COURSE NAME

Chemistry for B.Sc. 1st Year

PAPER TITLE
Inorganic chemistry-I
Paper-I

UNIT
Unit V: p-Block Elements

TOPIC
p - Block Elements - 3

OBJECTIVES

After going through the contents of this module you should be able to,

 To study the physical and chemical properties of Group 14 elements

 To learn about the concepts like allotropy, catenation etc
 To analyze the effect of inert pair effect on the properties of Group 14
elements
 To understand the mechanism of hydrolysis of halides of the group 14
elements.

Introduction

Hello viewers, in this e-content we are going to discuss the chemistry of group 14
elements this is also called carbon family. The e-content has been divided into the
introduction of group 14 elements followed by physical characteristics or you can say
the physical properties and then by chemical properties.

 14 Group Elements
Now first of all we should take up the introduction of 14 group element. Now the
elements in this group ranges from a non-metallic carbon to the metallic tin and
lead, with the intervening element – germanium showing semi metallic behavior.
Carbon has been known from pre-history as the charcoal resulting from partial
combustion of organic matter. Carbon is an essential constituent of all living matter.
Silicon is the second most abundant element in the earth’s crust, tools made of flint,
a form of SiO2, were used in the Stone Age time.

Physical Properties
Now these are the physical characteristics of group 14 elements.

General electronic configuration

They have a general configuration of ns² np², there are four valence electrons. You
can see the configuration here with reference to noble gas. Now carbon has a
configuration of helium and 2s², 2p² that is here these are four valence electron 2s²
2p² and therefore valence electron is same in all cases for Si it is neon and 3s² 3p²
here argon we have got 4s² 4p² and so on.
Covalent Radii
You can see the covalent radii of this, it will increase down the group, carbon will
have minimum radii because as we move down the group there is additional shell
added to it and therefore the atomic radii increases.

Ionization Energy
Now ionization energy is very high. As we move across the period the ionization
energy increases and ongoing down the group it decreases. So you can see that there
is a decrease in ionization energy, carbon at 1086 and silicon at 786 followed by
germanium at 762 and this is also because of an addition of shell.

Electronegativity
Electronegativity decreases down the group.

Melting and Boiling Point

Melting point again decreases down the group, boiling point you can see here will
decrease down the group, and M-M bond energy also decreases down the group.

Oxidation State
As in the previous p¹ group that is 13 group , the higher elements tend to show inert
pair effect and thus, the +2 oxidation state becomes more relevant, same happens in
the case of tin and lead, whereas carbon, silicone and germanium show a oxidation
state of +4. Now you can see that the commonly observed oxidation states in this
group are +4 and +2 and we already said that they show +2 oxidation state because
of the inert pair effect which is well discussed in group 13 elements. Now carbon and
silicon are generally tetravalent but on descending the group the stability of the +4
oxidation state decreases due to inert pair effect.

Now the +2 oxidation state becomes important progressively and lead is present
predominantly in divalent oxidation state. Therefore, Pb(IV) compounds like PbCl4
and PbO2 are strong oxidizing agent and PbO2 may oxidize hydrochloric acid to
chlorine. So you can see the oxidation property or the stability of Pb²⁺ ion, because
Pb⁴⁺ is getting reduced to Pb²⁺, it will oxidize chloride to Cl2. Now you can see here in
the reaction
PbO2 + 4HCl → PbCl2 + 2H2O + Cl2

Here the oxidation state of Pb is +4 and it gets reduced to +2, and you can see that
chlorine has a oxidation state of -1, and thus gone to 0, so that is the oxidizing power
of PbO2. And as we know, lower the oxidation state more ionic is the compound. As
M⁴⁺ is smaller than M²⁺ and covalency is favored by large charge on cation and small
size. In tetravalent compounds of the Group 14, element is sp³ hybridized. Carbon
has greater electronegativity and may form carbide as well that is these compound
have C⁴⁻ and C2²⁻ charge on that.

Catenation
Now carbon has a remarkable property of forming long chains and rings when bound
to itself. This is a unique property which carbon possesses and no other element in
the periodic table has. It can form chains of very long type and also ring. This is the
only property which is present in carbon and in fact carbon has much greater
number of compounds then the compounds of all the other elements present in the
periodic table. Apart from that there is another property which carbon possesses
that is formation of double and triple bond which is also not very common with
other element in the same group. Now I have shown here you can see that this is
due to the formation of pπ- pπ bonds with itself and other electronegative elements
e.g. C=C, C≡C, C=O, C=S and C≡N linkages are known. So these two properties of
carbon that is formation of chains and ring and formation of double, triple bond
mixed with very important element itself. The other elements do not form such
bonds. Chemists have been exploring the tendency of formation of such types of
bond in the silicon and have resulted in finding some compounds which have similar
type of bonding. You can see here there is dimethyl silicon, you can see here which is
bonded to carbon here in double bond manner was isolated about 10 years later. In
view of the extensive chemistry of alkenes it was natural to search for analogous
compounds containing the > Si = Si < bond. The first such compound,
tetramesityldisilene, was isolated in 1981.

 Allotropy
Now another important feature is allotropy. What is an Allotrope? Now allotropes
are different physical forms of a pure element. Now most of the elements in this
group exist in different physical form. For example carbon has mainly three types of
physical forms which include Diamond, Graphite, and Fullerene. You can see that
Diamond, Graphite, and Fullerene, however, there are many more recently
discovered and engineered forms of carbon, these are called Graphenes and
Nanotubes. Now nanotubes are basically made by graphene, graphene sheets are
folded by a technology and that turn into to nanotube.

Now diamond is the hardest substance known, having a very rigid structure. Now
each carbon atom is sp³ hybridized and linked to four other carbon atoms. The unit
cell (repeating unit) which makes up a crystal of diamond is known as adamantane.
Diamond is a very poor electrical conductor, but generally a good thermal conductor.
Now thermal means heat conductor.

Graphite has a layer – structure in which weak Vander Waal’s forces hold individual
layers of fused six membered rings together. The carbon atoms are sp² hybridized
and out of four valence electrons, three are involved in σ - bond formation whereas
the fourth electron is involved in delocalized π - bonding formation. Because of this
delocalization, (delocalize means it is mobile, localize means it is stationary) and
formation of delocalized π bonding the electrons move freely and therefore they are
good conductors and also has lubricating property. Because of the layer structure
there is a difference between the layers and if you press them they have a lubricating
property. And conductivity is due to the mobility of electron and which is the result
of the formation of π bonding.

Now you can see here we have compared the properties of diamond and graphite.
The density of diamond is 3.51 and 2.26, we all know that physical properties of an
element may vary but chemical properties generally remain the same. Now you can
see the density of diamond is 3.51 and in case of graphite it is 2.26, you can see the
electrical resistivity which is 1x10¹¹ and this is about 1.3x10⁵ for graphite so we can
see this is much greater than graphite, the resistance is in fact opposite of
conductance. So you can see diamond has a very high resistance and graphite has a
lower resistance, having lower resistance means graphite is a good conductor. Now
the C-C bond distance can be seen here is 154.4 and in case is 141.5, you can see
here the interlayer distance is also given here is about 355.4pm. Now at room
temperature graphite is thermodynamically more stable and can be converted into
diamond at a very high pressure and temperature. Now Fullerenes, Fullerenes were
discovered by a research group lead by Harry Kroto, Richard Smalley, and Robert Curl
in 1985. The first observed fullerene was C60, or as it is also named as
Buckminsterfullerene.

The name 'Fullerenes' is derived from the architect Buckminster Fuller, who designed
geodesic domes which were constructed by interlocking hexagons and pentagons;
identical to those seen within the structure of Fullerenes. Therefore this name is
coming Buckminster fullerene. The most famous of the Fullerenes, C60, takes the
form of a 'football' consisting of 20 hexagons, and 12 pentagons. C60 is not the only
size of Fullerene to be discovered. There are a number of these type of compound
with different number of carbon atoms as you can see here. The other well
characterized Fullerenes include C70, C84, and C540; although in theory, an unlimited
number of Fullerenes could exist, based upon 12 pentagonal faces, and any number
of hexagonal faces. Fullerenes have two distinct bond lengths within their structure.
The shorter one is 135 pm in length which corresponds to a double bond, and a
longer one is 146 pm which corresponds to a single bond. These double and single
bonds are similar to those in benzene, allowing the delocalization of electrons across
the entire structure. Heating graphite in an electric arc in an inert atmosphere
(helium or argon) results in a sooty materials consisting of C60 with smaller amounts
of C70 and other such material called fullerenes, which contain even number of
carbon atoms. Now you can see the structure of diamond here this is the central
carbon atom it is attached tetrahedrally to four other carbon atom, here 1, 2, 3, 4,
you can see all the carbon atom attached to it. In case of graphite, you can see,
central carbon attached to three carbon atoms, if it is take the central carbon atom
there is 1, 2, an third carbon, so each carbon atom is attached to three other carbon
atom and there is a structure of graphite. In the next structure we have shown you
structure of fullerenes. You can see here there is a hexagonal ring, you can see
1,2,3,4,5,6 and if you see this ring this is a pentagonal ring or pentagonal 1,2,3,4,5 so
you can see that this has hexagonal and pentagonal ring structure and graphite has
all hexagonal rings and in diamond has all tetrahedral carbon atoms. So there is a
difference between the structure of three.

Now fullerenes are known to behave like a “radical sponge” as they can sponge-up
and neutralize 20 or more free radicals per fullerene molecule. Now they have
shown performance 100 times more effective than current leading antioxidants such
as Vitamin E. Fullerene is highly soluble in almond oil and thus it can be used for
screening test for ocular tissue toxicity indicating no adverse effect. Now they also
behave as catalysts. They have marked ability to accept and to transfer hydrogen
atoms i.e. they can cause hydrogenation and hydro alkylations. This will be done in
organic chemistry highly effective in promoting the conversion of methane into
higher hydrocarbons. Now Silicon and germanium predominantly crystallize in
diamond structure and both are semiconductors. Now Tin exists in a diamond form
(α) and metallic form β while lead exists only in metallic form. All the elements form
covalent hydrides but the number of hydrides formed, their stability and ease of
formation decreases down the group. And we know about carbon there are millions
and trillions of hydrocarbons which we know about, so we are not going to take up
the hydrocarbons of carbons because that is dealt by the organic chemists. We will
take up the hydrides of other members like silicon, germanium, tin, lead.
  Hydrides
Now carbon forms a large number of hydrides involving chains, rings and multiple
bonds between carbon atoms which we have already told you earlier also. So these
hydrides form the basis of organic chemistry, again I mentioned earlier that this is
better taken up in organic chemistry rather than inorganic chemistry.

Hydrides of Silicon
Now Silicon forms a limited number of hydrides, the silanes which is represented by
the formula Sin H2n+2. They are very similar to alkane, Now Monosilane, SiH4, is the
most stable and is tetrahedral, like methane. So you can see that even structure is
very similar that is tetrahedral SiH4 or monosilane also have tetrahedral structure.

Now silanes containing up to eight silicon atoms have been synthesized but their
stability decreases with increase in chain – length and this is probably because the Si-
Si bond is not very strong. Now you can see the preparation here that is silanes are
prepared by reacting, Mg2Si with H2SO4 giving SiH4 and some higher silanes.

Now monosilane can be prepared by reaction of SiCl4 with lithium aluminium hydride
or sodium hydride. Now what will happen is if you react with sodium hydride NaH,
SiCl4, it will form SiH4 and HCl and NaCl, you can see that it is the reaction of silicon
tetrachloride SiCl4 with lithium aluminum Li[AlH4] hydride giving SiH4 + LiCl + AlCl3 .
Now NaH you can as I have told you earlier SiCl4 will react with NaH giving SiH4 there
is monosilane + 4 NaCl.

Now silanes are more reactive than the corresponding alkanes, various reasons are
attributed to this. The Si –Si bond is slightly weaker than the C-C bond, bond energies
are 340 & 368 KJmol-1 respectively. The Si-H bond is weaker than the C-H bond, bond
energies 393 & 435). Silicon has vacant low- lying d orbitals, which can accept
electrons from nucleophiles and form reactive intermediates. There is a main reason
behind the high reactivity of silicon in comparison to carbon the carbon does not
have any vacant d-orbital or in fact does not have a d-orbital and therefore it reacts
in a different way to silicon compounds. Now silanes decompose to give silicon of
high purity by elimination of SiH2. So there is a reaction, we trying to show you here
these are silanes and there is intermediate forming SiH4, SiH2, there is Si2H6 basically
disilane, there is intermediate forming monosilane and SiH2 and this is not stable,
therefore it decomposes into silicon and hydrogen. This silicon is very pure. The
electronegativity values of Si, C, you can see the electronegativity of three elements
silicon, carbon and hydrogen they are 1.8, 2.5 and 2.1 respectively. So the polarity of
Si-H and C-H bonds differ and are depicted as Si – H and C-H. Now silicon is more
susceptible to nucleophilic attack than carbon as the larger size of silicon provides
greater surface area for the nucleophilc attack. Now Germanes that is GeH4
germanium containing upto five germanium atoms and represented by the formula
Gen H2n+2 as again similar formula as we have seen earlier are known. They are less
stable than the silanes. The Tin forms only two hydrides SnH4 and Sn2H6 which are
even less stable. The stability of hydride decreases down the group, lead also forms
tetrahydride but this is highly unstable. In fact PbH2 will be very stable as compared
to PbH4 because of inert pair effect.
Tetra-halides
Now all the elements form tetrahalides with the formula MX4 but the compound of
lead is likely to be more unstable because of the inert pair effect. It generally forms,
hydride in +2 form and can act as a very good oxidizing agent because from +4 it is
getting reduced to +2 oxidation state and hence all lead 4 compound, tend to act as
a very good oxidising agent and we can see here PbI4 is not even known. But PbI2 we
now it do exist.

The stability of the tetra-halides decreases down the group. The reason is very
obvious, as we go down the group the inert pair effect is taken into account, and
thus the stability of +2 oxidation state will be increased. The fluorides, by virtue of
high electronegativity of fluorine, are the most ionic. SnF4 and PbF4 are high melting
solids and the others are covalent, tetrahedral and volatile. Now you can understand
the fact that SnF4 and PbF4 are high melting solid because the fluorine has very high
electronegativity and the difference between Sn and Fluorine electronegativity is
quite high and therefore will become ionic in character and hence have high melting
point.

The halides can generally be prepared by some reactions which I have shown below:
SiC + 4F2 → CF4 + SiF4
CH4+ 4Cl2 → CCl4 + 4HCl
CCl4+ HF → CCl3F + HCl

Now similarly,

SiC + 4X2 → CX4 + SiX4 X= Br, Cl

  Hydrolysis of tetrahalides

The halides of carbon are inert towards water; however the halides of silicon readily
hydrolyze. Now you can see in the reaction

SiCl4 + 4H2O → Si(OH)4 + 4HCl

Whereas, tetrachloride does not react with water. Now the reason is because of the
presence of d-orbital. Now the lone pair of water in the intermediate are placed in
the empty d-orbital present on the silicon as it will be seen in the next slide.

The hydrolysis proceeds via an intermediate where silicon has a coordination

number of five. Now you can see here, the lone pair on oxygen here the lone pair of
oxygen is donated to silicon which has a vacant d-orbital. So we are showing here
and there is an intermediate form and then we get the resultant compound
hydroxide here. Now here we are showing only one step, and if we add further water
another water molecule will act in a similar way and you will get dihydroxide and if
we add third water molecule this will be replaced in a similar way and the final
product would be Si(OH4) which we have shown above.

Now, this process continues till Si-OH bonds replace all the Si-Cl bonds, this is what I
meant in the diagram there. Now since carbon does not have any d-orbitals it cannot
form such an intermediate and therefore tetra-halides of carbon do not hydrolyze.
Now Germanium, tin and lead form both tetra-halides and di-halides, however the
dihalides become more stable as we go down the group.
Now, the tetra-halides have a tendency to hydrolyze, but the hydrolysis can be
suppressed by addition of appropriate halogen acid. Now you can see this if we take
chloride say tintetrachloride and add water it gets hydrolyzed to Sn(OH)4, now if you
want to reduce this, add HCl, if it was Br here then we would have added
hydrobromic acid but now since it is Cl4, so the appropriate acid will be HCl in this
case, and if we add this then there is an equilibrium here and the hydrolysis can be
prevented. So that is what we meant by this the hydrolysis can be suppressed by
adding the appropriate halogen acid. So in this case HCl is the most appropriate. Now
the halides of Si, Ge, Sn and Pb can increase the coordination number to 6 by
forming complexes of the type like [SiF6]²⁻, [SnCl6]²⁻ etc where the vacant d orbitals
are used.

Now you can see this we are just showing you the hybridization which is present, the
hybridization is present in sp³d². Now there is a ground state of silicon. We know that
silicon has 4 electron in the valence shell, 2 in the 3s orbital, 1 each in the 2p orbital,
and on excited state one of the electron is promoted to the p orbital, so you have got
4 singly occupied orbital they will mixed to form sp³ hybridisation. But as I said, that
this is sp³ hybridization, if I involved these two vacant d-orbital, the net result would
be formation of sp³d², now I am showing here 4 electron from F-atoms which are
shown here you can see the normal bond formation and these two orbitals, these
are d-orbitals, now they are basically used up they are provided lone pair from other
fluoride ions and therefore the hybridization becomes sp³d², and the resultant
structure would be octahedral. So there is the overall configuration which we are
showing, you can see that 1s, 3p and 3d, two 3d orbitals I involved and the net result
is sp³d² hybridization and the structure would be octahedral.
Now lead (II) halides are the most stable di-halides of this group. In fact, lead is the
only element of this group with well- defined cation, Pb²⁺. All the lead halides are
insoluble in water. Now in qualitative analysis Pb (II) is precipitated in group I of
qualitative analysis as PbCl2 and is confirmed as the yellow PbI2 (s).

There is an increase in stability of dihalides on moving down the group, as we can see
here
SiX2 << GeX2 < SnX2 < PbX2
Now SiF2 can be made at high temperature by the reaction:
SiF4 + Si → 2SiF2

you can see this equilibrium basically it is not stable and it decomposes back or it can
react back to give you the same product.

Now divalent germanium halides are quite stable. GeF2 is polymeric having fluorine
bridges. Tin (II) halides are well – characterized and very important in the sense that
they act as a very good reducing agent in presence of HCl. It undergoes partial
hydrolysis and is soluble in organic solvents. It is a mild reducing agent as shown by
the following reactions: Now you can see the reaction here
2FeCl3 + SnCl2 → 2FeCl2 + SnCl4
2HgCl2 + SnCl2 → Hg2Cl2 + SnCl4
Hg2Cl2 + SnCl2 → 2Hg + SnCl4

So you can see here in all these reactions, the reducing property of tin.
Summary
In the end I’ve just very summarized the whole e-content, now today we have
discussed the introduction of p-block Elements specially the Group 14, and then we
have also discussed the physical properties like ionization energy, melting point,
physical point, the physical appearance, structure etc and finally we have discussed
the chemistry of 14th group halides. In the next e-content we will take up the other
chemical properties of the group 14 elements.