THE GROUP13 ELEMENTS (BORON GROUP)

GENERAL PROPERTIES
Electronic configuration
Element Electronic configuration ( ns 2 np 1 )

5B 1s 2 ,2 s 2 2 p 1 or [He ] 2 s 2 2 p 1

13 Al 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 1 or [ Ne ] 3 s 2 3 p 1

31 Ga 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 1 or [ Ar ] 3 d 10 4 s 2 4 p 1

49 In 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 6 4 d 10 ,5 s 2 5 p 1 or [Kr ] 4 d 10 5 s 2 5 p 1

81 Tl 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3 d 10 ,4 s 2 4 p 6 4 d 10 4 f 14 ,5 s 2 5 p 6 5 d 10 ,6 s 2 6 p 1 or [ Xe ] 4 f 14 5 d 10 6 s 2 6 p 1

Physical properties
(1) A regular increasing trend in density down the group is due to increase in size.
(2) Melting points do not vary regularly and decrease from B to Ga and then increase.
(3) Boron has very high m.pt because it exist as giant covalent polymer in both solid and liquid
state.
(4) Low m.pt of Ga (29.80C) is due to the fact that consists of only Ga2 molecule; it exist as liquid
upto 20000C and hence used in high temperature thermometry.
(5) Boiling point of these elements however show a regular decrease down the group.
(6)The abrupt increase in the atomic radius of Al is due to greater screening effect in Al (it has 8
electrons in its penultimate shell ) than in B (it has 2 electrons in its penultimate shell)
(7)The atomic radii of group 13 elements are smaller than the corresponding s-block elements.
This is due to the fact that when we move along the period, the new incoming electron occupy
the same shell whereas the nuclear charge increases regularly showing more effective pull of
nucleus towards shell electrons. This ultimately reduces the atomic size.
(8) The atomic radius of Ga is slightly lesser than of Al because in going from Al to Ga, the
electrons have already occupied 3d sub shell in Ga. The screening effect of these intervening
electrons being poor and has less influence to decrease the effective nuclear charge, therefore
the electrons in Ga experience more forces of attractions towards nucleus to result in lower size
of Ga than Al
(9) Oxidation state
(i) All exhibit +3 oxidation state and thus complete their octet either by covalent or ionic union.
(ii) Boron being smaller in size cannot lose its valence electrons to form B3+ ion and it usually
show +3 oxidation no. The tendency to show +3 oxidation no. however decreases down the
group Even Al shows +3 oxidation no. in most of its compounds.
(iii) Lower elements also show +1 ionic state e.g Tl +, Ga+. This is due to inert pair effect. The
phenomenon in which outer shell ‘s’ electrons (ns2) penetrate to (n-1) d electrons and thus
become closer to nucleus and are more effectively pulled the nucleus. This results in less
availability of ns2 electrons pair for bonding or ns2 electron pair becomes inert. The inert pair
effect begins after n  4 and increases with increasing value of n.
(iv) The tendency to form M+ ion increases down the gp. Ga+1 < Tl+1
(10) Hydrated ions : All metal ions exist in hydrated state.
(11) Ionisation energy
 (i) Inspite of the more charge in nucleus and small size, the first ionisation energies of this
group elements are lesser than the corresponding elements of s block. This is due to the fact
that removal of electron from a p-orbitals (being far away from nucleus and thus less
effectively held than s-orbitals) is relatively easier than s-orbitals.
(ii) The ionisation energy of this group element decrease down the group due to increases in
size like other group elements.
(iii) However, ionisation energy of Ga are higher than that of Al because of smaller atomic
size of Ga due to less effective shielding of 3d electrons in Ga. Thus valence shell exert
more effective nuclear charge in Ga to show higher ionisation energies.
(12) Electropositive character
(i) Electropositive character increases from B to Tl.
(ii) Boron is semi metal, more closer to non-metallic nature whereas rest all members are
pure metals.
(iii) Furthermore, these elements are less electropositive than s-block elements because of
smaller size and higher ionisation energies.
(13) Oxidation potential
(i) The standard oxidation potentials of these element are quite high and are given below,
B Al Ga In Tl
E op for M  M + 3e –
0 3+
+1.66 +0.56 +0.34 +1.26
E op for M  M + e
0 +
– +0.55 – +0.18 +0.34
(ii) However Boron does not form positive ions in aqueous solution and has very low
oxidation potential.
(iii) The higher values of standard oxidation potentials are due to higher heats of hydration
on account of smaller size of trivalent cations.
(iv) Aluminium is a strong reducing agent and can reduce oxides which are not reduced even
by carbon. This is due to lower ionisation energy of aluminium than carbon. The reducing
character of these elements is Al > Ga > In > Tl.
(14) Complex formation : On account of their smaller size and more effective nuclear charge as
well as vacant orbitals to accept elements, these elements have more tendency to form
complexes than-s block elements.

Chemical Properties
(1) Occurrence : The important of this group elements are given below,

Boron : Borax (Tincal) (Na2B4O7.10H2O), Colemanite(Ca2B6O115H2O)

Boracite (2Mg3B8O15.MgCl2), Boronatro calcite(CaB4O7.NaBO2.8H2 O),
Kernite(Na2B4O7.4H2O), Boric acid (H3BO3)

Aluminium : Corundum (Al2O3), Diaspore (Al2O3.H2O), Bauxite (Al2O3. 2H2O), and Cryolite
(Na3AlF6).

(2) Hydrides
(i) Elements of gp 13 do not react directly with hydrogen but a number of polymeric hydrides
are known to exist.
(ii) Boron forms a large no. of volatile covalent hydrides, known as boranes e.g. B2
H6,B4H10,B5H11 ,B6H10 Two series of boranes with general formula BnHn + 4 and BnHn + 6
are more important.
(iii) Boranes are electron deficient compounds. It is important to note that although BX 3 are
well known, BH3 is not known. This is due of the fact that hydrogen atoms in BH3 have no
free electrons to form p-p back bonding and thus boron has incomplete octet and hence
BH3 molecules dimerise to form B6H6 having covalent and three centre bonds.
(iv) Al forms only one polymeric hydride (AlH3)n commonly known as alane It contains
A1…..H……Al bridges.
(v) Al and Ga forms anionic hydrides e.g. LiAlH4 and Li Ga H4 ,
4 LiH  AlCl 3   Li[ AlH 4 ]  3 LiCl
ether

(3) Reactivity towards air

(i) Pure boron is almost unreactive at ordinary temperature. It reacts with air to form B2O3
when heated It does react with water. Al burns in air with evolution of heat give Al2O3.
(ii) Ga and In are not effected by air even when heated whereas Tl is little more reactive and
also form an oxide film at surface. In moist air , a layer of Tl (OH) is formed.
(iii) Al decomposes H2O and reacts readily in air at ordinary temperature to form a protective
film of its oxides which protects it from further action.

(4) Oxides and hydroxides

(i) The members of boron family form oxide and hydroxides of the general formula M 2O3 and
M (OH)3 respectively.
(ii) The acidic nature of oxides and hydroxides changes from acidic to basic through
amphoteric from B to Tl.
B2O3 and B(OH)3> Al2O3 and Al(OH)3 >Ga2O3 and Ga(OH)3> In2O3 In (OH)3> Tl2O3 Tl(OH)3
(acidic) (amphoteric) (amphoteric) (basic) (strong basic)

Note : B(OH)3 or H3BO3 is weak monobasic Lewis acid.

(iii) Boric acid, B(OH)3 is soluble in water as it accepts as it accepts lone pair of electron to act
as Lewis acid. Rest all hydroxides of group 13 are insoluble in water and form a gelatinous
precipitate.
B(OH)3 + H2O B(OH)41-+H+
(iv) Al2O3 being amphoteric dissolves in acid and alkali both.
Al2O3 + 3H2SO4 Al2 (SO4)3 + 3H2O ; Al 2 O 3  2 NaOH  
fuse
2 NaAlO 3  H 2O
Sodium meta aluminate

(v) One of the crystalline form of alumina (Al2O3) is called corundum. It is very hard and used
as abrasive. It is prepared by heating amorphous form of Al2O3 to 2000 K.

(5) Action of Acids

(i) Boron does not react with non oxidizing acids, however, it dissolves in nitric acid to form
boric acids.
(ii) Al, Ga and In dissolve in acids forming their trivalent cations; however, Al and Ga become
passive due to the formation of protective film of oxides.
(iii) Thallium dissolves in acids forming univalent cation and becomes passive in HCl due to
the formation of water insoluble TICl.

(6) Action of Alkalies

(i) Boron dissolves only in fused alkalis, 2B + 6NaOH (fused)2Na3BO3 + 3H2

(ii) Al and Ga dissolves in fused as well as in aqueous alkalis,
2Al + 2 NaOH + 2H2O 2NAl O2 + 3H2
(iii) Indium remains unaffected in alkalies even on heating.

(7) Halides

(i) All the group 13 elements from the trihalides, MX3 on directly combining with halogens.
M + X2  MX3
(ii) All the trihalides of group 13 elements are known except Tl (III) iodide.
(iii) Due to small size and high electronegativity of boron, all boron halides are covalent and
Lewis acids. These exist as monomeric molecules having plane triangular geometry (sp 2
hybridization).
(iv) All Boron trihalides except BF3 are hydrolysed to boric acid.
BX3+ 3H2O B(OH)3 + 3HX; [X=Cl,Br,I]
However, BF3 forms as addition product with water, BF3 + H2O  H+ [BF3OH]-
BF3 having less tendency for hydrolysis as well as Lewis acid nature, is extensively used as a
catalyst in organic reactions e.g. Friedel- Crafts reaction.
(v) Boron atom, in BX3, has six electrons in the outermost orbit and thus it can accept a pair of
electrons form a donor molecule like NH3 to complete its octet. Hence boron halides act as
very efficient Lewis acids. The relative Lewis acid character of boron trihalides is found to
obey the order ;
BI3 > BBr 3 > BCl3 > BF3.
However, the above order is just the reverse of normally expected order on the basis
relative electronegativities of the halogens. Fluorine, being the most electronegative, should
create the greatest electron deficiency on boron and thus B in BF3 should accept electron
pair from a donor very rapidly than in other boron trihalides. But this is not true.
This anomalous behaviour has been explained on the basis of the relative tendency of the
halogen atom to back-donate its unutilised electrons to the vacant p orbitals of boron atom.
In boron trifluoride, each fluorine has completely filled unutilised 2p orbitals while boron
has a vacant 2p orbital. Now since both of these orbitals belong to same energy level (2p)
they can overlap effectively as a result of which fluorine electrons are transferred into the
vacant 2p orbital of boron resulting in the formation of an additional p – p bond. This
type of bond formation is known as back bonding or back donation. Thus the B- F bond
has some double bond character. Back bonding may take place between boron and of the
 three fluorine atoms and thus boron trifluoride is regarded as a resonance hybrid of some
structures.
Resonance in boron trifluoride is also evidenced by the fact that the three boron-fluorine
bonds are indentical and are shorter than the usual single boron-fluorine bond As a result of
back bonding, the electron deficiency of boron is reduced and hence Lewis acid nature is
decreased. The tendency for the formation of back bonding (p- p bond) is maximum
in BF3 and decreases very rapidly from BF3 to BI3 This is probably due to the fact that
overlapping of the vacant 2p orbitals of boron cannot take place easily with the p-orbitals
of high energy levels (3p in Cl, 4p in Br and 5p in iodine). Thus BI3 Br3 and BCl3 are
stronger Lewis acids than the BF3.
(vi) Lewis acid character of halides of the group 13 elements decreases in the order,B > Al >
Ga > In
(vii) Boron halides form complex halides of the type, [BF4 -], in which boron atom extends its
coordination number to four by utilising empty p-orbital. It cannot extend its coordination
number beyond four due to non availability of d-orbitals. However, the other trihalides of
this group form complex halides of the type (AlF6)3-, (GaCl6)3- and (InCl6)3-, etc where the
central atom extends its coordination number to 6 by the use of d-orbitals.
(viii) The fluorides of Al, Ga In and Tl are ionic and have high melting points. The high melting
points of metal fluorides can be explained on the basis that their cations are sufficiently
large and have vacant d-orbitals for attaining a coordination number of six towards the
relatively small fluorine atom.
(ix) Other halides of Al, Ga, In and Tl are largely covalent in anhydrous state and possess low
m.pt. These halides do not show backbonding because of increases in the size of the
element. However, the make use of vacant p-orbitals by co-ordinate bond i.e. metal atoms
complete their octet by forming dimers. Thus aluminium chloride, aluminium bromide and
indium iodide exist as dimers, both in the vapour state and in non-polar solvents.

Note : The dimer structure for Al2Cl6 is evidenced by the following facts,
(a) Vapour density of aluminium chloride measured at 400 0C corresponds to the formula Al2 Cl6.
(b) Bond distance between aluminium chlorine bond forming bridge is greater (2.21A0) than the
distance between aluminum-chlorine bond present in the end (2.06 A0). The dimeric structure
disappears when the halides are dissolved in water This is due to high heat of hydration which split
the dimeric structure into [M(H2O)6]3+ and 3X- ions and the solution becomes good conductor of
electricity.
Al2Cl6 + 2H2O 2[Al(H2O)6]3++6Cl- ; Therefore Al2Cl6 is ionic in water.
The dimeric structure may also split by reaction with donor molecules e.g. R 3N. This is due to the
formation of complexes of the type R3NAl Cl3 The dimeric structure of Al2 Cl6 exist in vapour
state below 473 K and at higher temperature it dissociates to trigonal planar AlCl 3 molecule.

Note: Boron halides do not exist as dimer due to small size of boron atom which makes it unable
to co-ordinate four large-sized halide ions.
(x) BF3 and AlCl3 acts as catalyst and Lewis acid in many of the industrial process.

Some dissimilarities of boron with other elements of this group

(i) Boron is a nonmetal, while all other elements of this group are metals.
 (ii) Boron forms only covalent compounds, while other elements of this group form both covalent and
ionic compounds.

(iii) Boron shows a maximum covalency of four, while other elements of this group show
a maximum valency of six, absorbs neutron and is steel grey in colour. Its density is
2.34 gm/cc.

BORON
ISOLATION OF BORON
Ores of boron
(i) Borax or tincal : Na2 B4O7 . 10 H2O
(ii) Kernit or Rasorite : Na2 B4O7 . 10 H2O
(iii) Colemanite : Ca2 B6O11 . 5 H2O
(iv) Orthoboric acid : H3BO3 (It occurs in the jets of steam called soffioni escaping from ground
in the volcanic region of the Tuscany). Boron is present to a very small extent (0.001%) in earth’s
crust.
(i) Reduction of boric oxide with highly electropositive metals like Na, K and Mg in the absence of
air.

B2O3 (s) + 6K(s)   2B(s) + 3K2O(s)

B2O3 (s) + 3Mg(s) 
 2B(s) + 3MgO(s)

The product thus obtained is boiled with HCl and filtered when K2O and MgO dissolves, leaving
behind elemental B. The powdered B thus obtained is thoroughly washed with water to free it from
HCl and is finally dried
(ii) Modern Method

B is obtained these days by the electrolysis of a fused mixture containing boric anhydride, MgO
and MgF2 at 1100C. The electrolysis is done in a carbon crucible, which acts as anode and Fe rod
is used as cathode. The Mg discharged at cathode reduces B2O3 to B.

2MgO  2Mg + O2

B2O3 + 3Mg  2B + 3MgO

B thus obtained is heated electrically in vacuum at 1100C, when the impurities are volatilised off
and pure boron is obtained.
(iii) By thermal decomposition of BI3 over red hot tungsten filament (Van Arkel method)

2BI3  2B(s) + 3I2(g)

W
1173 K

Chemical properties of boron

Crystalline B is not active while amorphous B reacts. The reactions are

as follows.

(a) Reaction with air

700°C
4B + 3O2 2B2O3
 700°C
2B + N2 2BN

The above reaction accompanies red flame.

High temp. & press.
BN + 3H2O      H3BO3 + NH3

(b) Action of alkali and acid

2B + 2NaOH + 2H2O  2NaBO2 + 3H2

High temp .
2B + 3H2O   
 B2O3 + 3H2
oxidation
2B + 3H2SO4 2H3BO3 + 3SO2
oxidation
2B + 6HNO3 2H3BO3 + 6NO2

(c) Boron reacts with Mg and consequent hydrolysis gives diborane.

3Mg + 2B  Mg3B2

3Ca + 2B  Ca3B2

Mg3B2 + 6HCl  3MgCl2 + B2H6

B2H6 + 6H2O  2H3BO3 + 6H2

(d) Boron reduces SiO2, CO2

3SiO2 + 4B  2B2O3 + 3Si

3CO2 + 4B  2B2O3 + 3C

COMPOUNDS OF BORON

Boron halides

(a) Boron trifluoride (BF3)

Preparation:

B2O3 + 3CaF2 + 3H2SO4 (conc.)  3CaSO4 + 2BF3 + 3H2O

B2O3 + 6KBF4 + 3H2SO4  3K2SO4 + 8BF3 + 3H2O

Properties: BF3 undergoes hydrolysis as

4BF3 + 3H2O  B(OH)3 + 3HBF4

B(OH)3 + 4HF  HBF4 + 3H2O

Two stage hydrolysis of BF3 is

H2O + BF3  H+ (BF3 OH)– 2 H[BF2(OH)2] + HF

H O
(b) Boron trichloride (BCl3)

Preparation:

B2O3 + 3C + 3Cl2  2BCl3 + 3CO

(volatile liquid)

When B2O3 is heated with PCl5 at 150°C, it forms BCl3

B2O3 + 3PCl5  2BCl3 + 3 POCl3

Properties
BCl3 hydrolyses as follows
BCl3 + 3H2O  B(OH)3 + 3HCl

H[BCl4] does not exist but H[BF4]exists

–50°C
BCl3 + 3NH3 B(NH2)3 + 3HCl

BCl3 + C2H5OH  BCl2 (OC2H5) + HCl

BCl3 + NOCl  [NO]+ [BCl4]–

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

Ether

Let us now discuss the acidic character of boron trihalides.

The shape of the BF3 molecule is a planar triangle with bond angles of 120°. This is predicted by
VSEPR theory as the most stable shape for three outer electron pairs around B. The valence bond
theory also predicts a planar triangle with hybridisation of one s and two p orbitals used for
bonding. However, the B atom only has six electrons in its outer shell and this is termed electron
deficient.
1s
Electronic structure of
boron atom excited state

three singly occupied orbitals form bonds with

unpaired electrons from three halogen atoms
2
shape: triangular planar (sp hybridization)

The bond lengths in BF3 are 1.30 Å each and are significantly shorter than the sum of the covalent
radii (B = 0.80 Å, F = 0.72 Å). The bond energy is very high: 646 kJ mol1, which is higher than for any
single bond. The shortness and strength of the bonds is interpreted in terms of a pp interaction, that is
the bonds possess some double bond character. The empty 2p z atomic orbital on B which is not involved
in hybridisation is perpendicular to the triangle containing the sp2 hybrid orbitals. This p z orbital may
accept an electron pair from a full pz orbital on any one of
the three fluorine atoms. Thus, a dative  bond is formed and the B atom attains an octet of electrons. If
one localized double bond existed, then there would be one short bond and two longer ones. However, all
measurements show that the three bond lengths are identical. The old valence bond explanation of this was
resonance between three structures with the double bond in different positions. The modern explanation is
that the double bond is delocalised. The pz atomic orbitals from B and the three F atoms form a
fourcentre  molecular orbital covering all four atoms which contains two bonding electrons .
 2p
2p
F
F B
F

The acidic strength of the trihalides is in order

BBr3 > BCl3 > BF3

The order is the reverse of what would be normally expected on the basis of electronegativity of
halogen and also on the basis of steric grounds.

This is explained on the basis of BX bonding. The tendency to form the pp double
bond is maximum in BF3 and decreases very rapidly as we move to BCl3 and BBr3.

Orthoboric acid (H3BO3)

Structure of orthoboric acid

Orthoboric acid contains triangular BO 33 units. In the solid, the B(OH)3 units are hydrogen
bonded together into twodimensional sheets with almost hexagonal symmetry. The layers are
quite a large distance apart and thus the crystal breaks quite easily into very fine particles.
H H

H H H H
B

H B H H B H

H H H H

H B H H B H

H B H
H H

H H
Hydrogen bonded structure of orthoboric acid

Preparation

Na2B4O7 + 2HCl + 5H2O  2NaCl + 4H3BO3

2CaO + 3B2O3 + 2SO2 + 9 H2O  2CaSO3 + 6H3BO3

2CaSO3 + 2H2O + 2SO2  2Ca (HSO3)2

Properties

H3BO3 + H2O  [B(OH4)] + H+ (aq)

Acidic properties of H3BO3 or B(OH)3 :

Since B(OH)3 only partially reacts with water to form H3O+ and [B(OH)4], it behaves as a weak acid.
Thus H3BO3 or [B(OH)3] cannot be titrated satisfactorily with NaOH, as a sharp end point is not obtained.
If certain organic polyhydroxy compounds such as glycerol, mannitol or sugars are added to the titration
 mixture, then B(OH)3 behaves as a strong monobasic acid. It can now be titrated with NaOH and the end
point is detected using phenolphthalein as indicator (indicator changes at pH 8.3  10.0).

B(OH)3 + NaOH Na[B(OH)4]  NaBO2 + 2H2O

Sodium metaborate

The added compound must be cisdiol, to enhance the acidic properties in this way.
(This means that it has OH groups on adjacent carbon atoms in the cis configuration). The cisdiol forms
very stable complexes with the [B(OH)4] formed by the forward reaction above, thus effectively
removing it from solution. The reaction is reversible. Thus removal of one of the products at the right
hand side of the equation upsets the balance and the reaction proceeds completely to the right. Thus all the
B(OH)3 reacts with NaOH, in effect it acts as a strong acid in the presence of the cisdiol.

 

COH HO OH CO OH HOC CO OC
2H2O 2H2O
+ B B + B
COH OH OH
HO CO HOC CO OC

H3BO3 forms chelate complex with glycol and thereby shows strong acidity with Ka value. The
acidity is due to the high stability of the conjugate bone chelate complex.

–
CH–OH CH O O CH
HB(OH)4 + 2 B + H+ + 4H2O
CH–OH CH O O CH

Catechol, salicylic acid also form similar complexes but ethanol is failure
O
O O – –
O O–C
B B
O O , O
COO

140°C strong heating

100°C
H3BO3 HBO2 –H2O H2B4O7 2B2O3
–H2O –H2O

meta boric acid Boron sesquioxide

Again B2O3 + H2O  H3BO3

BF3 is a strong Lewis acid and forms adduct with NH3

Uses of Boric acid

(i) Boric acid is used in the manufacture of enamels and pottery glazes.

(ii) Boric acid is used in medicines as an eye wash.

(iii)Boric acid is used for making borosilicate glass.

Boric acid on heating gradually loses its water of crystallisation to finally give borontrioxide.

4H3BO3  
375 K
4HBO2  
435 K
H2B4O7  
red heat
2B2O3(s)
 4H2O H2O H2O

boric acid metaboric acid tetraboric acid boron trioxide

Boron sesquioxide (B2O3)

Preparation:

H3BO3 100°C (1) red heat

HBO2 B2O3
Boric acid heat, (2) 400°C
H2O (3) reduced pressure
½ H2O

Properties: The crystalline variety melts at 450°C. It reacts with CuO, CoO, P 2O5 etc.

B2O3 + CuO  Cu (BO2)2 [Borax Bead]

B2O3 + CoO  Co(BO2)2

B2O3 + P2O5 2BPO4

Structures of some orthoborates and metaborates are given as follows,

O O 3
B
O

orthoborates (Planar triangular)

O– O–
O O O 3 B B
B B
O O O O O O
O O B B B
B ,
O– O– O–
O
B3O6–3 ion B2O4–2 ion

Borax (Na2B4O7.10H2O)

Structure of Borax
 In borax, two boron atoms are in triangular geometry and two boron atoms are in tetrahedral
geometry. The ion is [B4O5(OH)4]2 and the remaining eight water molecules are associated with
the two sodium ions. Hence, the borax contains tetranuclear units [B 4O5(OH)4]2 and therefore is
formulated as Na2[B4O5(OH)4].8H2O.

OH
B
O O
HOB O BOH
O O
B
OH
Structure of borax anion

Borax occurs naturally as tincal (contains about 55% borax) in certain inland lakes of India, Tibet
and California (U.S.A.).

Borax can also be prepared from certain other minerals such as boracite, colemanite and
boranatrocalcite. The minerals are powdered and boiled with sodium carbonate solution.

Ca2B6O11 + 2Na2CO3  2CaCO3 + Na2B4O7 + 2NaBO2

Borax is crystallised from the filtrate. Sodium metaborate, present in the mother liquor, is
converted into borax by passing carbon dioxide through it

4NaBO2 + CO2  Na2B4O7 + Na2CO3

sod. metaborate

Two important hydrates of borax are known. These are,

(i) Pentahydrate, Na2B4O7.5H2O.

(ii) Decahydrate or monoclinic borax, Na2B4O7.10H2O.

The pentahydrate is obtained when the solution is crystallised at above 60°C, while the monoclinic
variety is obtained when crystallisation is carried out below 60°C. Both the varieties on heating
form anhydrous borax.

Properties of Borax

(i) Borax is a colourless, crystalline solid sparingly soluble in cold water but dissolves readily in hot
water. It forms two important hydrates: octahedral borax Na2B4O7.5H2O and monoclinic borax
Na2B4O7.10H2O.
Basic nature

Borax is slightly hydrolysed in solution. As boric acid is a weak acid, the solution is alkaline in
nature.

B 4 O 72 + 7H2O 2OH + 4H3BO3

Action of acids

Borax reacts with HCl or H2SO4 to form boric acid. On cooling, the white flakes of boric acid are
obtained

Na2B4O7 + 2HCl + 5H2O  2NaCl + 4H3BO3

boric acid
Action of heat

When powdered borax is heated strongly in a bunsenflame, it loses water of crystallization and
forms colourless, transparent glasslike bead which is made up of sodium metaborate and boric
anhydride.
 
Na2B4O7.10H2O  Na2B4O7  2NaBO2 + B2O3
borax sod. Metaborate boron oxide

transparent bead
Uses of Borax

(i) for manufacturing enamels, glazes and optical glass.

(ii) as a flux for soldering and welding.

(iii)as an analytical reagent, e.g. in borax bead test.

Boron Nitride (Inorganic Graphite)

1200°C
Na2B4O7 + 2NH4Cl 2 NaCl + H2O + 2B2O3 + 2NH3

B2O3 + 2NH3  2BN + 3H2O

Structure of boron nitride Structure of Graphite

B B B C C C
N N N C C C
N C
B B B B C C C C
N N N C C C

They are soft and used as lubricating material.

Boranes

Structures of the boranes

The bonding and structure of the boranes are of great interest. They are different from all other hydrides.
There are not enough valency electrons to form conventional twoelectron bonds between all of the
adjacent pairs of atoms and so these compounds are termedelectron deficient.

In diborane there are 12 valency electrons, three from each B atom and six from the
H atoms. Electron diffraction results indicate the structure shown in given figure.

H H
H 1.33 Å 1.19 Å
B B 1.19 Å
H H 1.33 Å
H

The two bridging H atoms are in a plane perpendicular to the rest of the molecule and prevent rotation
between the two B atoms. Specific heat measurements confirm that rotation is hindered. Four of the H
atoms are in a different environment from the other two. This is confirmed that diborane cannot be
methylated beyond Me4B2H2 without breaking the molecule into BMe3.

The terminal BH distances are the same as the bond lengths measured in nonelectrondeficient
compounds. These are assumed to be normal covalent bonds, with two electrons shared between
two atoms. We can describe these bonds as twocentretwoelectron bonds (2c2e), with two
electrons shared between two atoms.

Thus, the electron deficiency must be associated with the bridge groups. The nature of the bonds in
the hydrogen bridges is now well established. Obviously, they are abnormal bonds as the two
bridges involve only one electron from each boron atom and one from each hydrogen atom,
making a total of four electrons. An sp3 hybrid orbital from each boron atom overlaps with the 1s
orbital of the hydrogen. This gives a delocalised molecular orbital covering all three nuclei,
containing one pair of electrons and making up one of the bridges. This is a
threecentretwoelectron bond (3c2e). A second threecentre bond is also formed.

It contains two 3centre 2electron banana bonds (B … H … B). Two electrons from two H atom
and two from two Boron atoms consist of four electrons. An overlap of sp 3 hybrid orbital of B and
1s hydrogen orbital gives the delocalised molecular orbitals of a B … H … B bridge.

H
H
B B
 
B
B  
B – H –B bridge

None of the group III elements react directly with hydrogen, but several interesting hydrides are
known. The boron hydrides are sometimes called boranes by analogy with the alkanes
(hydrocarbons). Almost 20 boranes have been reported and 11 are well characterized. They fall
into two series:
1. BnH(n + 4) (called nidoboranes).

2. A less stable series BnH(n + 6) (called arachnoboranes).

Boron hydrides differ from carbon hydrides (i.e. hydrocarbons) that they don’t occur in nature
because of their great affinity for H2O and O2. The compound BH3 which would be analogous to
BF3 doesnot exist because Hatom lacks the electrons that would be needed to participate in BH
bonding and compensate for the incomplete octet of B. BH3 can exist only in complex
formation with donors such as BH3.CO, BH3.N(CH3)3. Molecules of BH3 apparently dimerize
spontaneously when they come in contact with each other to form diborane, B 2H6.

Method of preparation
heat
Mg3B2 + 6HCl 3MgCl2 + B2H6

3LiAlH4 + 4BF3  3LiF + 3AlF3 + 2B2H6

3LiBH4 + 4BF3  3LiBF4 + 2B2H6

Borazole (B3N3H6) (Inorganic Benzene)

heat at
3B2H6.2NH3 2B3N3H6 + 12H2
200°C

Structure of B3N3H6 is

H H H H
+
N B N B
+
HB NH HB + 
NH
N B N B
H H H H

CH3 H
N B
200°C
B2H6 + CH3NH2 HB NCH3
N B
CH3 H

H H H Cl
H – Cl
+
H N B N B
– + H 50°C
B3N3H6 + 3HCl B N ClB NH
(i) + –
Cl N B H
N B
H H H Cl H Cl
Hydrochloride of Borazole B-trichloro borazole

(ii) B3N3H6 + 9H2O  3H3BO3 + 3NH3 + 3H2

ALUMINIUM AND ITS COMPOUNDS

(1) Ores of Aluminium : Bauxite ( Al 2 O 3 .2 H 2 O), Cryolite ( Na 3 AlF6 , Felspar (KAlSi 3 O 8 ),
Kaolinite ( Al 2 O 3 . 2 SiO 2 .2 H 2 O) , Mica (K 2 O.3 Al 2 O 3 . 6 SiO 2 .2 H 2 O), Corundum ( Al 2 O 3 ) ,
Diaspore ( Al 2 O 3 .H 2 O), Alunite or alum stone [K 2 SO 4 . Al 2 (SO 4 )3 . 4 Al(OH )3 ].

(2) Extraction : Aluminium is obtained by the electrolysis of the oxide (alumina) dissolved in
fused cryolite. This involves following steps,

Purification of ore
(i) Baeyer's process
 Roasted ore 
Bauxite Roasted    Filtrate Filtered
Caustic soda solution
  Pure Al 2 O3 Heat
 Al (OH ) 3
Finely powdered FeO  Fe 2O3 o
High pressure (150 C, 80 atm) (Sod. Aluminate) CO2
(red) filtered, Fe 2O3 as residue

(ii) Hall's process

 Na
CO
Bauxite 2 CO
3 Solution o 2 Precipitat e Al(OH)3   Pure Al 2 O 3
Heat
(Finely powdered) Fused, extracted with 50 - 60 C and filtered.
(red) water. Residue Fe 2 O 3 Filtrate (Na 2 CO 3 )

(iii) Serpek's process

Bauxite  Coke
 N 2
  Silica reduced to  Alumina form AlN    Pure Al 2 O 3 
Hydrolysis
  Al(OH ) 3
Heated
(Finely powdered) Heated to
o
Si which volatalis es aluminium nitride
(white) 1800 C

(iv) Hall and Heroult process : It is used for extraction of aluminium. In this process a fused
mixture of alumina (20%), cryolite (60%) and fluorspar (20%) is electrolysed using carbon
electrodes. Whereas cryolite makes Al 2 O 3 conducting fluorspar decreases the m.pt. of alumina.
Note : Aluminium is refined by Hoope's electrolytic process.

COMPOUNDS OF ALUMINIUM

Aluminium oxide or Alumina (Al2O3)

Methods of preparation
 
2Al(OH)3 
 Al2O3 + 3H2O ; Al2(SO4)3 
 Al2O3 + 3SO3

(NH4)2SO4.Al2(SO4)3.24 H2O 
 Al2O3 + 2NH3 + 4SO3+ 25H2O
strong 
2AlF3 + B2O3   Al2O3 + 2BF3

Aluminium Halides
The fluorides of Al, Ga, In and Tl are ionic and have high melting points. The other halides are
largely covalent when anhydrous. AlCl3, AlBr3 and GaCl3 exist as dimers, thus attaining an octet
of electrons. The dimeric formula is retained when the halides dissolve in non-polar solvents such
as benzene.
Cl Cl Cl

Al Al
Cl
Cl Cl

When the halides are dissolved in water, the high enthalpy of hydration is sufficient to break the
covalent dimer into [M.6 H2O]+3 and 3X ions. At low temperatures, AlCl3 exists as a close packed
lattice of Cl with Al+3 occupying octahedral holes. On heating, Al2Cl6 species are formed and the
volume of the solid greatly increases. This illustrates how close the bonding in this compound is to
the ionic/covalent border.

Alums
Alums are the compounds with general formula M 2SO4. M2(SO4)3.24H2O

M = Monovalent basic radical like Na+, K+, Rb+, Cs+, Tl+, NH4+

M = Trivalent basic radical like Al+3, Cr+3, Mn+3, Fe+3, Co+3\

Alums are obtained when hot solution of equimolar quantities of their constituent sulphates are
mixed and subjected to crystallization. These are acidic and swell on heating.

Oxide and Hydroxides of group III

On moving down the group, there is a gradual change from acidic through amphoteric to basic
character of oxides and hydroxides.
Al(OH)3 is amphoteric. It reacts principally as a base, i.e. it reacts with acids to form salts that
contain the [Al(H2O)6]+3 ion. However, Al(OH)3 show some acidic properties when it dissolves in
NaOH, forming sodium aluminate. (However, Al(OH) 3 is reprecipitated by the addition of CO2,
showing that the acidic properties are very weak).
excess NaOH
Al(OH)3    
 NaAl(OH)4
NaAlO2.2H2O
Sodium metaaluminate
The structure changes with both pH and concentration.

(i) Between pH 8 and 12, the ions polymerise using OH bridges and each aluminium is
octahedrally coordinated.

(ii) In dilute solutions, above pH value of 13, a tetrahedral [Al(OH) 4] ion exists.

(iii) In concentrated solutions above 1.5 M and pH > 13, the ion exists as a dimer
[(HO)3 Al –O -Al(OH)3]2-

Ga2O3 and Ga(OH)3 are both amphoteric like the corresponding Al compounds. Ga(OH) 3 is white
and gelatinous and dissolves in alkali, forming gallates. Tl2O3 and In2O3 are completely basic, and
form neither hydrates nor hydroxides.

TlOH is a strong base, and is soluble in water. Thus TlOH differ from the trivalent hydroxides and
resembles the Group I hydroxides. Where an element can exist in more than one valency state,
there is general tendency for the lowest valency state to be the most basic.