Group oxidation state and inert-pair effect

The maximum oxidation state shown by a p-block element is equal to the total
number of valence electrons (i.e., the sum of the sand p-electrons) called group
oxidation state

The oxidation state two unit less than the group oxidation state becomes
progressively more stable for the heavier elements in each group due to non-
participation of s electron . The occurrence of oxidation states two unit less than the
group oxidation states are sometime attributed to the ‘inert pair effect’.

Anomalous behavior of first element of the group

The first member of p-block differs from the remaining members of their
corresponding group in two major respects small size and lack d orbitals in second
period elements, some examples of anomalous behavior are :

 Using these d-orbitals the third period elements can expand their covalence
above four. For example, while boron forms only [BF4] – , aluminium gives
[AlF6] 3– ion.
 The combined effect of size and availability of d- orbitals considerably
influences the ability of these elements to form π bonds. The first member of
a group differs from the heavier members in its ability to form pπ - pπ
multiple bonds to itself ( e.g., C=C, C≡C, N≡N) and to other second row
elements (e.g., C=O, C=N, C≡N, N=O). This type of π - bonding is not
particularly strong for the heavier p-block elementsThe heavier elements do
form π bonds but this involves d orbitals (dπ – pπ or dπ –dπ ).

Electronic Configuration

The outer electronic configuration of these elements is ns2 np 1

.

Atomic Radii

 On moving down the group, for each successive member one extra shell of
electrons is added and, therefore, atomic radius is expected to increase.
 Atomic radius of Ga is less than that of Al. The presence of additional 10
d-electrons offer only poor screening effect for the outer electrons from the
increased nuclear charge in gallium. Consequently, the atomic radius of
gallium (135 pm) is less than that of aluminium (143 pm).
 effective nuclear charge increases and thus, size decreases. The elements of
this group have smaller size than the corresponding elements of second
group.

Ionization energies

 The sharp decrease in I.E. from B to Al is due to increase in size.

 In case of Ga, there are ten d-electrons in its inner electronic configuration.
 The very high value of 3 rd I.E. of thallium indicates that +3 O.N. state is not
stable, rather +1 is more stable for thallium.
Electropositive (or metallic) character

 The elements of group13 are less electropositive as compared to elements of

group2.
 On moving down the group the electropositive (metallic) character increases
because ionization energy decreases. For e.g., Boron is a non-metal while
the other elements are typical metals.

Oxidation states

 The common oxidation states of group13 elements are +3 and +l.

 The stability of the +1 oxidation state increases in the sequence
Al<Ga<In<Tl due to inert pair effect

Hydrides

 None of the group13 elements reacts directly with hydrogen.

B2H6:
 INUDUSTRIAL PREPARATION:- 2BF3(g) + 6LiH(s) → B2H6(g)+ 6LiF(s)
• Laboratory method: (i) By the reaction of iodine with sodium borohydride in
a high boiling solvent. 2NaBH4 +I2 →B2H6 +2NaI +H2

(ii) By reduction of BCl3 with LiAlH4

4BCl3 +3LiAlH4 →2B2H6 +3AlCl3 +3LiCl

Structure of Diborane, B2H6

Some important characteristics of boranes

Structure of diborane:
o In this structure, there are 2 types of Hydrogen atoms.
o The types: 4 terminal Hydrogen and 2 Hydrogen atoms are called bridged
atoms.
o The 4 terminal Hydrogen are bonded by normal covalent bond and 2 bridged
Hydrogen atoms by are bonded by 3 centre electron pair bonds as shown :
o Both the Boron will have in total 2 empty d orbital.
o Each 2p orbital overlaps with 1s orbital of H atoms.
o The 2 hybrid orbital left on each Boron atom contain an unpaired electron and
other is empty.
o The orbital containing one electron of one boron atom and the other empty
orbital of second boron atom form a bond with hydrogen atom simultaneously to
give B-H-B bond.
o Each Boron form 2 covalent bond.
o Out of 3 unpaired electrons, the left electron of both the boron is 2 and of 2
Hydrogen atom is also 2.
o Therefore, it forms 3 bonds instead of 2 bonds.

ii) They undergo spontaneous combustion in air due to strong affinity of boron for
oxygen.

B2H6 +3O2 →B2O3 +3H2O+Heat

iii) Boranes react with alkali metal hydrides in diethyl ether to form borohydride
complexes.

B2H6 +2MH→2M + [BH4] - (M=Li or Na) Meta lborohydride

iv)Diborane reacts with ammonia to give borazine at 450K

. B2H6 +6NH3 →3B3N3H6 +12H2

AlH3 is a colorless solid polymerized viaAl-H-Al bridging units. These hydrides are
weak Lewis acids and readily form adducts with strong Lewis base (B:) to give
compounds of the type MH3 (M=AlorGa). They also form complex-tetrahydrido
anions, [MH4]-.

The most important tetrahydrido compound is Li[AlH4] ether

4LiH+AlCl3―――→LiAlH4 +3LiCl

OXIDES & HYDROXIDES • M2O3 & M(OH)3

 .

3. The melting and boiling point of boron are much higher than that of Al.

4. Boron forms only covalent compounds where as Al forms even some ionic
compounds.

[Link] hydroxides and oxides of boron are acidic in nature where as those of
aluminium are amphoteric. [Link] trihalides of boron exist as monomers. On the
other hand, aluminium halides exist as dimers. [Link] hydrides of boron are quite
stable while those of aluminium are unstable •

1. Ortho boric acid

Chemical Formula :- H3BO3 or B(OH)3
 Preparation: It is prepared from Borax.
Na2B4O7.10H2O + HCl +H2O-->H3BO3 + NaCl
Borax hydrochloric acid boric acid sodium chloride
Properties
o It is white crystalline solid with soapy touch.
o It is sparingly soluble in cold water but soluble in hot water.
o At 373k, it forms metaboric acid.

o It behave as Lewis acid because of its formula B(OH)3

Uses
1. It is used in manufacturing of enamels.
2. It is used as food preservative.
3. It is used in medicines for eye wash.

Diagonal relationship boron and silicon

• Boron and silicon exhibit the typical properties of non-metals. These donot
form cations.
• Both exist in amorphous as well as crystalline forms.
• Boron oxide (B2O3) and silica (SiO2) both are acidic and dissolve in alkali
solutions to form borates and silicates respectively.

B2O3 +6NaOH→ 2Na2BO3 +3H2O

 SiO2+2NaOH→ Na2SiO3 +H2O

• The chlorides of both B and Si get hydrolyzed by water to boric acid and
silicic acid respectively.

BCl3 +3H2O→H3BO3 +3HCl

SiCl4 +3H2O → H2SiO3 +4HCl

• The hydrides of Boron and Silicon are quite stable. Numerous volatile
hydrides are also known which catch fire on exposure to air and are easily
hydrolyzed.
• Both elements are semiconductors.

Behaviour in Aqueous Solutions

1 Al, Ga, In and Tl exhibit a well-defined aqueous chemistry in their tripositive

states. Species like [M(OH)4] - ,[M(H2O)2(OH)4] - ,[M(OH2)6] 3+ for M=Al, Ga, in exist
in aqueous solution.

2. Al, Ga. In and T1 ions exist as octahedral aqua ions, [M(H2O)6]3+ in aqueous
solution and many salts like halides, sulphates, nitrates and perchlorates exist as
hydrates.

[Link] sulphate forms double salts- called alum, having the general formula
M2SO4.Al2(SO4)3.12H2O, where M=Na + or K + .

GROUP 14 ELEMENTS

The Carbon Family Group 14 includes carbon(C), silicon(Si), germanium(Ge),

tin(Sn) and lead (Pb). General electronic configuration of carbon family is ns2
np2 .

Covalent radius:-Covalent radius expected to increase from C to Si, From Si to

Pb small increase is found due to weak shielding d orbitals

Ionization Enthalpy:-The first ionization enthalpies of group 14 elements are

higher than those of the corresponding group13 elements due to greater effective
nuclear charge.

Electronegativity:-Group 14 elements are smaller in size as compared to group

13 elements that’s why this group elements are slightly more electronegative than
group 13

Chemical properties:- Carbon and silicon mostly show +4 oxidation state.

Germanium forms stable compounds in +4 state and only few compounds in +2
state. Tin forms compounds in both oxidation states. Lead compounds in +2 state
are stable and in +4 state are strong oxidizing agents.

Exception:-PbF4 and SnF4 are ionic in nature.

 Except CCl4 other tetrachlorides are easily hydrolysed by water. Since
carbon does not have d-orbitals and hence cannot expand its coordination
number beyond

4 CCl4+H2O → No Reaction

SiCl4+4H2O → Si(OH)4+4HCl Silicic acid

Allotropes of Carbon:-The three types of allotropes are– 148

1-Diamond 2-Graphite 3-Fullerence Diamond:-In diamond each carbon atom under

goes SP 3 hybridisation. Each carbon is tetrahedrally linked to four other carbon
atoms.

Graphite:-In graphite, carbon is SP2 -hybridized graphite has a two-dimensional

sheet like structure consisting of a number of hexagonal rings fused together.
Graphite conducts electricity along the sheet. It is very soft and Slippery

Fullerene was discovered collectively by three scientists namely [Link], [Link]

[Link]

Some Important Compounds Of Carbon and Silicon Carbon monoxide:-It is

prepared by direct oxdisation of C in limited supply of oxygen. 2C+O2(g) → 2CO(g)
Commercially it is prepared by the passage of steam over hot coke

:-It is prepared by complete combustion of carbon and carbon fuels in excess of air.

C(s)+O2(g) → CO2(g)

Laboratory method:- In laboratory it is prepared by the treatment of dil HCl on

CaCO3 CaCO3(s)+2HCl(aq) → CaCl2(aq)+CO2(g)+H2O(l)

Silicon dioxide:-Silicon dioxide is a COVALENT THREE DIMENSIONAL NETWORK

SOLID. Each silicon atom is covalently bonded in a tetrahedral manner to four
oxygen atoms.

Silicones:-Silicones are the synthetic organo-silicon polymers having general

formulae (R2SiO)n in which R=alkyl (methyl, ethyl or phenyl) Silicates:-Silicates
exist in nature in the form of feldspar, zeolites, mica and asbestos etc. The basic
structure of silicates is SiO4 4- 149 Zeolites:-Zeolites is a alumino-silicate of metal.
Metal cations participating in formation of Zeolite are usually Na + ,K + ,or Ca 2+ .
Zeolites are used to remove permanent hardness of water.