed by high
temperature reduction of SiO2 with Si, but its existence at room temperature is in doubt.
SiO2 + Si  2SiO
SiO2 is commonly called silica, and it is widely found as sand and quartz. Group IV elements
typically form four bonds. Carbon can form p- p double bonds and hence CO 2 is a discrete
molecule and is a gas. Silicon cannot form double bonds in this way using
pp orbitals. Thus, SiO2 forms an infinite three-dimensional structure and hence SiO2 is a high
melting solid.

Hydrolysis of SiCl4
The hydrolysis of SiCl4 is rapid because Si can use a d-orbital to form a five-coordinate
intermediate, and the reaction occurs by an SN2 mechanism.

H
Cl O
Cl Cl

Si add OH eliminate

S
Cl Cl Cl
Si
Cl HO Cl
Cl Cl
Cl
Cl
A lone pair of electrons from the oxygen is donated to an empty d orbital on Si, forming a five-
coordinate intermediate, which has a trigonal bipyramidal structure.
3s 3p 3d
Si (in excited state)
Si having gained four
electrons in SiCl4
3
sp hybridization
 SiCl4 having gained a
lone pair from –OH in
the intermediate 3
sp d hybridization
If the hydrolysis is performed on an asymmetrically substituted and consequently optically active,
silicon compound such as MeEtPhSi*Cl, then Walden inversion will occur, resulting in inversion
of the structure from d to l or vice-versa. In a similar way, the reduction of R1R2R3Si*Cl with
LiAlH4 to give R1R2R3Si*H also involves inversion of structure.

Sodium Silicate, Na2SiO3 (Water glass)

It is commercially called water glass. Chemically it is sodium metasilicate containing an excess of

silica. Its composition may vary from Na2SiO3 . SiO2 to Na2SiO3.3SiO2.

It is obtained by fusing soda ash (Na2CO3) with pure sand at a high temperature.

Na2CO3 + SiO2  Na2SiO3 + CO2 

The resulting mass is extracted with water and the solution is evaporated to get a syrupy mass
known as water glass.

Properties

It is soluble in water. The solution is alkaline due to hydrolysis.

Na2SiO3 + 2H2O 2NaOH + H2SiO3

If in a solution of sodium silicate of density 1.1, some coloured salts like cobalt nitrate, nickel
chloride, ferrous sulphate, copper sulphate, etc., are placed and whole solution is left as such for a
night, beautiful hollow tubes of metallic silicate gels possessing different colours shoot up from
these crystals and look like plants. This is called silica garden or chemical garden.

Uses: It is used

(a) in fire proofing of wood and textiles.

(b) as a preservative for eggs.

(c) as an adhesive cement for joining pieces of china clay.

(d) in the soap industry as a filler for a cheaper variety of soap.

(e) in paint industry and calico printing.

(f) for making silica gel SiO2 xH2O. When a solution of Na2SiO3 is acidified with HCl, a
gelatinous precipitate of silicic acid (H2SiO3) is slowly formed.

Na2SiO3 + 2HCl  2NaCl + H2SiO3

If most of the water is carefully removed, the jelly like precipitate of H 2SiO3 is converted into a
solid product, which is called silica gel. It possesses excellent absorption property of gases and
vapours.
Silicones
These are organosilicon polymers containing SiOSi linkages. These are formed by the
hydrolysis of alkyl or aryl substituted chlorosilanes and their subsequent polymerisation. The alkyl
or aryl substituted chlorosilanes are prepared by the reaction of Grignard reagent and silicon
tetrachloride.
RMgCl + SiCl4  RSiCl3 + MgCl2

Grignard reagent

2RMgCl + SiCl4  R2SiCl2 + 2MgCl2

3RMgCl + SiCl4  R3SiCl + 3MgCl2
R stands for –CH3, –C2H5 or –C6H5 groups.
Hydrolysis of substituted chlorosilanes yield corresponding silanols, which undergo
polymerisation.
R R
Si
O O
R R
Si Si
R O R
Cyclic silicone

R3SiCl on hydrolysis forms only a dimmer

R3Si OH + HOSiR3  R3SiOSiR3 + H2O

Properties

(i) The lower silicones are oily liquids but higher members containing long chains or ring
structures are waxy and rubber like solids.
(ii) Silicones are stable towards heat.
(iii) Chemical reagents have no action on silicones.
(iv) These are nontoxic.
(v) Viscosity of silicone oils remains the same at different temperatures.
(vi) Silicones are good electrical insulators.
(vii) These are water repellents.
Uses

(i) Silicone oils are used for high temperature oil baths, high vacuum pumps and low temperature
lubrication.
(ii) These are used in making water-proof cloth and paper by exposing cloth or paper to the
silicone vapour.
(iii) These are used as insulating materials for electric motors and other electrical appliances.
(iv) These are mixed with paints and enamels to make them resistant to the effects of high
temperature, sunlight, chemicals and damp.
(v) These are used in making Vaseline like greases, which are used as lubricants in aeroplanes.
 (vi) Siliconerubbers are useful as they retain their elasticity over a range of temperatures.

Silicates
Silicates are metal derivatives of silicic acid, H4SiO4 or Si(OH)4. Silicates are formed by heating
metal oxide or metal carbonates with sand, e.g.

Na2CO3 Fused with sand Na4SiO4, Na2(SiO3)n, etc.

SiO2

O–
O

–
O O
Si
–
O Oxygen
 – –
O O O Silicon
Plane projection of
silicate ion

Silicates have basic unit of SiO44–, each silicon atom is bonded with four oxide ions tetrahedrally.

There are following types of silicates.

(i) Orthosilicates:

These silicates contain single discrete tetrahedral unit of SiO 44–

e.g., Zircon ZrSiO4; Forsterite or Olivine Mg2SiO4
Phenacite Be2SiO4; Willemite Zn2SiO4

(ii) Pyrosilicates:
These silicates contain two units of SiO 44– joined along a corner containing oxygen atom. These
are also called as island silicate.
–O O– O– –
O

Si Si
– O –
–
O O
O–
–
O– O
–O O–
e.g., Thorteveitite Sc2Si2O7;
Hemimorphite Zn3(Si2O7) Zn(OH)2H2O)

(iii) Cyclic structure:

Cyclic or ring silicates have general formula SiO 32 n or SiO 3 n .
2n 

Structure and example of cyclic silicates containing Si 3 O 96 and Si 6 O12 

18 ions are given below.
 O–
–
O –

– –
– O O O O
– –
O O O O
– –
– – –
O O O O–
– –
O O–
–
O
(iv) Chain silicates
(a) Simple chain silicates or pyroxenes are formed by sharing two oxygen atoms by each tetrahedral.
Anions of such chain silicates have general formula (SiO 3 )n2n
– –
O O

– –

O O O O O O
– – –

O– O– O–
(b) Double chain silicates can be formed when two simple chains are joined together by shared oxygen
atoms. These minerals are called amphiboles. The anions of such silicates have general formula
(Si 4 O11 )n6n
O– O–
– –

O –
O O –
O O –O

O O O
– –
–
O O O O O O
– –

– –
O O
e.g., Synthetic silicates Li2SiO3, Na2SiO3
Spodumene LiAl(SiO3)2
Enstatite MgSiO3 ;
Diopsite CaMg(SiO3)2
Tremolite Ca2Mg5(Si4O11)2 (OH)2

(v) Two dimensional sheet silicates

In such silicates, three oxygen atoms of each tetrahedral are shared with adjacent SiO 44 –
tetrahedral units. Such sharing forms twodimensional sheet structure with general formula
(Si 2 O 5 )n2n .
 O– O–
– –

O –
O O –
O O –O

O O O
– – –
O O O O O O
– –

O O
– –

O O O O
–
O O
–

–O –O –O
e.g., Talc Mg2(Si2O5)2 Mg(OH)2
Kaolin Al2(OH)4 (Si2O5)

(vi) Three dimensional sheet silicates:

These silicates involve all four oxygen atoms in sharing with adjacent SiO 44 – tetrahedral units.
e.g. Quartz, tridymite, crystobalite, feldspar, zeolite and ultramarines .

Glass
Glass is an amorphous and transparent solid which is obtained by solidification of various silicates
and borates of potassium and calcium.
(1) Preparation : Ordinary glass is a mixture of sodium and calcium silicates and is produced by fusing
together a mixture of sodium carbonate, calcium oxide and silicon dioxide ( Silica) in a furnace at
about 1700K
Na 2 CO 3  SiO 2  Na 2 SiO 3  CO 2  ; CaO  SiO 2  CaSiO 3
On continuously heating the entire amount of CO 2 is driven out and clear viscous fused mass is
obtained. It is poured into moulds to get different types of articles, which are allowed to cool
gradually.
This typed of glass is called soda glass or soft glass which has the approximate composition,
Na 2 SiO 3 , CaSiO 3 ,4 SiO 2 .

(2) Various varieties of glass : The different varieties of glasses and their special constituents are given below,
Type of glass Constituents Special use
Soft glass Na 2 CO 3 , CaCO 3 , SiO 2 Ordinary glass for window panes, test tubes, bottles, etc.
Hard glass K 2CO 3 , CaCO 3 , SiO 2 For combustion tubes and chemical glassware
High refractive index glass Lead oxide, K 2 CO 3 For making lenses cut glasses
Pyrex glass Na 2 CO 3 , Al 2 O 3 , B 2 O 3 or For high quality glass apparatus cooking utensils
borax, sand
Crook’s glass K 2 CO 2 , PbCO 3 , CeO 2 , sand Absorbs ultra violet rays, for making lenses
(3) Coloured glass : Addition of transition metal compounds to glass give coloured glasses. Small
amounts of Cr(III), Mn(IV), Co(II) and Fe(III) compounds impart green, violet blue or brown
colour respectively
Compound added – Colour imparted Compound added – Colour imparted
Cobalt axide ( CoO) – Blue Chromium oxide ( Cr2 O 3 ) – Green
Cuprous oxide ( Cu 2 O ) – Red Auric chloride ( AuCl 3 ) – Ruby
Cadmium sulphide (CdS) – Lemon yellow Manganese dioxide ( MnO 2 ) – Purple

OXIDES AND CHLORIDES OF LEAD

Lead Monoxide (PbO)
It is known in two forms:
(i) a yellow powder commonly known as massicot and
(ii) a buff coloured crystalline form known as litharge.
Preparation
It is obtained by heating lead or lead sulphide in air at 300°C (massicot form). When the
temperature of oxidation is kept at 900°C, litharge is formed.
2Pb + O2  2PbO

2PbS + 3O2  2PbO + 2SO2

It is also formed by heating lead nitrate or lead carbonate.

2Pb(NO3)2  2PbO + 4NO2 + O2

PbCO3  PbO + CO2

Properties
It is insoluble in water. It is an amphoteric oxide. It dissolves both in acids and alkalies.
PbO + 2HNO3  Pb(NO3)2 + H2O

PbO + 2NaOH  Na2PbO2 + H2O

On heating in air at 470°C, it forms red lead.

6PbO + O2  2Pb3O4 (red lead)

Red Lead (Pb3O4)

Preparation
It is obtained by heating litharge at 470°C in air.
470 o C
6PbO + O2  2Pb3O4

Properties
It is a red powder, insoluble in water. When heated, it becomes almost black, but it again becomes
red on cooling. On heating above 470°C, it decomposes into PbO and O 2.
 2Pb3O4  6PbO + O2
When treated with concentrated HNO3, lead nitrate and brownish black insoluble oxide, PbO2, are
formed. This indicates that Pb3O4 is a compound oxide containing both PbO2 and PbO in the ratio
of 1 : 2.
Pb3O4 + 4HNO3  2Pb(NO3)2 + PbO2 + 2H2O
With H2SO4, it evolves oxygen,
2Pb3O4 + 6H2SO4  6PbSO4 + 6H2O + O2
It acts as an oxidising agent.
Pb3O4 + 8HCl  3PbCl2 + 4H2O + Cl2
Pb3O4 + 4C  3Pb + 4CO
Pb3O4 + 4CO  3Pb + 4CO2

Lead Chloride (PbCl2)

It is made by adding hydrochloric acid to a cold solution of lead salt.
Pb(NO3)2 + 2HCl  PbCl2 + 2HNO3
It is only slightly soluble in cold water, but appreciably soluble in hot water. It dissolves in
concentrated HCl forming a complex ion.
PbCl2 + 2HCl H2PbCl4
(Chloroplumbous acid)

Note : Most of the plumbic compound are unimportant because they decompose readily on heating
and are hydrolysed to PbO2 by even cold water. An exception is tetraethyl lead, Pb(C2H5)4, a
colourless liquid which is used as an antiknock agent in petrol.

OXIDES AND CHLORIDES OF TIN

Stannous Oxide (SnO)

Preparation
SnCl2 + 2NaOH  Sn(OH)2 + 2NaCl
Stannous chloride
Sn(OH)2    SnO + H2O
Heat in CO2 Atmosphere

SnCl2 + Na2CO3      SnO + CO2 + 2NaCl

Heat in atm of CO2

Stannous chloride

Properties:
(i) It is a dark grey or black powder. It is insoluble in water.
(ii) It is burns in air with incandescence forming stannic oxide, SnO 2.
2SnO + O2  2SnO2
(iii)It is an amphoteric oxide. It dissolves both in acids and alkalies.
SnO + 2HCl  SnCl2 + H2O
Stannous
chloride
SnO + 2NaOH  Na2SnO2 + H2O
 Sodium stannite
Stannites are known only in aqueous solutions. Stannites absorb oxygen from air and are
oxidised to stannates which are stable in nature.
2Na2SnO2 + O2  2Na2SnO3
Sodium stannate

Stannic Oxide (SnO2)

It is found in nature as Cassiterite or tin stone.
Preparation:

Sn + O2  SnO2
Sn + 4HNO3  H2SnO3 + 4NO2 + H2O

H2SnO3  SnO2 + H2O
Metastannic acid

Properties:
It is a white powder, insoluble in water. It is somewhat unreactive. However, it dissolves in
concentrated H2SO4 forming stannic sulphate.
SnO2 + 2H2SO4  Sn(SO4)2 + 2H2O
When the solution is diluted, stannic oxide is reprecipitated.
Sn(SO4)2 + 2H2O  SnO2 + 2H2SO4
It readily dissolves in alkalies forming stannates.
SnO2 + 2KOH  K2SnO3 + H2O

Stannous Chloride (SnCl2)

Preparation:

(i) Hydrated stannous chloride SnCl2.2H2O is prepared by dissolving tin in hot concentrated
hydrochloric acid and subjecting the solution to crystallisation.

Sn + 2HCl  SnCl2 + H2

Hydrated stannous chloride consists of two molecules of water as water of crystallisation

(SnCl2.2H2O).

Anhydrous salt cannot be obtained by heating the hydrated salt as it undergoes hydrolysis and a
white solid of tin hydroxy chloride is formed.

SnCl2.2H2O  Sn(OH)Cl + HCl + H2O

(ii) Anhydrous stannous chloride is formed when dry HCl gas is passed over hot tin.

Sn + 2HCl(g)  SnCl2 + H2

It can also be obtained when a mixture of Sn and calculated quantity of mercuric chloride is
heated.

Sn + HgCl2  SnCl2 + Hg

Properties:
 (i) It is a white crystalline solid. It is soluble in water, alcohol and ether.
(ii) In water, it is soon hydrolysed. However in presence of HCl (acid), hydrolysis is revered.
(iii)It forms a white precipitate with alkalies. The precipitate of stannous hydroxide, however,
dissolves in excess of alkali.
SnCl2 + 2NaOH  Sn(OH)2 + 2NaCl
Sn(OH)2 + 2NaOH  Na2SnO2 + 2H2O
Sodium stannite
(iv) It forms a dark brown precipitate of stannous sulphide on passing H 2S through its solution. The
precipitate dissolves in yellow ammonium sulphide.
SnCl2 + H2S  SnS + 2HCl
SnS + (NH4)2S2  (NH4)2SnS3
Yellow ammonium Ammonium thiostannate
sulphide
(v) It is a strong reducing agent. Few examples are given below:
(a) It reduces mercuric chloride to mercurous chloride (white ppt) and finally to metallic mercury
(dark grey or black).
2HgCl2 + SnCl2  Hg2Cl2 + SnCl4
Mercurous chloride
Hg2Cl2 + SnCl2  2Hg + SnCl4
(b) It reduces ferric salts to ferrous salts and cupric salts into cuprous salts.
2FeCl3 + SnCl2  2FeCl2 + SnCl4
2CuCl2 + SnCl2  2CuCl + SnCl4
(c) It decolourises iodine and thus can be titrated with it.
SnCl2 + 2HCl + I2  SnCl4 + 2HI
(d) Organic nitro compounds are reduced to amino compounds.
C6H5NO2 + 6HCl + 3SnCl2  C6H5NH2 + 3SnCl4 + 2H2O
Nitrobenzene Aniline
(e) It reduces gold chloride to metallic gold.
2AuCl3 + 3SnCl2  2Au + 3SnCl4
Colloidal gold
SnCl4 undergoes hydrolysis forming stannic acid which absorbs colloidal particle of gold and thus
forms purple of cassius.

Stannic Chloride (SnCl4)

Preparation:
Sn + 2Cl2  SnCl4
(fused) dry
Properties:
(i) It is a colourless fuming liquid having disagreeable smell.
(ii) It is hygroscopic and forms crystalline hydrates containing 3, 5, 6 and 8 molecules of water as
water of crystallisation. The pentahydrate SnCl4.5H2O, is known as “butter of tin” or
“oxymercurate of tin”.

(iii)It is soluble in water in which it undergoes hydrolysis.

SnCl4 + 4H2O  Sn(OH)4 + 4HCl

 It is also soluble in organic solvents showing that it is a covalent compound.

(iv) It dissolves in concentrated HCl forming chlorostannic acid. In presence of ammonium

chloride, it forms ammonium salt of this acid.

SnCl4 + 2HCl  H2SnCl6

Chlorostannic acid

SnCl4 + 2NH4Cl  (NH4)2SnCl6 (Ammonium chloro stannate)