VELAMMAL BODHI CAMPUS, PANCHETTI.

IVA GROUP ELEMENTS

SUB : CHEMISTRY
Introduction:
 Carbon, silicon, germanium, tin and lead are IVA group elements.
 General electronic configuration is ns2np2.
 No. of valence electrons, is 4, valency wrt ‘H’ is 4 and valency wrt
oxygen is 4.
 These elements belong to p-block and representative category.
 Carbon has two electrons in the penultimate shell, Si has 8
electrons while other elements have 18 electrons in the
penultimate shell.
Abundance:
 Carbon is the most abundant element of IVA group in plant and
animal kingdom.
 Silicon is the most abundant IVA group element in earth’s crust.
 Cassiterite is the ore of tin (SnO2)
 Galena is the ore of lead (PbS)
Atomic radius:
 Increases from carbon to lead.
Order : C < Si < Ge < Sn < Pb
 From carbon to lead, the increase in atomic radius is very high due
to higher screening effect of S and P electrons of inner shell of
silicon.
 From silicon to lead, the increase in atomic radius is comparatively
low due to the poor screening effect of inner d and f electrons .
 IVA group elements have lower atomic radii than corresponding
IIIA group elements due to higher nuclear charge of IVA group
elements.
Atomic volume:
 Increases from C to lead.
Order : C < Si < Ge < Sn < Pb
 IP: Irregular order; C > Si > Ge > Pb > Sn
 The slight increase in IP from Sn to Pb is due to lanthanide
contraction and poor screening effect of d and f-electrons.
 M.P. : Irregular order; C > Si > Ge > Pb > Sn.
 Tin and lead have very low melting points because they do not use
all the four valence electrons in metallic bonding.
 E.N. : Irregular order; C > Pb > Si = Ge = Sn.
Metallic character:
 Increases from C to Pb.
 C  non-metal; Si, Ge  semimetals; Sn, Pb  metals
 Valency : All the elements show a maximum valency, 4
Oxidation states:
 Common oxidation state is +4
 Heavy metals show +2 due to inert pair effect

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  From C to Pb, the stability of +4 oxidation state decreases and that
of +2 increases due to inert pair effect.
4+¿ ¿
4 +¿> Pb ¿
¿
¿ 4+¿> Sn
2+ ¿< Pb
2+¿ ¿
¿
2 +¿<Sn ¿
¿
 The compounds of Ge(II) are readily converted as Ge(IV)
compounds. Hence Ge(II) compounds act as good reducing agents
 The Pb(IV) compounds are readily reduced to Pb(II) compounds.
Hence Pb(IV) compounds act as good oxidising agents.
Catenation:
 Formation of long chairs due to the self linkage between identical
atoms is called catenation.
 The element with the highest catenation power is carbon.
 From carbon to lead, catenation power decreases.
 The higher catenation power of carbon is due to higher C – C –
bond energy.
Multiple bonding:
 Carbon has the highest tendency of forming multiple bonding
(double bond or triple bond). It forms stable P - P bonds.
 Si and other elements are reluctant to from P - P bonds due to
their higher atomic size.
 Due to the presence of d-orbitals generally these elements form
d - p bonds with nitrogen and oxygen atoms
Maximum covalency:
 Carbon shows a maximum covalency of 4 due to the absence of d-
orbitals.
 Si and other elements can show a maximum covalency of 6 due to
the presence of d-orbitals.
Reactivity:
 These elements are generally less reactive.
 From carbon to lead, the reactivity increases.
 Lead is more unreactive than expected due to the coating of the
protective oxide layer on its surface.
Action with air:
On heating with oxygen, these elements form corresponding oxides.
C + O2 CO2 ; Si + O2 SiO2;
Ge + O2 GeO2; 2P + O2 2PbO
 Except SiO, all monoxides like CO are also known.
Action with water:
C, Si and Ge do not react with cold water. However on strong
heating these elements liberate H2 gas from water.

 Pb is unaffected by water due to protective oxide film.

Action with acids:
 C and Si are not affected by dil. HCl.
 Ge on reacting with a steam of HCl gas, germanium chloroform is
formed.

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  Sn and Pb dissolve in dil. HCl slowly liberating H 2 gas.

(Chloroplumbous acid)
 Sn dissolves in dil. H2SO4, conc. H2SO4, dil. HNO3 and conc. HNO3.

(meta stannic acid)

 Pb is not affected by dil. H2SO4.
 Pb reacts with conc. H2SO4 but the reaction becomes slower due to
the formation of insoluble PbSO4.
 HNO3 is the best solvent for lead.

Action with alkalies:

 Carbon is not affected by alkalies.
 Si, Sn and Pb reacts slowly with cold. aq.NaOH but rapidly with
hot aq. NaOH.

Nature of hydrides:
 All elements form MH4 type covalent hydrides.
 Thermal stability decreases from CH4 to PbH4, hence reducing
nature increases from CH4 to PbH4.
 Silicon hydrides are best stable to hydrolysis.
 Silanes are more reactive than alkanes due to large size of silicon &
availability of d-orbitals in silicon.
 Mono silane on pyrolysis gives pure silicon which is used as
semiconductor.

Nature of halides:
 All elements form MX4 type covalent tetra halides.
o PbBr4 and PbI4 do not exist.
 From CX4 to PbX4 thermal stability decreases.
 From CF4 to CI4, thermal stability decreases.
 Except carbon halides, other halides are readily hydrolysed by
water due to the presence of d-orbitals.
 The tetra halides of Ge, Si, Sn and Pb are strong Lewis acids.

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  Except carbon, all other elements form di halides. Thermal
stability increases from SiX2 to PbX2 due to inert pair effect.

Nature of oxides:
 All elements form MO2 type dioxides.
 From CO2 to PbO2, the acidic nature decreases and basic character
increases.
CO2, SiO2 acidic
GeO2, SnO2, PbO2 amphoteric
 MO2 dissolves in alkali to form carbonates, silicates, germanates,
stannates and plumbates.

 They form MO type monoxides.

o SiO is least stable
o CO is neutral while SnO and PbO are amphoteric.
Compounds of carbon:
a) Carbon monoxide:
Preparation:
1) Oxalic acid or formic acid on reacting with conc. H 2SO4 gives CO.

2) Oxides of heavy metals on reduction with carbon give CO.

3) At high temperature, CO2 on reduction with carbon or zinc gives CO.

(or)
4) Carbonates of Ca, Mg (or) Ba on heating with zinc give CO.

5) Potassium ferro cyanide power on reacting with Conc. H2SO4 gives CO

 In this reaction, the intermediate compounds formed are HCN,

formic acid & NH3.
 In this reaction, instead of conc. H2SO4, dil. H2SO4 should not be
used because it gives poisonous HCN gas.
Properties:
1) It is a colourless and odour less gas, slightly soluble in water.
2) It burns with blue flame.

3) It is poisonous in nature. When it is inhaled, it reacts with

haemoglobin by which it fails to act as oxygen carrier. This
phenomenon is called ASPHYSIA.
4) It is thermally stable and neutral to litmus.
5) CO acts as good reducing agent, in the extraction of metals.

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 6) Due to the presence of lone pair, CO forms addition products.

7) It forms metal carbonyl with metals.

 In metal carbonyl oxidation state of metal is zero.

Uses :
1) It is used as a fuel in the form of water gas (CO + H 2) and produces
gas (CO + N2)
2) In the extraction of iron, it is used as reducing agent.
3) It is used in the extraction of nickel by Mond’s process.
Structure of carbon monoxide:

:C :::O: (or) :CO: (or) :C = O:

 In CO, carbon atom undergoes ‘sp’ hybridisation.
 Due to the presence of lone pair on carbon atom, CO acts as
ligand.
b) Carbon dioxide (CO2):
Preparation:
1) Carbon on complete combustion produces carbon dioxide.

2) Carbonates and bicarbonates on reacting with dil. acids liberate CO 2

gas.

3) Carbonates of less electropositive metals on heating liberate CO 2 gas.

4) Bicarbonates of all metals on heating release CO2 gas.

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 5) Lime stone on heating gives CO2 gas.

6) During fermentation of molasses, when glucose is changed to ethyl

alcohol, CO2 gas is produced.

Properties :
1) It is colourless, odour less, tasteless gas which is slightly soluble in
water.
2) It can be liquefied easily.
3) Solid form of CO2 is called dry ice, which is used as refrigerant under
the name drikold.
4) It is neither combustible nor helper of combustion. But burning
magnesium continues to burn in CO2.

5) CO2 acts as oxidising agent.

6) CO2 is acidic oxide.

i) (carbonic acid)

ii)

iii)

iv)
7) It is useful in photosynthesis.

Uses:
1) Solid CO2 is used as refrigerant.
2) The mixture 90% O2 and 10% CO2 is called carbogen, used for
artificial respiration for CO victims.
3) CO2 is used as fire extinguisher.
4) It is used solvay process and in the manufacture of white lead.
Structure of CO2:
 In CO2, carbon atom is SP hybridised.
 It is a linear molecule with zero dipolemoment.
O=C=O
 The C – O bond length is less than expected C = O bond length due
to resonance.
⨁ ⊝ ⊝ ⨁
O=C=O OC–O O–CO

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c) Carbonic acid (H2CO3):
i) CO2 dissolved in water to give carbonic acid

ii) It is a weak dibasic acid.

iii) It forms acidic salts (bicarbonates) and normal salts. (Carbonates)

iv) Except alkalimetal carbonates all other carbonates are insoluble in water.
v) The bicarbonates are soluble in water.
vi) All bicarbonates on heating produces CO2(g)

vii) In Alkalimetal carbonates only Li2CO3 decomposes of heating.

viii) All other carbonates give CO2 on heating.

ix) Both bicarbonates and carbonates liberate CO2 gas on reacting with
dilute acids.

x) Aqueous MgSO4 can distinguish carbonates and bicarbonates. Soluble

carbonates give insoluble white ppt. With aq. MgSO 4.

Bicarbonates donot give any white ppt. with cold MgSO 4 but on heating a
white ppt. forms.

(soluble)


xi) Soluble carbonates give pink colour with phenophthalien while

bicarbonates donot give pink colour with phenophthalien.

Compounds of silicon:
a) Silicon carbide (carborundum):
i) Silica on strong heating with carbon in an electric furnace gives
carborundum.

 To the reaction mixture salt is added to act as flux and saw dust is
added to make the mass porous.
ii) Pure carborundum is colourless. It is very hard mass but less harder
than diamond.
iii) It is chemically inert to all reagents but it reacts with fused caustic soda.

iv) It is used abrasive, it is used in making grindstones, knife sharpeners.

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b) Silicones:
 The organosilicon polymers containing Si – O – Si linkage are called
silicones.
 Grignard reagent on reacting with SiCl4 gives alkyl or aryl substituted
chloro silanes.

These chlorosilanes on hydrolysis give corresponding silanols.

R Cl H – OH R OH
Si + Si
R Cl H – OH R OH

These silanols on polymerisation give corresponding silicones.

 Dialkyl silandiol on polysmerisation gives linear thermoplastic
polymer.
R R R R
H – O – Si – OH + HO – Si – OH HO – Si – O – Si – OH
R R R R
 Polymerisation continues on both the ends by which the chain length
increases.
 RSiCl3 on hydrolysis gives a croslinked silicone as follows.
Cl OH
i) R – Si – Cl R – Si – OH
Cl OH

R R R
ii) HO – Si – OH + HO – Si – OH + HO – Si – OH
OH OH OH

R R R
HO – Si – O – Si – O – Si – OH
OH OH OH

R R R R R R
iii) HO – Si – O – Si – O – Si – OH -O – Si – O – Si – O – Si – O -
OH OH OH O O O
+ - O – Si – O – Si – O – Si –O -
OH OH OH R R R
HO – Si – O – Si – O – Si – OH (Cross linked silicone)
R R R

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 When water is eliminated from the terminal OH groups of linear
silicone then cyclic silicone is formed.
R R
Si
O O
R R
Si Si
O
R R
(Cyclic silicone)
 R3SiCl on hydrolysis gives only a dimer.

Properties of silicones:
i) Lower silicones are oily liquids while higher silicones are waxy
solids.
ii) Silicones are stable towards heat and non toxic .
iii) Chemical reagents have no action on silicones.
iv) These are good electrical insulators and water repellants.
v) Viscosity of silicone oils remains same at different temperatures.
Uses:
i) Silicone oils are used for high temperature oil baths, vacuum
pumps and low temperature lubrication.
ii) These are used in making waterproof clothes.
iii) These are used as insulating material in electrical devices.
iv) These are used in making Vaseline like grease.
v) Silicone rubbers are useful, because their retain their elastacity
over a wide range of temperatures.
c) Silicates:
i) Silicates are metal derivatives of silicic acid (H4SiO4)
ii) Metal oxide or metal carbonate on heating with sand gives silicate.
−¿ ¿
iii) Silicates have basic unit of SiO4 where each silicon atom is linked
with four oxide ions tetrahedrally.
iv) Silicate ion is represented as

Types of silicates:
a) Ortho silicates:
−¿ ¿
 These silicates contain single discrete unit of SiO4 .

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 Eg: Zircone (ZrSiO4), phenacate (Be2SiO4) Olivine (Mg2SiO4),
Willemite(Zn2SiO4)

b) Pyrosilicates:
−¿ ¿
 These silicates contain two units of SiO4 joined along a corners, where
an oxygen atom is common,
6−¿¿
 Basic unit is Si2 O7
Eg: Thortveitite (SC2Si2O7)
Hemimorphite (Zn3Si2O7. Zn(OH)2, H2O)

c) Cyclic silicates:
 Cyclic or ring silicates have the general formula ¿ ¿
6−¿¿ 12−¿¿
 These silicates contain Si3 O9 (or) Si6 O18 ions.
Eg : Beryl (Be3Al2Si6O18)
Benitoite (BaTiSi3O9)
Wollastonite (Ca3Si3O9)
Catapleite (Na2ZrSi3O9. 2H2O)

d) Chain silicates:
 By sharing two oxygen atoms of each tetrahedral unit chain silicates
are formed.
2 n−¿¿
 The onions of chain silicates have two general formulae, ( SiO3 )n and
6 n−¿¿
( Si 4 O11 )n .
Eg: Spodunene (LiAl(SiO3)2)
Jadeite (NaAl(SiO3)2)
Enstatite (MgSiO3)
Diopside (CaMg(SiO3)2)
Tremolite (Ca2Mg5(Si4O11)2(OH)2)

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e) Two dimensional sheet silicates:
 In these silicates three oxygen atoms of each tetrahedral unit are in
sharing.
2 n−¿¿
 General formula is ( Si 2 O5 )n
Eg: TalC (Mg(Si2O5)2. Mg(OH)2)
Kaolin (Al2(OH)4Si2O5)

f) Three dimensional sheet silicate:

 In these silicates all four oxygen atoms are in sharing.
Eg : Quartz, Tridimity, Crystobalite, Feldspar, Zeolite and
ultramarines.
Important compounds:
i) Water glass – Na2SiO3
 Carborundum  SiC
 Litharge  PbO;
Red lead (or) Minium (or) Sindhur  Pb3O4
 Sugar of lead  (CH3COO)2pb
 White lead  2pbCO3pb(OH)2
 Black lead  Graphite (C), plumbugo
 Anglesite  pbSO4
 Cerusite  pbCO3
 Lanarkite  pbO.pbSO4
 Water gas  CO + H2
 Produces gas  CO + N2
 Semi water gas  CO + H2 + N2
 Coal gas  H2 + CH4 + CO + N2 + C2H4 + C2H2 + CO2 + O2
 Natural gas  CH4 + C2H6 + C3H8 + C4H10 + N2
 Buckminster fullerene  C60

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