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p- Block Elements

Groups 13 to 18 of the periodic table are the p-block elements.


They are also called as representative elements or normal elements.
Oxygen, silicon and aluminium are most abundant in earth's crust.
Carbon and sulphur are the two p-block elements that occur in free
state. The general electronic configuration of these elements is ns2
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np1-6.

GROUP 13 (IIIA) ELEMENTS

Boron B, Aluminum Al, Gallium Ga, Indium In, and


Thallium Tl.
The first element, boron is a nonmetal, but the others are
fairly reactive metals. The metallic character as well as the
electropositivity increase markedly from boron to
aluminum
and then decreases from aluminum to thallium.
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Element

B
Boron

Al
Aluminium

Ga
Gallium

In Indium
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Tl
Thallium

simple electron
config.

2,3

2,8,3

2,8,18,3

2,8,18,18,3

2,8,18,32,1
8,3

electron config.

[He]
2s22p1

[Ne]
3s23p1

[Ar]3d1
4s24p1

[Kr]4d10
5s25p1

[Xe]4f145d10
6s26p1

Atomic Wt.

10. 8

26. 98

69. 7

114. 8

204. 0

+3

+3

+1, +3

+1, +3

+1, +3

melting pt./oC

2300

661

30

156

304

boiling pt./oC

3659

2467

2400

2080

1457

density/gcm-3

2.3

2.7

5.9

7.3

11.9

atomic radius/ A

0.88

1.43

1.22

1.63

1.70

oxidation states

13

31

81

M3+ radius/ A
1st IE/ kJmol-1

na

0.57

0.62

0.92

1.05

801

577

579

558

589

2nd IE/kJmol-1

2420

1820

1980

1820

1970

3rd IE/kJmol-1

3660

2740

2960

2700

2870

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electronegativity

1.61

1.81

1.76

3
1.80

Chemistry of Group 13 elements in relation to Electronic


Structure:
1-The electronic configuration of elements of this group is
characterized by having a pre-outerorbital with 18 electrons (except
for B and Al) and the apparent valency of this group is the (+3)
oxidation state.
2-Because of the small size of the ions, their high charge and the
large values for the sum of the first three ionization energies, the
elements are largely covalent. Boron is always covalent and many
simple compounds like AlCl3 and GaCl3 are covalent when
anhydrous. However, in solution, the large amount of hydration
energy evolved offsets the high ionization energy and all the metal
ions exist in hydrated state.
3-The covalent radii of the atoms do not increase in a completely
regular way from B to Tl as was found on descending groups 1&2.
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This is because the inner electronic configuration of Ga, In and Tl


contains ten d electrons. These shield the nuclear charge less
efficiently than the s and p electrons, so the outer electrons are
more firmly held by the nucleus (shielding decreases s>p>d>f).
Thus atoms with d10 inner shell are smaller and consequently have
higher ionization energies than would otherwise be expected. In a
similar way the inclusion of fourteen even more poorly shielding f
electron further affects the size and ionization energy of Tl.
4-Unlike the s-Block elements, some of the elements of this group
show lower valency states in addition to the group valency. The
heavier elements show an increased tendency to form univalent
compounds, and in fact univalent thallium (thallous) compounds
are the most stable. Mono-valency is explained by that the s
electrons in the outer shell remain paired, and do not participate in
bonding because the energy to un-pair them is too great. This
occurs particularly among heavy elements in the p-block and is
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called the inert pair effect.

5-The electropositive or metallic character of the elements


increases from boron to aluminum and then decreases from
aluminum to thallium. The increase in electropositive from B to Al
is the usual trend associated with increased size. However, B and
Al follow immediately after the s-Block elements, while Ga, In and
Tl follow the d-block. These extra d electrons do not shield the
nuclear charge very effectively, so that the orbital electrons are
more firmly held, and the metals are less electropositive. This is
illustrated by the increase in ionization energy between Al and Ga
even though the larger atom would be expected to have a lower
value.
6-The basic character of elements of Gp 13 is less than that for the
preceding two groups. This is mainly attributed to their smaller
atomic volume and hence they have a higher ionization potential.
On descending down the group, the basic character increases due to
the increase in ionic size and consequently the ionization potential
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decreases downwards.

Thus boron has weak basic properties as shown by its tendency to


combine with the anions of some acids forming neutral salts as for
example boron phosphate BPO4, or acidic salts as boron hydrogen
sulphate B(HSO4)3.
The latter salt, unlike boron phosphate is an unstable compound
and hydrolyses easily in aqueous solutions as well as decomposes
by heating.
Aluminum has amphoteric properties and its ions Al3+ form
amphoteric oxide which can react as an acid forming aluminates
with strong alkalis. Al2O3 + NaOH NaAlO2 +H2O
The basic character increases further down the group. And while
gallium forms an amphoteric oxide like aluminum, we find that
thallium and indium sesquioxides are completely basic. Where an
element can exist in more than one valency state, there is a general
tendency for
the
lower
state
to
be
the
most
basic.
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Chemical Reactivity.
As previously mentioned, the ionization potential of Gp 13
elements decreases with increase of atomic number, hence the
chemical reactivity increases in the same direction (that is, with
increase of ionic size)

1-Reaction with Air:


Finely divided amorphous boron is usually impure and burns in air
to form the oxide and nitride. Pure crystalline boron in contrast, unreactive except at very high temperatures or with reagents such as
hot concentrated sulphuric acid or sodium peroxide.
The metals Al, Ga, In and Tl are silvery white. Aluminum is stable
in air because it develops an oxide film, which renders the metal
un-reactive and protects it from further attack. If the oxide layer is
removed, the metal is rapidly oxidized and decomposes cold water.
Gallium and indium are stable in air and are not attacked by water
except when free oxygen is present. Thallium is a little more
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reactive and
is superficially oxidized in water.

2-Reaction with Oxygen:


Elements of this group react with oxygen to form oxides M2O3 and
hydroxides M(OH)3.
Sesquioxides M2O3 of all the elements can be made by heating the
elements in oxygen, though B2O3 is more usually made by
dehydrating boric acid.
Almost all the elements of group 13 form oxides and hydroxides of
the composition M2O3 and M(OH)3 respectively. The nature of
these oxides / hydroxides changes from weakly acidic to
amphoteric and amphoteric to basic in moving down the group
from B to Tl.

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Reason
As one moves down the group, the atomic size of elements goes on
increasing whereas the ionization energy decreases. As a result, the
strength of M-O bond goes on decreasing accounting for the
increase in basic character down the group or conversely explains
the decrease in acidic character.
Aluminium and gallium hydroxides show amphoteric behavior.

In contrast to Tl(OH)3, which is insoluble in water, T1(OH) is


soluble and is a strong base. Many of the T1(I) compounds are
similar to the corresponding alkali metal compounds.
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Oxygen containing compounds of Boron

These represents most important compounds of boron namely: boronoxide


and hydroxides (B2O3 and B(OH)3), the later usually known as orthoboric
acid.

Boron oxide (B2O3)

Boron sesquioxide B2O3 is a nonmetallic oxide which has acidic properties


and is the anhydride of orthoboric acid.

H 3 BO3 100
C HBO2 red
heat
B2 O3

Orthoboric acid

Metaboric acid

Orthoboric acid H3BO3 behaves as a weak monobasic acid that acts, not
as a proton donor, but as a Lewis acid accepting OHOH

B
HO

OH -

HO

OH

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Triangular Planar

HO

OH

Tetrahedral metaborate ion

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Boric acid and borates form very stable complexes with diols or
polyols. The acidity of boric acid is increased by complexing and
the addition, for example, of glycerol, allows the acid to be titrated
directly with NaOH.
3H3BO3
C

glycerol

H+ + B3O3 (OH)4 - + 2H2O


OH

O
B
O

pKa= 6. 84

Complexing of B(OH4)- with diol


OH

The increase in acid strength occurs because the diol forms


complexes and effectively removes B(OH)4- from solution, thus
upsetting the balance of the revisable reaction, hence all the H3BO3
ionizes and maximum number of H+ are produced.
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3-Reaction with Hydrogen:


None of the group 13 elements react directly with hydrogen, but a
number of interesting hydrides are known besides the simple covalent
trihydrides MH3, elements of this group can also form complex hydrides
such as LiAlH4 and GaAlH4, the stability of hydrides generally decrease
from boron to gallium. Aluminum hydride can be made from LiH and
AlCl3 in ether solution, but with excess LiH, lithium aluminum hydride
LiAlH4 is formed. LiH + AlCl3 (AlH3)n LiAlH4

The Boron Hydrides (Boranes)


The boron hydrides are sometimes called boranes by analogy with the
alkanes (hydrocarbons). There are seven well-characterized boranes,
which fall into two series:
BnHn+4 and a less stable series BnHn+6. Typical molecular hydrides of
these series and B2H6, B4H10, B9H15, B10H14 and B20H16.
Diborane B2H6 is a gas (bp 92. 6C) spontaneously flammable in air
and instantly hydrolyzed by water to H2 and B(OH)3.

B2H6 +6H11/24/16
2O 2B(OH)3 +6H2

13

It may be prepared by variety of methods;


2BCl3 +6H2

silent
electric

discharge

B2 H6 +6HCl

4BCl3 +3LiAlH4 2B2H6 +3AlCl3 +3LiCl


The boranes are of great interest since there are not enough valency
electrons to form the expected number of covalent bonds; that is, they
are electron deficient. Thus in diborane there are twelve valency
electrons three from each boron atom and six from the hydrogen atoms.
Electron diffraction results indicate the structure:
H
H
H

B
H

The two bridge hydrogen atoms are in a plane perpendicular to the rest
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molecule and prevent rotation between the two boron atoms.
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Chemical Properties of Boranes


The boranes are volatile and decompose to boron and hydrogen at red
heat. They burn or explode in air and are decomposed by water or
aqueous alkali
B2H6 + 6H2O 2H3BO3+6H2
Diborane reacts with ammonia to give borazine at 450 K.

Borazine has a cyclic structure similar to benzene and thus, it is called


inorganic benzene.
H

H
N:
B
H

:N

..

B
H

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Borazine

H
-

BN+
H

C
C

H
Benzene

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Reaction with Halogens:


Al, Ga, In and Tl react with halogens to give binary halides. All the
halides of group 13 elements are known except Tl(III) iodide. The
fluorides are ionic and have high melting points. The chlorides, bromides
and iodides are essentially covalent compounds with low melting points.
The boron trihalides are covalent in nature and exist as monomeric
molecules having planar triangular geometry. In these halides boron
assumes sp2 hybrid state and the three B-X bonds are formed by axial
overlap of sp2 hybrid orbital of boron and p-orbital of halogen.
Since there are only six electrons in the valence shell of boron atom in
boron trihalides, therefore, they have a great tendency to accept two
more electrons in order to acquire a stable octet.

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2s

2p

sp2

2s

2p

Boron atom excited

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sp2

17

The empty 2p orbital on B which is not involved in hybridization is


perpendicular to the triangle, and this may accept an electron pair
form a full p orbital on any one of the three fluorine atoms, forming
an additive bond, thus making an octet of electrons round the B
atom.

The B atom in the BX3 molecule can readily accept a lone pair of
electrons from a donor atom such as O, N, P or S.

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