4.

0 GROUP III Elements

Group members comprise boron, aluminium, gallium, indium and thallium. The small
size and high nuclear charge density, makes boron a nonmetal. The rest are metals. The abrupt
increase in metallic character from B to Al is associated with the increased atomic size of Al. The
increase in atomic size in this group is not regular. This is due to the presence of d electrons in the
penultimate shells of heavier members, which are poor shielding effect than s and p orbitals.

Table 3. Some physical properties of group III elements

Metal B Al Ga In Tl
Atomic 5 13 31 49 81
number
Electronic [He] 2s22p1 [Ne] 3s23p1 [Ar] 3d104s24p1 [Kr] [Xe]
configuration 4d 5s 5p 4f145d106s26p1
10 2 1

Atomic radius 80 125 126 144 148

(pm)
Ionic radius 20 52 60 81 95
(pm)- +1 ion
Density 2.33 2.7 5.93 7.3 11.85
(g/cm3)
First I.E 801 577 579 558 589
(kJ/mol)
M.pt (0C) 2300 660 30 157 304

4.1 Occurrence

Boron occurs as Borax Na2B4O7•10H2O and calcium borate or colemanite (Ca2B6O11.5H2O). Al

occurs as bauxite, Al2O3•2H2O, cryolite (Na3AlF6) and also as aluminosilicates
(Al2O3.2SiO2.2H2O) and in clay. Ga and In occur in trace amounts in Zn and Al ores. Thallium is
rare, recovered from pyrites, FeS2 , CuFeS2

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4.2 Extraction

(i) B From borax

𝑁𝑎2 𝐵4 𝑂7 ∙ 10𝐻2 𝑂 + 𝐻𝐶𝑙 ⟶ 4𝐵(𝑂𝐻)3 + 2𝑁𝑎𝐶𝑙 + 5𝐻2 𝑂

B(OH)3 B2O3 + H2O

B2O3 + 3Mg 2B + 3MgO This is followed by washing with NaOH and HF to get

an amorphous solid

However, boron is normally used as borax. Most of the borax is prepared from colemanite.
Colemanite is treated with appropriate amounts of sodium carbonate to form borax and some
sodium metaborate. By passing CO2 through the mother liquor, the sodium metaborate is
converted to borax.

Ca2B6O11 + Na2CO3 2CaCO3 + Na2B4O7 + 2Na2BO2

4Na2BO2 + CO2 Na2CO3 + Na2B4O7

(ii) Aluminium

Al is obtained from bauxite especially where hydro-electric power is cheap available. The first
step is to separate Al from chunk of silicates and other metals such as Fe followed by precipitation
of the .hydroxide.

1. 𝐴𝑙2 𝑂3 + 𝑂𝐻 − + 3𝐻2 𝑂 ⟶ 𝐴𝑙(𝑂𝐻)−

4 + 𝑠𝑖𝑙𝑖𝑐𝑎𝑡𝑒𝑠

2. Precipitation with Al(OH)3 (seeding)

𝐴𝑙(𝑂𝐻)−
4 + 𝐴𝑙(𝑂𝐻)3 ⟶ 𝐴𝑙(𝑂𝐻)3 + 𝑂𝐻
−

(As seed)

Al(OH)3 Al2O3 + 3H2O

3.

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 4. Dissolve in cryolite (Na3AlF6) and electrolse using graphite(block) anode and graphite
cathode (bain)

Cathode 𝐴𝑙 3+ + 3𝑒 − ⟶ 𝐴𝑙
Anode 𝑂2− ⟶ 𝑂2 + 2𝑒 −
Ga, In, Tl are obtained from electrolysis of their salts.

4.3 Chemical Properties

4.3.1 Oxidation states

B is a nonmetal and does not form cations. Ionization energy is too high and cannot be
compensated by formation of a stable lattice. Other elements essentially metallic. Trivalent state
becomes less stable down the group

Al forms only Al3+. Some Ga(I) and In(I) are known. GaCl2 is actually GaCl/[GaCl3](mixed
oxidation state species). Tl + chemistry is quite common.

Tl3+ + 2e- Tl+ E0 = +1.25V

down hill

Tl2O3 Tl2O + O2
unstable 100oC stable

Electro positive character increases from B to Al then decreases from Al to Tl. Increase from B to
Al is expected, but not for heavier members. The extra d and f-electrons do not shield the nucleus
efficiently so that the valence electrons are held more firmly and the metals become less
electropositive; hence the ionization energy increases from Al to Th. Tl + (Thallous) compounds
are the most stable. The s electrons do not participate in bonding because the energy to unpair them
is too high. This is called inert pain effect.

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4.3.2 Reaction with air

Sesquioxides M2O3 of all the elements can be made by heating the elements in air.

𝐵(𝑠) + 𝑂2 (𝑔) ⟶ 𝐵2 𝑂3(𝑠) + 𝐵𝑁(𝑠)

 Al gets coated with tough Al2O3 layer.

o
𝐴𝑙 𝑔 + 𝑂2 800
⟶ C𝐴𝑙2 𝑂3 + 𝑠𝑜𝑚𝑒 𝐴𝐿𝑁

 Ga, In , stable in air but burn to from the oxides. Tl slowly oxidizes in air to Tl2O3
Structure: consists of triangular BO3 units each O binding to two B’s.

O
B
O O
B B
O O O

 B2O3 is acidic, reacting with water to form Boric acid B(OH)3.

B2O3 + H2O B(OH)3. Boric acid is a weak nonprotonic acid (Lewis acid).

B(OH)3 + H2O [B(OH)4]- pKA = 6.94

On reaction with NaOH,

𝐵2 𝑂3 + 2𝑁𝑎𝑂𝐻 ⟶ 2𝑁𝑎𝐵𝑂2 + 3𝐻2 𝑂

Sodium metaborate

 Al as well as Al2O3 is amphoteric.

2Al(s) + 6HCl(ag) 2 AlCl3(ag) + 3H2(g)

2Al(s) + 6H2O(l) + 2OH-(aq) 2[Al(OH)4]-(aq) + 3H2(g)

(strong base)

Al is made passive by nitric acid due to the formation of a protective layer of oxide.
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2Al(s) + 2HNO3(aq) Al2O3(s) + 2NO(g) + H2O(l)

Al2O3 + 6H+ 2Al3+ + 3H2O …..as a base.

Al2O3 + 2OH- + 3H2O 2[Al(OH)4]- …..as acid

Aluminate ion

 Ga2O3 is also amphoteric, forming GaCl3 and BaGaO2 (sodium gallate) on reaction with
HCl and NaOH, respectively.

 In2O3 is basic - InCl3

- No reaction with NaOH
- TI2O3 is basic unstable 𝑇𝐼2 𝑂3 ⟶ 𝑇𝐼2 𝑂 + 𝑂2
Hydroxides

Al Hydroxide is amphoteric.

Al3+ + H2O H+ + Al(OH)3 + OH- [Al(OH)4]-

Ga(OH)3 is amphoteric. In(OH)3 is basic. TI forms TI(OH) (Thallous hydroxide)

𝑇𝐼2 𝑂 + 𝐻2 𝑂 ⟶ 2𝑇𝐼𝑂𝐻 or

Or 𝑇𝐼2 𝑆𝑂4 + 𝐵𝑎(𝑂𝐻)2 ⟶ 𝐵𝑎𝑆𝑂4 + 2𝑇𝐼𝑂𝐻

4.3.3 Reaction with hydrogen

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Boron does not react directly with H2 to form hydrides. They are prepared indirectly by reduction
of their chlorides with LiH or LiAlH4. B forms a series of volatile, electron deficient hydrides
called boranes such as BnHn+4 series-B2H6 (diborane), B5H9 (pentaborane-9) and BnHn+6 series-
B5H11 (pentaborane-11), B10H16 (decaborane-16).

Synthesis
ether

4𝐵𝐶𝑙3 + 3𝐿𝑖𝐴𝑙𝐻4 ⟶ 2𝐵2 𝐻6 + 𝐴𝑙𝐶𝑙3 + 3𝐿𝑖𝐶𝑙

H
H H
B2H6 B B
H H
H

Boranes react with water to form boric acid, liberating hydrogen.

𝐵2 𝐻6 + 6𝐻2 𝑂 ⟶ 2𝐻3 𝐵𝑂3 + 6𝐻2

On heating with hydrogen, Al forms AlH3.

2Al(s) + 3 H2(g) 2AlH3(s)

Ga and In form polymeric electron-deficient hydrides of the form (MH3)

Synthesis

3𝐿𝑖𝐻 + 𝑀𝐶𝑙3 ⟶ 3𝐿𝑖𝐶𝑙 + 𝑀𝐻3

𝑥𝑀𝐻3 ⟶ (𝑀𝐻3 )𝑥 M = Ga, In

With excess LiH form LiMH4

3𝐿𝑖𝐻 + 𝑀𝐶𝑙3 ⟶ 𝐿𝑖𝑀𝐻4− + 𝐿𝑖𝐶𝑙

No hydride of Tl is known. Tl+ resembles Ag+ rather than alkali metals.

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 4.3.4 Reaction with nonmetals
(i) Reaction with halogens
All elements form tri-halides. B forms gaseous covalent BX3 which is SP2 hybridized (trigonal
planner)
Synthesis

CaF2
B2O3 BF3
H2SO4

On heating, B reacts with chlorine to form the chloride.

2B + 3Cl2 2BCl3

BCl3 readily hydrolyzed in water. BF3 partially hydrolyzed

BCl3 + 3H2O H3BO3 + 3HCl

4BF3 + 6H2O BF4- + 3B(OH)3 + 3H3O

AlF3 is ionic and sparingly soluble in water (only ionic halide of Al)

2Al + 3F2 AlF3

Tri-chlorides of Al, Ga, In are partly covalent and dimeric (M2Cl6). Are fairly soluble in water

2M + 3Cl2 ⟶ MCl3

MCl3 + 3H2O M(OH)3 + 3HCl

Reaction of AlCl3 with water is interesting. On addition of small amount of water, white fumes of
HCl are formed together with the hydroxide. On addition of more water, they dissolve to form
Al3+

AlCl3(s) + H2O(l) Al(OH)3(s) + HCl(g)…….Small amount (drop) of water

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AlCl3(s) + H2O(l) AlCl3(aq)……..Large amount of water

Aluminium salts form acidic aqueous solutions due to the reaction;

[Al(H2O)6]3+ H2O [Al(H2O)5OH]2+ + H3O+

TlCl3 is unstable. Readily forms thallous chloride, TlCl.

Hydrolysis of BCl3 is similar to that of SiCl4 (diagonal relationship)

𝐵𝐶𝑙3 + 𝐻2 𝑂 ⟶ 𝐵(𝑂𝐻)3 + 𝐻𝐶𝑙

𝑆𝑖𝐶𝑙4 + 𝐻2 𝑂 ⟶ 𝑆𝑖(𝑂𝐻)4 + 𝐻𝐶𝑙

Al2Br6 and Al2I6 similar to Al2Cl6

The di-halides MCl2 (m = Ga, In) are actually (M+Cl- /M3+3Cl-)-mixed oxidation state halides.

Nitrides

BN and AlN made by action of NH3 or N2 on boron or B2O3 with C in a stream of N2.

𝐵2 𝑂3 + 𝐶 + 𝑁2 ⟶ 3𝐶𝑂 + 2𝐵𝑁
Very stable

AlN is hydrolyzed by cold water.

𝐴𝑙𝑁 + 3𝐻2 𝑂 ⟶ 𝐴𝑙(𝑂𝐻)3(𝑠) + 𝑁𝐻3

Ga and In nitrides made by heating the metals in NH3. They are very stable. This forms TlN with
NH3(l).

(ii) Carbides
B4C3 is very hard and very stable (similar to SiC)

Al4C3 is readily hydrolyzed

electric discharge
B + 4C B4C3

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 1000oC
Al + C Al4C3 + 12H2O Al(OH)3 (S) + 3CH4 (g)

Ga,In and Tl carbides are not known. This implies that Al is more electropositive than Tl

(iii) Sulphides; M2S3

Made by heating the elements with S.

Are readily hydrolyzed

𝑀2 𝑆3 + 6𝐻2 𝑂 ⟶ 3𝐻2 𝑆 + 2𝑀(𝑂𝐻)3 M=B, Al, Ga

In2S3 is not hydrolyzed

Tl2S3 is unstable instead it forms Tl2S e.g.

2𝑇𝑙𝑁𝑂3 + 𝐻2 𝑆 ⟶ 𝑇𝑙2 𝑆 + 2𝐻𝑁𝑂3

(iv) Oxysalts
M2(SO4)3 form alums and readily hydrolyzed: m = Al, Ga, In, Tl

𝑀2 (𝑆𝑂4 )3 + 6𝐻2 𝑂 ⇌ 2𝑀(𝑂𝐻)3 + 3𝐻2 𝑆𝑂4

Tl2SO4 is soluble in water but not hydrolyzed . M(NO3)3 is soluble in water and readily
hydrolyzed.

TlNO3 not.

4.3.5 Complex formation

Group III elements form complexes much more readily than the S-block elements due to their
small size and high charge density. B forms NO cationic complex (only anionic).

e.g. [BCl4]-, [BF4]-. These are tetrahedral complexes – utilizing s and p orbitals in sp3 hybridization.

Al, Ga, and In form cationic and anionic c and omplexes such as [Al(H2O)6]3+, [GaCl6]3- [InCl6]3-
which are octahedral- utilizing s,p as well as d orbitals in sp3d2 hybridization.
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4.3.6 Uses of group II elements and compounds

(i) Borax has many uses such as in manufacture of detergents, as insecticide, antiseptic and
antifungal.

(ii) Borax is an additive in the manufacture of chemically resistant glassware.

(iii) Aluminium is used in the manufacture of cookware and cutlery

(iv) Aluminium alloys are used in the manufacture of automobile and aircraft parts due to its light
weight and high tensile strength.

(v) Alum is used as a flocculant in water treatment.

(vi) GaAS is used in manufacture of semiconductors as well as LEDs, diodes and lasers.

Differences between B and other group III Members

(i) B is the only nonmetal in group III

(ii) B does not form a cationic complex. Only anionic complexes.
(iii) Its chloride BCl3 is hydrolysed to form boric acid. Others form hydroxides.

Diagonal relationship – B and Si

1. Similar physical properties and both are practically non-condensers of heat and electricity.
2. Both are made by reduction of oxide with and electropositive metal e.g. Mg
3. Their chlorides (BCl3 and SiCl4) are hydrolyzed by water to give acids
4. Form a series of volatile covalent hydrides
Boranes and silanes
B2H6 SiH4
5. Both B2O3 and SiO2 are acidic
6. B4C3 and SiC are hard, chemically unreactive substances

10