VELAMMAL BODHI CAMPUS, PANCHETTI.

IIIA GROUP ELEMENTS

SUB : CHEMISTRY
Introduction:
 B, Al, Ga, In and Tl are IIIA group elements.
 General electronic configuration is ns2np1.
 No. of valence electrons is 3, valency wrt. Hydrogen is 3 and valency wrt oxygen
is 3.
 The metallic nature of IIIA group elements is less than that of IA and IIA group
elements.
 The most abundant metal in earth crust is Al.
Atomic radius: B < Al > Ga < In < Tl.
 The lower atomic radius of gallium is due to the poor screening effect of 3d-
electrons.
 Tl has nearly same atomic radius of In, due to the poor screening effect of
f-electrons.
 Ionic radius : Increases from B to Tl
Order : B3+ < Al3+ < Ga3+ < In3+ < Tl3+
 Density : Increases from Boron to Thalium
Order : B < Al < Ga < In < Tl
 Melting point : Irregular trend.
Order : B > Al > Tl > In > Ga
 Boiling point : Decreases from B to Tl
Order : B > Al > Ga > In > Tl
 Due to large difference between the melting point (300C) and boiling point
(22400C), Gallium is used in high temperature thermometers.
 IP : Irregular trend.
Order : B > Tl > Ga > Al > In
 The IP1, of IIIA group elements is lower than that of IIA group elements.
Reason : IIA group elements have stable ns2 configuration
 IP2 values of IIIA group are very much higher than IP1 values because the second
electron is to be removed from ns2 orbital.
 Electro positivity:
 Due to small size and higher IP1 value IIIA group elements are less electropositive
than IA and IIA group elements.
 E.P. increases from B to Al while later it decreases, i.e, Ga, In and Tl are less
metallic than Al.
 Boron is semimetal while other elements are metals.
 Al is amphoteric in nature.
 Standard oxidation potential :
 Boron has lower SOP value while Al has higher SOP value. Thus Al acts as
stronger reducing agent.
 Oxidation states:
 Common oxidation state is +3.Boron shows only +3 oxidation state while other
elements show +1 oxidation state also in addition of +3.

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  In heavy metals like thalium, the two ns electrons are reluctant to uncouple and
donot participate in reactions. Due to this Tl shows stable +1 oxidation state
instead of +3. This is called inert pair effect.
 From B to Tl, the stability of +3 state decreases and the stability of +1 state
increases due to inert pair effect.
 Nature of bonding:
 Due to small size, higher charge, higher electronegativity and higher value of
(IP1 + IP2 + IP3) IIIA group elements mainly form covalent compounds.
 The compounds like AlCl3, GaCl3 etc are covalent in solid state but ionic in
aqueous solution state due to the higher hydration of M3+ ion.
 The compounds BCl3, AlCl3, BF3 etc have six electrons around the central atom.
Hence these are regarded as electron deficient compounds and act as Lewis
acids.
 IIIA group elements form complex compounds more readily than s-block
elements.

Chemical properties:
a) Action with air:
 Crystalline boron is unreactive towards air
 Amorphous boron on heating in air gives B2O3.

 Aluminium is stable in air due to the formation of protective oxide layer.

 Ga & In are not affected by air.

 Tl forms an oxide layer on its surface.
b) Action with water:
 Boron is not affected by water. However red hot boron is affected by steam.

 Aluminium decomposes cold water also if protective oxide layer is not

present.

 Ga & In are not affected by water.

 Tl forms TlOH in moist air

c) Action with acids:

 Boron is not affected by HCl & H2SO4 while other elements liberate H2 gas
from dil. acids.

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  All elements react with oxidising acids like conc. H2SO4 and conc. HNO3.

Action with alkalies:

 B, Al and Ga react with alkali solution to liberate H2 gas.

 In & Tl are not affected by alkalies.

Action with non-metals:
 All these elements combine with halogens to form corresponding halides.

Eg:
Action with metals:
 Only boron combines with metals to form borides.

Compounds of boron:
a) Borax :
Preparation :
1) The naturally occurring tincal is dissolved in hot water & insoluble
impurities are filtered off. The resulting solution is concentrated and
cooled when crystals of borax are obtained.
 Borax is highly soluble in hot water and least soluble in cold water.
2) Boric acid on reacting with soda ash gives borax.

 Properties:
1) The aqueous solution of borax is alkaline due to anionic hydrolysis.

2) On heating, borax first swells up due to the elimination of water

molecules. On further heating it melts to a liquid and then solidfies to
give a transparent glassy mass.

(Sod. meta (boric anhydride)

Borate)
Borax bead test:
 When hot glassy mass is mixed with a coloured salt and heated
then coloured metaborates of the respective metals are obtained.

eg:
(Blue)
Based on the colour of the metaborate, the metal is identified.
 Cu  Blue; Fe – Green; Co  Blue; Cr  Green; Ni  Brown.

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 3) Aqueous solution of borax acts as buffer because it contains weak
acid and its salt with a strong base.

Structure of borax:
OH

O B O
Na2 HO B O B OH . 8H2O
O B O

OH
 Two boron atoms are sp2 and another two boron atoms are sp3
hybridised.
 It has two tetrahedral and two triangular units joined together.
Uses :
1) Borax bead test is used qualitative analysis, 2) As a flux, 3) as an
antiseptic, 4) in water softening, 5) in making optical glasses
and heat resistant borosilicate glass, 6) for impregnating match-
sticks to prevent after glow, 7) for glazing paper and playing cards
and 8) for stiffening of candles.
b) Orthoboric acid (H3BO3):
Preparation :
1) Borax solution on treating with conc. H2SO4 gives boric acid crystals.

4H3BO3
2) Colemanite mineral is powdered and mixed with boiling water through
which SO2 gas is circulated where the suspension of boric acid is
formed.

6H3BO3
Properties:
1) It is less soluble in cold water and more soluble in hot water.
2) It is a weak monobasic acid. It does not act as proton donor, ie, not a
protonic acid but acts as Lewis acid, ie, electron pair acceptor.

3) On heating,

(Meta boric (Tetra boric

acid) acid)
4) A mixture of boric acid and ethyl alcohol burns with green edged
flame due to the formation of volatile ethyl borate.

(ethyl borate)
Uses :
1) It is used as antiseptic and as eye wash under the trade name, ‘boric
lotion’.
2) Used in glass industry.
3) Used as food preservative.

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 Structure of Boric acid:
3 −¿ ¿
 In H3BO3 (i.e, BO3 ) the boron atom is sp2 hybridised and shape is
planar trigonal. BO33 −¿ ¿ units are joined by hydrogen bonds to give
layered structure.
c) Diborane (B2H6):
Preparation :
1) Boron trichloride on reacting with lithium aluminium hydride gives
diborane.

2) By passing silent electric discharge through the mixture of boron

trichloride and H2, diborane is obtained.

B2H6 + 6HCl
3) Boron trifluoride on reacting with lithium hydride, diborane is formed.

Properties:
1) It is a colourless gas with disagreeable odour.
2) On strong heating, it decomposes to give boron and H2.

3) It burns in oxygen. The reaction is highly exothermic.

4) It easily reacts with water liberating hydrogen gas.

5) It reacts with strong alkalies to form metaborates.

6) It reacts with chlorine to form BCl3.

7) In the presence of AlCl3, it reacts with dry HCl to give H2 gas.

(chloro diborane)
8) It forms addition product while reacting with carbon monoxide.

9) It reacts with sodium amalgam to form addition compound.

10) At low temperature it reacts with ammonia to form an addition

compound which on heating at 2000C gives borazole.

(Borazole)

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  Due to its similarity in structure, borazole is called inorganic
benzene.
H H

B C
H N N H H C C H

H B B H H C C H

N C

H H
(Borazole) (Benzene)

Structure of diborane:
i) Diborane has only twelve valency electrons, while a similar stable
compound ethane has 14 valency electrons hence it doesnot have
ethane like structure.
H H

H C C H

H H
ii) When diborane is subjected to methylation, tetramethyl diborane
[B2(CH3)4. H2)] is obtained. Hence in diborane four hydrogen atoms
are normally bonded and another two hydrogen atoms are
differently bonded.
iii) According to electron bifraction studies diborane is found to be
containing two coplanar BH2 groups while other two hydrogens are
lying one above the plane and one below the plane.
H H
H

B B
H H H

iv) In diborane.
a) Two coplanar BH2 groups,
b) Four terminal hydrogens,
c) Two bridged hydrogen atoms and
d) Two, three centred two electron bonds are present.
v) Each B – H – B bond is called three centred two electron bond or
banana bond or tau bond.
vi) In diborane boran atom is sp3 hybridised. The overlapping of
orbitals is as follows.

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COMPOUNDS OF ALUMINIUM:
a) Alumina (Al2O3):
Important minerals:
1) Corundum : Al2O3
2) Diaspore : Al2O3. H2O
3) Bauxite : Al2O3. 2H2O
4) Gibbsite : Al2O3. 3H2O
Preparation:
1) Alumina is prepared by igniting aluminium hydroxide, aluminium sulphate
or ammonium alum.

2) The mixture of aluminium fluoride and boric oxide on strong heating gives
alumina.

Properties :
1) White solid, insoluble in water and un reactive substance.
2) Al2O3 is amphoteric in nature.
3) When Al2O3 is fused with the oxides of chromium, iron and cobalt then
synthetic semi-precious stones are obtained.
Uses:
1) For making bauxite bricks which are used for furnace lining.
2) Fused alumina is used as refractory material.
3) On heating in an electric arc at 30000C, a hard powder known as
alundun is obtained, which is used as abrasive.
4) Mixing with lime, it is used as bauxite cement which is not affected by
sea water.
5) In chromatography, it is used as adsorbent.
b) Aluminium chloride:
Preparation:
1) When dry HCl gas or chlorine gas is passed over hot aluminium in the
absence of air, anhydrous aluminium chloride is obtained.

2) When the mixture of alumina, carbon and chlorine gas is heated at 10000C,
then anhydrous AlCl3 is obtained.

3) When aluminium metal or aluminium hydroxide is dissolved in dil. HCl,

then hydrated AlCl3 in obtained.

 HCl gas is circulated through the resulting solution to get the crystals of
hydrated aluminium chloride.

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Properties:
1) Anhydrous AlCl3 is a deliquescent white solid.
2) It exists as dimer, Al2Cl6.
Cl Cl Cl
Al Al
Cl Cl Cl

3) Anhydrous AlCl3 is covalent and does not conduct electricity in molten state.
4) It is soluble in organic solvents like alcohol, ether, benzene, etc.
5) In water, it exists as [Al(H2O)6]Cl3.
6) Anhydrous AlCl3 fumes in moist air due to evolution of HCl.

7) When dissolved in water it changes to hydrated aluminium chloride which is

ionic in nature.

 Aq. solution of AlCl3 is acidic due to cationic hydrolysis.

8) With ammonia gas, anhydrous AlCl3 forms addition product.

9) When ammonium hydroxide is added to aluminium chloride, a gelatinous

white ppt of Al(OH)3 is obtained.

(white)
10) When dil. NaOH is added to AlCl3 solution, white gelatinous ppt is formed
which dissolves in excess NaOH due to the formation of soluble sodium meta
aluminate.

(white)

(Soluble)
Uses:
1) As catalyst in Friedal-Crafts reaction.
2) It is used in dyes, drugs and perfumes.
c) Alums :
 Alums are double sulphates with 24 molecules of water of crystallisation.
 General formula is X2SO4. Y2(SO4)3. 24H2O where x is monovalent cation and
y is trivalent cation.
 In alums each cation is co-ordinately linked to 6 water molecules.
a) Potash alum (or common alum) – K2SO4. Al2(SO4)3. 24H2O
b) Soda alum (Na2SO4. Al2(SO4)3. 24H2O)
c) Ammonia alum ((NH4)2SO4. Al2(SO4)3. 24H2O)
d) Chrome alum (K2SO4. Cr2(SO4)3. 24H2O)

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 e) Ferric alum ((NH4)2SO4. Fe2(SO4)3. 24H2O)

Potash alum:
Preparation:
1) Bauxite powder is boiled with sulphuric acid to get aluminium sulphate. To
this calculated quantity of K2SO4 is added. The resulting solution is
concentrated and cooled to get the crystals of potash alum.

2) Alum stone mineral is powdered and boiled with sulphuric acid. To this
calculated quantity of K2SO4 is added. On cooling the crystals of potash
alum are obtained.

Properties :
1) It is white crystalline compound and soluble in water.
2) Aq. solution of alum is acidic due to cationic hydrolysis.
3) On heating, it swells up due to the elimination of water molecules.

¿
4) Aqueous solution of potash alum contains K+, Al3+ and SO 2−¿
4 ions.
Uses :
1) In dyeing industry, it is used as mordant.
2) In sizing cheap quality of paper.
3) In purification of water.
4) As antiseptic.
5) As septic to stop bleeding from cuts.
6) As coagulant to precipitates the colloidal solution.