Group IV Elements

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GROUP IV ELEMENTS

Group IV consists of Carbon – C, Silicon – Si, Germanium – Ge, Tin – Sn and Lead –
Pb.
This is one of the groups in which the transition from non-metals, C and Si through
typical metalloid Ge, to weakly electropositive metals, Sn and Pb can be clearly seen.

Valence shell – ns2np2

Table 1: Physical properties of Group IV elements

Property C(6) Si(14) Ge(32) Sn(50) Pb(82)


Electronic [He]2s22p2 [Ne]3s23p2 [Ar]3d104s24p2 [Kr]4d105s25p2 [Xe]4f145d106s26p2
configuration
Electronegativity 2.5 1.74 2.0 1.7 1.55
IE(kJmol-1) 1st 1086 787 760 707 715
2nd 2352 1577 1534 1409 1447
3rd 4619 3230 3308 2943 3087
4th 6220 4355 4409 3821 4081

Melting pt (oC) 3550(diamond) 1410 937 232 328


Boiling pt (oC) 4827 2355 2830 2260 1744
Density (g cm-3) 3.51(diamond) 2.32 5.38 7.31 11.48
2.22(graphite)

Occurrence
Among all the elements of this group, carbon is the only one to occur in the elemental
state as diamond and graphite. Silicon is the second most abundant element in the earth’s
crust forming about 27.7%. Silicates are present in the rocks. Clays are essentially
alumino-silicates of Na and Ca. Common sand is an impure form of silica. Glass is also a
mixture of silicates. Germanium is a rare element. It occurs in traces in coal, in rare
mineral argyrodite, 4Ag2S.GeS2, in germinate, Cu3(Ge.Fe)S4, and as admixture in zinc
and tin ores. Tin occurs mainly as cassiterite or tin stone,SnO2 and Lead as galena, PbS.

General characteristic and Important features of the Group

1. Carbon and silicon are outstanding but different. Carbon forms so many organic
compounds; its chemistry is based on chains and rings of carbon atoms.
Silicon forms many silicate rocks and its chemistry is dominated by polymeric silicate
anions.
This is due to their medium atomic size and their atomic configuration, ns2np2. In sp3
hybridization, all the four electrons become equivalent. Here their coordination
number (4) is equal to the valence which gives the number of valence electrons which
an atom uses in bonding. Thus, the resulting tetrahedral structures are also very
symmetrical in their charge distribution since carbon and silicon have also medium
electronegativities.

2. The properties of Ge, Sn and Pb change gradually as the group is descended, the
metallic character increases down the group.

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3. Oxidation state or valence
They readily form tetravalent derivatives. However they show oxidn states of +2 and
+4 which are also the valencies shown by these elements, except carbon where
oxidation state varies from -4 to +4.
All compound of +4 oxdn state are covalent because the IE to form M4+ is too high to
allow the formation of such ions. The heavier elements readily form lower oxidn state
of +2; which become more ionic going down the group.
Tin(II) and its compounds are often ionic. Only carbon forms anions due to its
relatively high electronegativity, e.g., C22- in the carbides (acetylides) and C4- in
methanides.

4. Coordination number:
The maximum coordination number of carbon is four because it can never
accommodate more than 8 electrons in its valence shell. Other members can expand
the octet due to their d- orbitals. Thus, they can have higher coordination numbers and
form complex ions e.g., SiF62-, PbCl42- etc.

5. Catenation:
Is a property by virtue of which elements form long chins or rings compounds by
single or multiple bond formation between atoms of the same element.
The tendency to catenate decreases going down the group

C, Si, Ge, Sn, Pb


i.e., C> Si> Ge~ Sn> Pb
catenation decrease

Carbon shows this tendency to a remarkable extent because of its small size and high
bond energy. Si and Ge to a lesser extent and Sn and Pb to a very small extent.
E.g. Hydrides and halides
Carbon: there are alkanes e.g. ethane, propane, butane, etc.of the formular
CnH2n+2 n up to n= 100 are known.
There are also others like alkenes and alkynes etc.

Carbon also forms a number of catenated halides e.g., Polyvinylchlorides


(PVC). Their formular is
Cl

(CH2CH-)n

Silicon: forms silanes having the general formular SinH2n+2 where n 8


Its halides also catenation and have a general formular SinX2n+2
Where if X=F, n= 1- 14
X = Cl, Br or I, n = 1 – 10

Germanium: forms germanes GenH2n+2, where n = 1 – 9

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Halides form dimmers e.g., Ge2Cl6

Tin and Lead: while SnH4 & Sn2H6 have been prepared, preparation of PbH4 has failed.
No catenated halides are known for Sn and Pb

(6) Allotropy:
The existence of elements in two or more different forms. These forms are called
allotropes and the phenomenon is called allotropy.
Allotropy occurs because of different crystal structures and shapes in the solid state
and/ or combination of different numbers of atoms into molecules of simple
compounds.

Carbon:
Has two forms (allotropes) namely diamond and graphite.
They differ in their physical and chemical properties because of differences in their
arrangement and bonding of the atoms i.e. they have different structures. They are, infact,
macromolecules consisting of C atoms linked by a network of covalent bonds.

Diamond:
C

1.54Ao
C C C

C
• Diamond structure consisting of carbon atoms surrounded by a tetrahedral
arrangement of other carbon atoms at a distance of 1.54Ao. i.e. each carbon atom
is tetrahedrally surrounded by four other carbon atoms which are covalently
bonded to it.
E(C-C) bond energy = 355kJmol-1
• Each C atom displays sp3 hybridization.
• Since the structure possesses no free (mobile) electrons i.e. all valencies are
satisfied (saturated); it behaves as an insulator and it is inert.
• The rigid, strong three dimensional linkages make diamond one of the hardest
substances known.
• Since the covalent bonds must be broken before melting and boiling, it has an
extremely high m.pt (3550oC) and b.pt (4827oC).

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Graphite:

1.42Å

First layer

3.35Å

Second layer

• Graphite has a two dimensional layer structure. Its lattice consists of plane
layers or sheets in which carbon atoms are arranged in regular planar
hexagons.
• Carbon atoms are sp2 hybridized. Here each carbon atom is linked to other
three carbon atoms through 3 bonds and one electron which has a overlap.
This electron is delocalized over the whole planar layer.
• These delocalized electrons make graphite a good conductor of electricity
within the layer. Metallic lustre can also be attributed to these delocalized
electrons.
• Different layers are at a distance of 3.35Ao from each other and are thus held
by weak Van der Waals forces only. These layers can slide over one another
easily, imparting softness and slippery touch to graphite. Hence it is used as a
lubricant and in pencil.
• Due to its giant layer structure, it is very heat resistant and hence used for
crucibles.
• It is chemically very inert, thus, it is employed as an electrode material in
many electrolyses.

Silicon, Germanium & Lead:


They exhibit only one allotropic form. Si and Ge crystallize in the diamond structure
while Pb exhibit cubic closest- packed structure.

Tin:
Shows three modifications below its m.pt 232oC. They are interconvertible as shown in
the following equilibrium:

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– Sn – Sn – Sn
132oC 161oC

HYDRIDES
All the elements in group IV form covalent hydrides. The stability of the hydrides
decreases down the group because of the decreasing M–H bond energies. Thus, while
CH4 and other alkanes are stable compounds, PbH4 has not even been properly
characterised, so far.

Carbon:

Why there are so many hydrocarbons in C?


Because carbon undergoes catenation than any other element for both single and multiple
bonds i.e., C – C, C = C and C C.
This property is related to the bond strength
E.g.:
C-C = 346 kJmo-1 strong
-1
Si-Si = 226 kJmol
Ge-Ge = 186kJmol-1
-1
Sn-Sn = 151kJmol weak
Catenated Pb compounds are unknown.

The C–C bond strength is due to perfect overlap of the 2p orbitals which are also small in
size hence intensive interaction. As the group is descended i.e. from Si to Pb the elements
get larger and they possess d- orbitals. Thus, electrons partly diffuse into these vacant d-
orbitals hence weak overlap of p orbitals.
Si Ge Sn Pb

further weaker

Silicon, Tin and Lead:

There are no silicon analogues of alkenes and alkynes (e.g. C2H4, C2H2).
This is because poor overlap results from interaction of a 3p orbital of an atom of a 3rd
period element and a 2p orbital of 2nd period or of two 3p orbitals of two atoms of the 3rd
period elements.
SinH2n+2 (n 6) and GenH2n+2 (n 6) are known.

SnH4, Sn2H6 and PbH4 decompose slowly at room temperature and quickly when heated.

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HALIDES
All the elements of the group form dihalides (except carbon) and tetrahalides. All the four
tetrahalides, namely, fluorides, chlorides, bromides and iodides are known for all the
elements of the group, except PbBr4 and PbI4. Due to inert pair effect the stable oxidation
state of Pb is +2. Therefore Sn and Pb form all the dihalides.
Points to note:
• C–F, forms no complexes analogous to fluorosilicates SiF62- ions. This is
attributed to the absence of d orbitals in the valence of carbon atom. Others have d
orbitals available for coordination.
• There is steady decrease in the C–X bond energies i.e., C-F>C-Cl>C-Br>C-I. This
is because p –p overlap is weak due to size factor as you go down the group.
[Cl<Br<I Vs C]. And generally the bond strength (covalent) of M–X decreases
down the group.
• Although Si–Cl and Si–F have high bond energies yet they are very reactive. This
observation is due to high polarization of the bond, Si +–F -.
• The tetrahalides of carbon CX4 are relatively inert to hydrolysis while SiCl4 gets
readily hydrolysed to give silicic acid
SiCl4 + 4H2O Si(OH)4 + 4HCl.

FLUOROCARBONS
Fluorocarbons are the synthetic equivalents of hydrocarbons in which some or all of the
hydrogens have been replaced by fluorine atoms e.g., CF4, C2F4, C2F6, etc.
Replacement of H by F greatly increases both the thermal stability and the chemical
inertness because of the greater strength of the C–F bond and the larger size of the
fluorine compared to hydrogen atoms. The bond energy of C–F bond is 489kJmol-1
compared with C–H bond energy of 414kJmol-1.

Properties:
• Fluorocarbons are resistant to attacks by acids, alkalis, oxidizing and reducing
agents.
• Like hydrocarbons they are capable of forming carbon chains of indefinite
lengths.
• On burning, they split at C–C bond rather than at C–F bond.
• They are attacked by hot metals like molten sodium.

Teflon:
Tetrafluoroethane, C2F4, can be polymerized thermally or in aqueous emulsions to a
chemically inert plastic, “polytetrafluoroethane” (PTFE), commercially known as Teflon.

nC2F4 pressure (-CF2CF2-)n


heat

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Properties:
• Teflon has an extremely low coefficient of friction
• It is used as a protective coating in non-stick kitchen utensils, razor blades,
bearings, etc.
Freons:
Mixed chlorofluorocarbons such as CCl2F2, CFCl3 and CF3Cl are known as “Freons”.

Properties:
• They are volatile, thermally stable and chemically inert compounds with low
viscosity.
• Therefore, they are used in refrigeration, in aerosol propellants and in heat
transfer processes.
• CF3CHBrCl is a safe anaesthetic.

OXIDES

All the elements in the group form mainly mono and dioxides. The dioxides are all
thermally stable except for PbO2, the reason being an increase in stability +2 oxidation
state down the group.
Acidic character decreases down the group:

+4 +2

acidic CO2 CO weakly acidic


acidic SiO2 SiO unstable weaklybasic & neutral in character
acidic GeO2 GeO Amph
Amph SnO2 SnO Amph
Amph PbO2 PbO basic

stability decreases stability increases as +2 effect


as +4 becomes less becomes more vital.

Carbon forms multiple bonds with Oxygen while the rest form singe bonds:

C Si, Ge, Sn, Pb


CO2(gas) solids
CO(gas) solids

Why is CO2 a gas and SiO2 or SiO a solid?


O=C=O

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Bond energies
C-O 360kJmol-1
C=O 803kJmol-1
Si-O 464kJmol-1
Si=O 640kJmol-1

Carbon oxides:
CO2 is a simple linear molecule in which carbon is attached to two oxygen atoms by
means of two double bonds.
CO2 O=C=O C-O Vs C=O
-1
2(C-O) = 2x360= 720 kJmol OR 4(360) < 2(803)
E(C=O)>2E(C-O) 1440< 1606
I.e.803 > 720

Types of carbon oxide:


• Carbon dioxide CO2
• Carbon monoxide CO
• Carbon suboxide C3O2
• Carbon oxide C12O9

Carbon monoxide (CO) is a colourless and odourless gas. Because of its lack of smell, it
is very dangerous. If inhaled it forms a very stable compound, carboxyhaemoglobin, with
haemoglobin. Haemoglobin is the oxygen carrying protein in blood. Formation of
carbohaemoglobin prevents it from acting as an oxygen carrier and death eventually
occurs from asphyxia.
CO is an important reducing agent, reducing metallic oxides to the metals at high
temperatures forming carbon dioxide (CO2).
CO2 is a colourless gas with a faint smell. It can be easily liquefied by application of
pressure even at the ordinary ambient temperatures. If liquid CO2 is allowed to expand
rapidly, solid CO2 is obtained. Solid CO2 is known as dry ice. When it is used as a
refrigerant, it does not pass through the liquid phase (cf., water) Solid CO2 is also used as
a freezing mixture in organic solvents like acetone or methanol.

Silica:
Silicon dioxide, SiO2, is commonly known as silica. Its amorphous as well as crystalline
forms are known. Flint is the amorphous form of silica. The crystalline forms are quartz,
tridymite and cristobalite which have different structures. SiO2 forms a giant or
macromolecular structure in which each silicon atom is surrounded tetrahedrally by four
covalently bonded oxygen atoms and each oxygen, in turn, is bonded to two silicon
atoms. However, the overall stoichiometry or the silicon – oxygen ratio remains the same,
i.e. SiO2.

O=Si=O
2x640(Si=O) < 4x464(Si-O)
1280 << 1856
So Si-O is stable compared to O=Si=O

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Therefore, three dimensional structure is stable.
O=Si=O which is (2p-3d) is unstable. While for carbon (2p-2p) is strong compared to
(3p-2p) or (3p-3p) .

Si

Si
O O
Si
Si
O

Si

Structure of silicon dioxide

Types of Silicon oxide:


• Silica (SiO2)n
• Silicates

Anomalous behaviour of carbon

• Carbon has a maximum covalency of 4 and is not able to form complex


compounds.
• Carbon is the only element in the group to form stable derivatives with double and
triple bonds, which show special characteristics.
• Carbon forms gaseous oxides, i.e., CO and CO2 whereas others form solid oxides.
• Carbon has a much higher electronegativity and higher ionisation energy than
other elements in the group.
• Carbon has a unique capacity of catenation and forms a very large number of
stable compounds, with long chains or rings of carbon atoms, which can occur in
many isomeric forms.
• Carbon forms stronger bonds not only with itself but also with elements like
halogens, oxygen, nitrogen and sulphur than any other element in the group.

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USES

Uses of elements
Carbon:
• Diamonds are used in jewellery on account of their high refractive and dispersive
power.
• Due to their exceptionally hard nature, inferior quality diamonds are used for
industrial purposes mainly in the form of grit and powder in cutting, drilling,
grinding and polishing tools.
• Graphite electrodes are used in the extraction of aluminium. Graphite is also used
for making crucibles, as a lubricant in heavy machines and as pencil lead, etc.
Very pure graphite is used as a pure neutron moderator in nuclear reactors.
• Coke is mainly used in metallurgy.
• Carbon black is used to strengthen rubber, as a pigment in inks, paints, paper and
plastics.
• Activated carbon has enormous surface area and is used extensively in sugar
industry as a decolourising agent.

Silicon:
• Very pure silicon is used in making semiconductor devices, such as transistors
solar cells which are becoming increasingly important and microcomputer chips.
• Hyperfine Si is one of the purest materials used in the production of transistors.
Silicones are also widely used as lubricants. Their inert nature makes them ideal
for use in gas chromatography, e.g., methylphenyl silicones.

Germanium:
• Is used largely in transistors technology. However, its use in optics is growing; Ge
is transparent in infrared region and is, therefore, used in infrared windows,
prisms and lenses.

Tin:
• Due to its resistance to corrosion, tin is used to coat mild steel plate.
• Tin is also used for making various alloys like bronze, pewter, gun metal and for
solder (lead with tin), etc.

Lead:
• Is used as an inert material, e.g., for building roofs, and for cable sheathing. Lead
gets covered with a layer of PbSO4, which is insoluble and does not get attacked
by common reagent.
• Lead pipes were used in municipal water supply at one time. Soft water, however,
tends to dissolve lead and may cause lead poisoning. Therefore, galvanised iron
(GI) pipes are now used for water supply.
• Due to their low chemical reactivity, lead coated chambers are used in many
industrial preparations like that of sulphuric acid. In view of its high density, lead
is also used in making shielding blocks for radioactivity experiments.
• One of the major uses of lead still is in the storage batteries.

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Uses of compound

Carbon compounds:
• CO2 finds an important use as a fire extinguisher and in refrigeration as dry ice.

Silicon compounds:
• Silicates are used in glass and cement manufacture.

Lead compounds:
• Organolead compounds, e.g., tetraethyllead, Et4Pb and tetramethyllead, Me4Pb,
are used as antiknock additives to petrol for internal combustion engines.
However, in recent times, because of their polluting nature, many countries have
reduced or altogether stopped their use.

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