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Aluminium - Al
Gallium - Ga
Indium - In
Thallium - Tl
Members of Group13 are:
2
General Properties
Boron is the only group 13 element that is a non-
metal.
The remaining members of this group are fairly
reactive metals, and are called p-block elements.
Aluminium, Al, is the third most abundant element
in the Earth's crust and the rest elements are much
less common.
All elements show a stable oxidation state of +3,
except for thallium.
3
The small sizes of the ions, their high charge
and large values for their sum of the First
ionization energy suggest that the elements
are largely covalent.
4
Unlike the s-block elements, some of the elements
of this group display lower valency state in
addition to the group valency. The heavier
elements in this group show an increased tendency
to form univalent compounds, and univalent thallium
compounds are the most stable.
6
Appearance
Group 13 metals have silver luster and erratic
variation in melting points down the group. B(2300
C), Al(660.4 C), Ga(29.78 C), In(152.6 C) and
Tl(303 C),
8
Aluminium has a close-packed metallic
structure but is on the borderline between
ionic and covalent character in its
compounds.
9
It should be borne in mind that group 13 is the
first group of the periodic table to contain a
non metal (Boron). The remaining elements
of group 13 are metals (sometimes called
poor metals).
10
Reason
This increase of electropositivitity from Boron to
Aluminium is the the usual trend according or
associated with increasing size. However, B and Al
follows immediately after s block elements,
while Ga, In and Tl follows after d block
elements. So the extra d-electrons in Ga, In and Tl
do not shield the nuclear very effectively, so that the
orbital electrons are more firmly or tightly held and
the metal are less electropositive. This is evidenced
by the increase of ionization energy between Al and
Ga even though the large atom would be expected to
have a lower value
11
Occurrence and Extraction
Group 13 elements are not found free in nature, but
are all present in various minerals and ores.
Aluminiun is the most abundant metal in the Earth's
crust making up 8% of the Earth's crust and it is
occurring in igneous rocks such as:
12
Micas (group of sheet silicate mineral chemically
given by general formula X2Y4-6Z8O20(OH, F)4
where X = K, Na or Ca; Y = Al, Mg, Fe and Z = Si)
13
Spinel (MgAl2O4)
Bauxite (Al2O3..H2O)
14
Aluminum (Al), among Group 13 metals exists
as aluminosilicates in the Earths crust and is
more abundant than iron.
17
Introduction
Aluminum is the most important metal in the Boron
Family. It is a metal with the chemical symbol Al and
atomic number 13. It has the electron configuration
[Ne]2s22p1 and mainly have the oxidation state of +3.
20
EXTRACTION OF ALUMINIUM
The most important aluminium-containing minerals
are bauxite (Al2O3..H2O) and cryolite (Na3AlF6).
Aluminium is the most widely used element in this
Group.
It is obtained by the electrolysis of aluminium
oxide, which is purified from bauxite.
The melting point of the aluminium oxide is too
high for electrolysis of the melt, so instead it is
dissolved in molten cryolite, Na3AlF6 (Sodium
hexafluoroalumiminate)
21
Aluminium is quite an electropositive and
reactive and cannot be extracted chemically
using carbon as a reducing agent from its ore,
bauxite because it forms carbide.
22
Bayer Hall Herout processes 23
2Al2O3(l) + 3C 4Al (l) + 3CO2 (g)
2Al2O3(l) + 3C 4Al (l) + 3CO2 (g)
24
o Next, the Hall-Hroult process involves an
electrochemical cell and pure Al2O3 as the feed
material. It is dissolved in a molten Cryolite,
Na3AlF6, itself modified by the addition of AlF3,
CaF2 and others, which brings the melting point
to 9501000C). The addition of the cryolite
therefore saves energy operational cost.
o At the cathode, the Al2O3 is reduced to molten
Al. At the anode, oxygen from the alumina reacts
with the C electrode to form CO2(g). The overall
cell reaction is written as:
2Al2O3(l) + 3C 4Al (l) + 3CO2 (g)
25
Note that in this process, molten Bauxite
(Al2O3.nH2O) is the electrolyte. The melting point of
Bauxite is high above 2000C. This mean that large
amount of energy is needed. To minimize the energy
operational cost, some cryolite (Na3AlF6 ) reduces the
melting point to about 1000C. The aluminium metal
is produced at the cathode and oxygen is liberated at
the anode where it reacts with carbon electrode to
form CO2 gas.
26
The electrical conductivity of Al is about 60%
that of copper. Its use in electrical
transmission is favoured by its lightness and
prices
27
EXTRACTION OF BORON
28
Boron is found in ores widely distributed in
Earth's crust.
Largely, boron is found in concentrated
deposits, as borax, that is hydrated borates,
Na2B4O7.10H2O and similar tri, tetra and
pentaborates of calcium and sodium.
On reduction scale, Boron is formed by
magnesium or sodium reduction of the oxides
(B2O3) or using H2 in the BCl3 in the presence
of Tungsten (W) filament
29
Preparation of some boron compound from
Borax is as outlined below
30
Boron
o Boron is the top element of group 13 and is
the only non-metal of this group and the its
crystalline form is very hard, inert and non-
conducting.
o the amorphous form of Boron (which is more
common than crystalline) is much more
reactive.
o reacts directly with other metals to give hard,
inert binary compound of various formulae
called borides, which resembles the carbides
and nitrides, that is:
B + M M2B, MB, M3B4, MB2, MB4, MB6, MB12. 31
It has the electron configuration [He]2s22p1 and
mainly the oxidation state of +3.
32
Boron forms hydrides and the simplest boron
hydride found is diborane, B2H6. Boron hydrides
are used to synthesize organic compounds.
One main compounds used to form other boron
compounds is boric acid. Boric acid is a weak
acid and may be formed by the following
reaction
B2O3 (s) + 3 H2O (l) 2B(OH)3 (aq)
Boric acid
B(OH)3 (aq) + 2H2O(l) H3O+(aq) + B(OH)4-(aq)
33
Boric acid can be found in products that we
use in our daily lives, such as disinfectants,
insecticide, glass, bleaches, and dyes.
Boron produces a green flame.
Research indicates Boron may be beneficial
for the treatment of arthritis.
34
Gallium, Indium and Thallium
36
Gallium is one of three elements that naturally occur
as a liquid at or close to room temperature, the other
two being mercury and Cesium. Ga has a melting
point of 29.76 C and a boiling point of 2204 C
37
Gallium is an important element in the
electronics industry and has applications as
doping material in semiconductors. One of the
most important of these materials is gallium
arsenide, GaAs, which can produce laser light
directly from electricity and is used in diode
lasers and Light Emitting Diodes (LEDs)
The fluorescent compound MgGa2O4 is used
in photocopiers.
Due to it's melting point, gallium melts in our
hands.
38
Indium, In
Indium has the chemical symbol In and atomic
number 49. It has the electron configuration [Kr]
2s22p1 and may have +1 or +3 oxidation state.
However the +3 oxidation state is more
common. It is a soft malleable metal and similar
to gallium, indium can form InAs which is found
in photoconductors in optical instruments.
39
Indium is also extracted by electrolytic
process and like gallium is also an important
element in the electronics industry.
Many indium compounds find applications in
semi-conducting materials for transistors,
thermistors and photo-active devices, e.g. A
thin layer of indium tin oxide can be found on
LCD displays, such as through the monitor in
which you are reading (see next slide)
40
Screen on the keyboard containing a thin layer of
indium tin oxide
41
Thallium, Tl
Thallium has the chemical symbol Tl and atomic number
81. It has the electron configuration [Xe] 2s22p1 and has the
+3 or +1 oxidation state. Since thallium is heavier, it has a
greater stability in the +1 oxidation state (inert pair effect).
Hence, it is found more commonly in its +1 oxidation state.
Thallium is soft and malleable. It is very poisonous but
nevertheless it is still used, such as for high-temperature
superconductors. For its toxicity, thallium was widely used
in insecticide and rat poison but in 1975, its uses was
prohibited. Currently its usage is limited and must be
handled with care.
42
Thallium is extracted from the fine dusts from the
sulphide ores of other elements by dissolution in
warm dilute acids. It is then separated from
impurities and purified by electrolysis and deposition
43
The electrical conductivity of thallium sulphide
changes with exposure to infrared light, and
so this compound is used in photocells.
46
Physical Properties of Group 13 metals
47
Property B Al Ga In Tl
49
The influence of the non-metallic character in
this Group is reflected by the softness of the
metals.
The melting points of all the elements are
high, but the melting point of boron is much
higher than that of beryllium in Group 2,
whereas the melting point of aluminium is
similar to that of magnesium in Group 2
(diagonal relationship).
The densities of all the Group 13 elements
are higher than those of Group 2 elements.
50
The ionic radii are much smaller than the
atomic radii.
This is because the atom contains three
electrons in a quantum level relatively far
from the nucleus, and when they are
removed to form the ion the remaining
electrons are in levels closer to the nucleus.
In addition, the increased effective nuclear
charge attracts the electrons towards the
nucleus and decreases the size of the ion.
51
CHEMICAL PROPERTIES
GROUP 13 ELEMENTS
52
The chemical properties of Group 13 elements reflect
the increasingly metallic character down the group.
Here only boron and aluminium will be considered.
Boron is chemically unreactive except at high
temperatures.
53
Boron reacts with nitric acid and sulphuric acid and
liberates hydrogen with NaOH
56
Oxides (M2O3) -SESQUIOXIDE
The M2O3 of all the elements can be made by
heating the elements in oxygen:
4M (s) + 3O2(g 2M2O3 (s)
though B2O3 is more usually made by dehydrating
boric acid (refer the reaction profile provided below)
Note
Sesquioxide is an oxide containing three atoms of
oxygen with two atoms (or radicals of another
element. For example, aluminium oxide (Al2O3) is a
sesquioxide.
57
100 oC Red hot
-H2O -H2O
B(OH)3 HBO2 B2O3
Orthoboric acid +H2O +H2O Boron oxide
Metaboric acid,
which exists in
three crystalline
forms of which
contains the cyclic
unit
H OH
O B
OH B O
O B
OH
H
58
H3BO3 is a weak acid. Its weakly acidic nature is
due to its electron deficient tendency. The electron
deficiency B(OH)3 accepts an OH- ion from the self
ionization of water forming a complex ion:
-
B(OH)3 + 2H2O [B(OH)4] + H3O+
59
So a source of H3O+ in B(OH)3 (aq) is water
itself. The ionization and the fact that B(OH)3
is a monoprotic (not triprotic) acid imply that
the reasonable formula of boric acid is B(OH)3
and not H2BO3.
60
Upon titration with NaOH solution, H2BO3
gives salt of sodium and water:
61
Oxides of oxidation state +3 of the Group 13 Elements
Oxide Property
B2O3 Weak acid
many metal oxides gives glasses
with B2O3 as in the borax bead test
Al2O3 and Ga2O3 Amphoteric
In2O and Tl2O3 Weak basic
Tl2O3 gives O2 and Tl2O on heating
to 100 C
62
Boric oxide and borates find extensive
application. Borax (NaB4O7.10H2O) and other
borates find use in water treatment and in
preserving timber from insect. Large amount
of sodium or calcium borates and of boric
acid or oxides are used in glass manufacture.
64
B2O3, (s) is a non-metallic oxide which is acid in its
properties. On heating with metal oxide it gives
metaborates which often have characteristic colours.
This is the basis of the borax beads test
D
CoO (s) + B2O3 Co(BO2)2
65
Oxides of Aluminium
67
2Al(s) + 3H2O Al2O3 + 6H+ + 6e
Al2O3 is:
o an amphoteric and ionic compound. This is due
to small Al3+ ions and small O2- ion making a
strong ionic bond.
o made by dehydrating Al(OH)3 or from elements
68
Accordingly Al is used in the thermite
reduction of metal oxides
3Mn3O4 + 8Al 4Al2O3 + 9Mn
69
Al(OH)3 is an amphoteric and when
(i) acts as a base, gives salts with acids which
contain the [ Al(H2O)6 ]3+ ion
(ii) acts as acid give rise to salts called aluminates,
which contain AlO2- or AlO33-.
Al(OH)3 H+(aq) + AlO2- + H2O
Al(OH)3 3H+(aq) + AlO33-
71
HALIDES OF GROUP 13 ELEMENTS
All elements form trihalides. They are nonpolar trigonal
planar molecules in which the boron atom is sp2
hybridized
The halides of boron are BX3 are all volatile, highly
reactive, covalently bonded molecular compounds
and are gases
Boron halides are all hydrolyzed by water
The Boron fluoride (BF3) form fluoroborates, and the
other halides giving boric acids
BF3 + H2O [BF3OH] H
BCl3 + H2O H3BO3 + 3HCl
72
Boron (an electron deficient atom) in BX3 has
6 electrons in its outer shell. It can readily
accept a lone pair of electrons from a donor
atom (O, N, P or S ). This tendency makes
BF3 a useful organic catalyst for Friedel Craft
reaction such as:
Alkylations
Acylation
Estirification
Polymerization of olefines
73
The fluorides of: Al, Ga, In, and Tl are
ionic having high melting points. The other
halides are covalent when anhydrous. AlCl3 ,
AlBr3 and GaCl3 exist as dimers thus attaining
an octet of electrons
74
This dimeric formula is
retained or prevails when
the halides dissolves in
non-polar solvent (e.g.;
Benzene). But because of
high heat of hydration
when halides dissolves in
water, the covalent dimer
Figure. 1 is broken into [M.6H2O ]3+
and 3X -
75
Aluminium, Gallium and Indium all form
trifluorides, MF3 which are ionic in nature and
have high melting points (~ 1000 C).
The chlorides, bromides and iodides of
these metals are covalent and much more
volatile, having much lower melting points.
They exist as dimeric molecules with the
formula M2X6 using two halide atoms to
bridge the metals which have tetrahedral
configuration as shown in Figure 1 above.
They are also soluble in non-polar organic
solvents.
76
o The most important halide of boron is boron
trifluoride, which is a gas.
77
o Both boron chloride and aluminium chloride act
as Lewis acids to a wide range of electron-pair
donors, and this has led to their widespread
use as catalysts. Aluminium chloride is used in
the important Friedel-Crafts reaction
78
AlCl3 + C2H5 O C2H5
Lewis Acid dimethyl ether ( Lewis base )
79
o AlX3 is used in a number of reactions in which
by means of adduct formation they act as
catalyst. For example when BENZENE is
treated with Acyl halide (ClCOR ) in the presence
of anhydrous AlCl3 as catalyst Aromatic
ketone
80
SELF ASSESSMENT QUESTION ( SAQ)
a. By making use of chemical equation from a summary diagram
of the reaction chemistry, write chemical equation for the
successive conversions of borax to:
(i) B2O3
(ii) Boric acid
(iii) Impure boron metal
b. Using the summary diagram of the reaction chemistry, write chemical
equation for the sequence of the reaction by which borax is converted to
diborane and BF3
c. Predict the probable products of the following reaction and write the
balanced chemical equations
i. BF3 and excess NaF in acid aqueous solution
ii. BCl3 and excess NaCl in acidic aqueous solution
iii. BBr3 and excess NH(CH3)2 a hydrocarbon solvent
81
Compounds of Boron with Electronegative
Elements
BX3 (Boron halides) are very useful reagents and
Lewis acid catalysts.
83
Properties of Boron trihalides
84
Their structures are trigonal planar and
monomeric (they do not dimerized in the way
the BH3 does.) As an example, the structure of
BBr3 is shown below.
85
o The B-X bond distances are shorter than
might be expected, and the B-X bond
energies are correspondingly higher.
86
The structure of BX3
molecules. The boron
atom is sp2 hybridized.
Some evidence exists
that some - bonding
may occur between
the unhybridized 2p
orbital of the boron and
the filled (shaded) np
orbitals.
87
BX3 are Lewis acids and the order of their
strength in this role of Lewis acidity (i.e. the
sequence of acidic strength is
BF3 < BCl3 < BBr3
in contrary to the order of electronegativity of
the attached halogens (F > Cl > Br).
z z
p bond y
x x
p bond
90
BX3 (all) forms simple Lewis complexes with
suitable bases, e.g.;
BF3(g) + NH3(g) F3B-NH3
91
The boron halides, like boric acid, are Lewis
acids; that is they can readily accept a pair of
electrons into their vacant, unhybridized p
orbitals. Fox example
BF3 + F BF4-
BF3 + R-O-R F3BOR2
The chlorides, bromides and Iodides of Boron are
susceptible to protolysis by mild proton sources
such as: H2O, alcohol (ROH), Amine (RNH2). For
example on hydrolysis of BCl3:
92
BCl3(g) + 3H2O(l) B(OH)3 aq + 3HCl(aq)
The reaction is so rapid with the formation of
complex Cl3B-OH2, which then eliminates HCl
and reacts further with H2O
B(OH)3
B(NH2)3 H2O
B(OR)3
RNH2
PROT OLYSIS This reactivity chart
ROH
does not apply to
BX3 BF3, which resists
PR3 NR3 protolyis reactions
SR2
under mild conditions.
COMPLEX FORMATION
X3BPR3 X3BNR3
X3BSR2
Exercise 2
If Aluminium reacts with air and dissolves in
both acid and basic solution, explain why it
does not dissolve in pH-neutral water?
95
Sulphate of Group 13
Aluminium (III) sulphate is sometimes added
to water supplies in order to remove fine
particles, colour and bacteria.
97
Thallium (I) sulphate has been used as a
rodenticide, Note that Thallium (I) sulphate
was used by Saddam Hussein (and others)
as choice of poison for dealing with Iraqi
dissidents.
98
Hydroxides
99
When Al(OH)3 dissolves in a base, hydroxide
ion and water bonds to Al ion forming a
complex ion [ Al( H2O )2 (OH)4 ]- . The reaction
is as follows
100
Exercise 3
Insoluble hydroxide of Mg and Al can be
prepared by addition of a solution of a soluble
hydroxide (NaOH) to a solution of salts of Mg
or Al chlorides, nitrates or sulphates. Explain
why an excess of hydroxide solution is
avoided in the preparation of Al(OH)3 ?
Exercise 4
Explain why a lot of energy is consumed in the
electrolytic production of aluminium?
101
Hydrides
Special compounds that start of predominantly
covalent and become more ionic as we go down the
group.
102
The 8 well characterized boranes which fall
into two series BnHn+4 and less stable series
BnHn+6 are
1. B2H6 Diborane
2. B4H10 Tetraborane
3. B5H9 Pentaborane (stable)
4. B5H11 Pentaborane (unstable)
5. B6H110 Hexaborane
6. B9H15 Nonaborane (enneaborane)
7. B10H14 decaborane
8. B10H16 decaborane
103
Many boron compounds lack an octet of
electrons about the central boron atom. This
feature make:
boron compounds electron deficient, and therefore
make them strong Lewis acids.
The electron deficiency of some boron compounds
leads to bonding type that have not previously
encountered especially in boron hydride:
104
Definitions
105
No BH3 as it does not exist as separate molecules
The simplest hydride is B2H6 and is an example of
electron deficient molecules or compound
Boron Hydride
The molecule (borane, BH3) may exists as a reaction
intermediate, but it has not been isolated as a stable
compound.
The B-atom in BH3 lacks the complete octet (i.e. it
has only 6 electrons in the valence shell). The
simplest boron hydride that have been isolated is
diborane (B2H6).
106
The Structure of B2H6 (Diborane) Multicentre Bonds
108
Figure 4. The Structure of B2H6 (diborane) multicentre bonds.
Contains a 3-centre-2-electron bond (called a banana bond)
109
Bridging B-H have a bond order of and this
accounts for the 1600 cm-1 B-H str in the IR.
110
1s 2s 2p
Hybridization
1s 2s 2p
Hybridized orbital (sp3)
111
Now consider one of the B atoms
112
For each bridge therefore one sp3 orbital from
each of the B atoms combines with the 1s
orbital of the bridging H-atom to form three
new molecular orbitals [recall that n(AO) forms
n(MO)]. One B atom gives its remaining
valence electron to one bridge and the other B
atom gives to the other. Each bridge,
therefore, has two electrons, which fill our new
MO scheme starting with the lowest energy
bonding MO (Figure 4)
113
Figure 4. Molecular Orbital Energy diagram for
Diborane
114
This MO diagram are two sp3 hybrids from each B
and the two 1s AOs for the bridging H atoms.
115
The boranes are volatile and decomposes to
B and hydrogen (H2) at red heat
The boranes are volatile and decomposed by
water or aqueous alkali
B2H6 + 6H2O H3BO3 + 6H2 (g)
Boric acid
All boranes reacts with NH3 and the products
depends on the condition imposed. For
example
116
Excess NH3
B 2H 6 B2H6 .2NH3
Low temperature
Excess NH3
B 2H 6 ( BN )x ( Boron nitride)
High temperature
2NH3 : 1 B2H6
B2H6 B3N3H6 ( Borazole or Borazine )
Low temperature
117
B2H62NH3 D
B3N3H6 (Borazole or
Borazine formely called inorganic benzene)
Borazine
119
The Chemistry of B2H6
NaH + B2H6 NaBH4
sodium borohydride an excellent
reducing agent used in organic
chemistry
B2H6 spontaneously flammable in air
B2H6 + O2 B2O3 + H2O VERY EXOTHERMIC
B2H6 reacts with many Lewis bases, even
weak ones:
B2H6 + 2CO 2H3B-CO
also R3N: and R2O etc..
120
Boric Acid B(OH)3
Boron oxide is an acid anhydride that reacts with
water to afford boric acid.
B2O3 + 3H2O 2B(OH)3
Boric acid which in aq. solution is a mild antiseptic
eye and mouthwash, has a planar structure.
The boron atom assumes sp2-hybridization whereas
the oxygens are sp3. The
VSEPR theory predicts that the O-B-O bond angle is
120, whereas the B-O-H angle is somewhat less
than 109.5, due to the presence of the two lone
pairs on each oxygen
121
Complexes
However group 13 elements form complexes much
more readily than the s-block elements on account of
their small size and increased charge density. In
addition to the tetrahedral hydride and halide
complexes, LiAlH4 and H[BF4], many octahedral
complexes such as [GaCl6]3-, [ InCl6 ]3- and [ TlCl6 ]3-
are known.
O C O
CH
O C O M
M
C M
CH3 O C O N
O
3
3 3
Figure 5
123
Oxidation States and Ionisation Energies
124
The outermost p electron is easy to remove as
it is furthest from the nucleus and well
shielded from the effective nuclear charge.
The next two s electrons are also relativeIy
easy to remove. Removal of any further
electrons disturbs a filled quantum shell so is
difficult. This is reflected in the ionization
energies. The first three ionization energies
are low, and the fourth very much higher.
125
Industrial Information / application
Boron has limited uses, but is used in flares to
provide a highly visible green colour. Boron filaments
are now used extensively in the aerospace industry
as a lightweight yet strong material. Boric acic acid is
used as a mild antiseptic, and borax as a water
softener in washing powders. Borosilicate glass
contains boron compounds.
126
Aluminium is one of the most industrially
important materials.
It is light, non-toxic, has a high thermal conductivity,
can be easily worked and does not corrode due to its
oxide coating, which is very effective although only
10nm thick.
It has several domestic uses such as cooking
utensils, aluminium foil and bottle tops, and is widely
used in the building industry where a strong, light,
easily-constructed material is required. These
properties also make it invaluable in the building of
aeroplanes and spacecraft
127
Boron compounds are used in variable
products such as: adhesive, cement,
disinfectants, fertilizers, fire retardants
(extinguisher), glass, herbicides, metallurgical
fluxes and textile bleaches and dyes.
128
Conceptual Problems
1. In contrast, BX3, AlX3 are dimers in the gas phase.
For example Aluminium chloride has a molecular
formula Al2Cl6 in the vapour phase:
(a) Draw the structure of Al2Cl6
(b) Explain why the molecule is a self acid-base complex
(c) What is meant by dimer and what is the dimer of AlCl3
(give formula)
2. In the Down process, the starting material is Mg2+ in
sea water and the final product is Mg metal. This
process seems to violet the principle of
conservation of charge. Does it? Explain
129
3. Arrange the following compounds in the
expected order of increasing solubility in
water and give the basis for your choice or
arrangement: Li2CO3, Na2CO3 and MgCO3.
130