GROUP 13 ELEMENTS: THE BORON FAMILY
Boron is a fairly rare element, mainly occurs as orthoboric (ii) Lower elements also show +1 ionic state
acid (H 3 BO 3 ), borax (Tincal) Na 2 B 4 O 7 ·10H 2 O, kernite
Na2B4O7·4H2O, Colemanite (Ca2B6O115H2O)
In India borax occurs in Puga Valley (Ladakh) and Sambhar
Lake (Rajasthan).
The abundance of boron in earth crust is less than 0.0001%
by mass. There are two isotopic forms of boron 10B (19%) and
11
B (81%).
Aluminium is the most abundant metal and the third most
abundant element in the earth’s crust (8.3% by mass) after oxygen
(45.5%) and Si (27.7%). Bauxite, Al2O3. 2H2O and cryolite,
Na3AlF6, feldspar (K2O.Al2O3.6SiO2) are the important minerals
of aluminium.
In India it is found as mica in Madhya Pradesh, Karnataka,
Orissa and Jammu.
Gallium, indium and thallium are less abundant elements in
nature.
Physical Properties
Atomic Radii
Atomic radius of Ga is less than that of Al. This can be
understood from the variation in the inner core of the electronic
configuration. The presence of additional 10 d-electrons offer
only poor screening effect for the outer electrons from the
increased nuclear charge in gallium. Consequently, the atomic
radius of gallium (135pm) is less than that of aluminium (143
pm).
Tl > In > Al > Ga > B
Ionization Enthalpy
B  Tl > Ga > Al > In iH1
B > Ga > Tl > In > Al iH2
B > Ga > Tl > Al > In iH3
Electronegativity
Down the group, electronegativity first decreases from B to
Al and then increases marginally. This is because of the
discrepancies in atomic size of the elements.
B > Tl > In > Ga > Al
Boiling point and Melting Point
Boron has very high melting point because it exists as gaint
covalent polymer is both solid and liquid state.
B > Al > Ga > In > Tl (b.p)
B > Al > Tl > In > Ga (m.p)
Reducing character
Al > Ga > In > Tl
Oxidation state
(i) Boron being smaller in size cannot lose its valence electrons
to form B3+ ion and it usually show +3 covalence. The tendency
to show +3 covalence however decrease down the group even Al
shows +3 covalence in most of its compounds.
P- Block Elements Boran Family - 1
e.g Tl+, Ga+. This is due to inert pair effect.
(iii) The tendency to form M+ ion increase down the group
Al < Ga < In < Tl
Chemical Properties
(1) Hydrides
Boron form a large no of volatile covalent hydrides, know as
boranes e.g. B2H6, B4H10, B5H11, B6H10.
Most of higher boranes are liquids, but B6H10 and B10H14 are
solids.
As Molecular weight increaes, they gradually become more
stable.
Two series of borances with general formula BnHn+4 (Called
nidoboranes) and less stable BnHn+6 (called arachno-boranes)are
more important.
Al forms only one polymeric hydride (AlH3) commonly known
as alane. It contains Al.....H.....Al bridges.
Uses of boron hydrides
For making high energy fuels and propellants
(2) Reactivity towards air
Boron is unreactive in crystalline form.
Aluminium forms a very thin oxide layer on the surface which
protects the metal from further attack.
Amorphous boron and aluminium metal on heating in air form
B2O3 and Al2O3 respectively.
With dinitrogen at high temperature they form nitrides.

2E(s)  3O 2 (g)   2E 2 O3 (s)

2E(s)  N 2 (g)   2EN(s)
(E = element)
Boron trioxide is acidic and reacts with basic (metallic)
oxides forming metal borates.
Aluminium and gallium oxides are amphoteric
Indium and thallium are basic in their properties.
(3) Reactivity towards acids and alkalies
Boron does not react with acids and alkalies even at moderate
temperature
Aluminium dissolves in mineral acids and aqueous alkalies
and thus shows amphoteric character.
Aluminium dissolves in dilute HCl and liberates dihydrogen.
2Al(s) + 6HCl (aq)  2Al3+ (aq) + 6Cl– (aq) + 3H2 (g)
Concentrated nitric acid renders aluminium passive by
forming a protective oxide layer on the surface.
Aluminium also reacts with aqueous alkali and liberates
dihydrogen.
2Al (s) + 2NaOH(aq) + 6H2O(l) 2 Na+ [Al(OH)4]–(aq) + 3H2(g)
Sodium tetrahydroxoaluminate(III)
 P- Block Elements Boran Family - 2
3
(4) Reactivity towards halogens
These elements react with halogens to form trihalides (except
TlI3).
2E(s) + 3 X2 (g)  2EX3 (s) (X = F, Cl, Br, I)
All Boron trihalides except BF3 are hydrolysed to boric acid.
Tetrahedral
BX3 + 3H2O  B(OH)3 + 3HX ; (X = Cl, Br, I)
Dilute acids have no action of boron others liberate H2 from
BF3 forms an adidtion product with water.. them.

BF3  H 2 O  H  [BF3OH] 
2 H O
H 3O [BF3OH] Borates are more stable than aluminates.
Concentrated nitric acid oxidises boron to boric acid but no
 2[Al(H 2O)6 ]3  6Cl 
Al 2 Cl 6  12H 2 O 
such action is noticed other group memebers.
Lewis acid character B + 3HNO3  H3BO3 + 3NO2
BI3 > BBr3 > BCl3 > BF3 Diagonal relationship between Boron and Sillicon
(5) Oxides and hydroxides (1)

B2 O3 and B(OH)3  Al2 O3 and Al(OH) 3  BCl3 + 3H2O  B(OH)3 + 3HCl

(acidic) (amphoteric)
SiCl4 + 4H2O  Si(OH)4 + 4HCl
Ga 2 O3 and Ga(OH)3  In 2 O3 and In (OH)3  Tl 2O 3 and Tl(OH) 3
(amphoteric) ( Basic) (Strong basic) (2)
Oxides of both are acidic and can be reduced by limited aoount of
B(OH)3 or H3BO3 is weak monobasic Lewis acid
Mg. In excess of Mg boride and slicide are formed.
Boric acid B(OH)3 is soluble in water as it accepts lone pair
of electron to act as Lewis acid. Rest all hydroxides of group 13 B2O3 + 3Mg  3MgO + 2B ; SiO2 + 3Mg  2MgO + Si
are insoluble in water and form a gelatinous precipitate. (3)
B(OH)3 + H2O  B(OH)41– + H+ Both the metals and thier oxides are readily soluble in alkalies
Al2O3 being amphoteric disolves in acid and alkalies both
2B  6NaOH  2Na 3 BO 3  3H 2 
Al 2 O3  3H 2SO 4  Al 2 (SO 4 )3  3H 2O ( Borate)

Al 2 O3  2NaOH  2NaAlO 2  H 2 O

fuse Si  2NaOH  H 2 O 
(Silicate)
 Na 2SiO 3  2H 2 
sodium meta aluminate
B2O 3  6NaOH  2Na 3 BO3  3H 2 O
Al 2 O3  3C  3Cl 2 (dry) 
 2AlCl 3  3CO (g)
SiO 2  2NaOH  Na 2SiO 3  H 2 O
On heating AlCl 3 (aq) to dryness, Al 2O 3 is formed
2AlCl 3  6H 2 O 
 2Al(OH)3  6HCl SOME IMPORTANT COMPOUNDS OF BORON
2Al(OH)3 
 Al 2O 3  3H 2 O Boron Hydrides
One of the crystalline form of alumina (Al2O3) is called Diborne is a colourless highly toxic gas with a b.p of 180 K.
corundum. It is very hard and used as abrasive. It is prepared by Preparation
heating amorphous form of Al2O3 to 2000K.
ANOMALOUS PROPERTIES OF BORON 4BF3  3LiAlH 4 
 2B2 H 6  3LiF  3AlF3
Boron shows allotorpy and exists in two form cystalline and 8BF3  6Na 
450 K
 B2 H 6  6NaBF4 (Industrial method)
amophous. Aluminium is a soft metal and does not exist in 2NaBH 4  I 2 
Polyether
 B2 H 6  2NaI  H 2 (Lab method)
differnet forms.
Boron forms only covlaent compounds whereas aluminium Properties
and other elements of group 13 form even some ionic compounds. Diborane catches fire spontaneously upon exposure to air. It
The trihalides of boron (BX3) exist as monomers, on the other burns in oxygen releasing an enormous amount of energy
hand aliuminium halides exist as dimers (Al2X6) B2H6 + 3O2  B2O3 + H2O CH– = –1976 kJ mol–1
By forming dimer, AlCl3 acheived higher coordination number,, B2H6 + 6H2O  2H3BO3 + 6H2
becuase of which stablity increases.
B2H6 + 2CO  (BH3  CO)2
 P- Block Elements Boran Family - 3
Structure of Diborane Orthoboric acid
Orthoboric acid, H3BO3 is a white crystalline solid, with soapy
touch. It is sparingly soluble in water but highly soluble in hot
water. It can be prepared by acidifying an aqueous solution of borax.
Na2B4O7 + 2HCl + 5H2O  2NaCl + 4B(OH)3
It is also formed by the hydrolysis (reaction with water or
Fig . (a) The structure of diborane, B2H6
dilute acid) of most boron compounds (halides, hydrides, etc.). It
has a layer structure in which planar BO3 units are joined by
hydrogen bonds.
Boric acid is a weak monobasic acid. It is not a protonic acid but
acts as a Lewis acid by accepting electrons from a hydroxyl ion:
B(OH)3 + 2HOH  [B(OH)4]– + H3O+
3
Fig. (b) Bonding in diborane. Each B atom uses sp hybrids On heating, orthoboric acid above 370K forms metaboric
3
for bonding. Out of the four sp hybrids on each B atom, acid, HBO2 which on further heating yields boric oxide, B2O3.
one is without an electron shown in broken lines. The
terminal B-H bonds are normal 2-centre-2-electron bonds H 3 BO3 
373 K
 HBO 2 
433 K
 H 2 B4O7 
Red hot
B2 O3
but the two bridge bonds are 3-centre-2-electron bonds Boric acid Metaboric acid Tetra boric acid Boron oxide

The 3-centre-2-electron bridge bonds are also

referred to as banana bonds  NaBO2  Na[B(OH) 4 ]  H 2O
B(OH)3  NaOH 
Boron Halides
Borazine or Borasole or Triborine triamoine (B3N3H6)
BF3 and BCl3 are gases, BBr3 is a volatile liquid while BI3 is a
It is colour less liquid and is also called inorganic benzene.
solid
180 C
They acts as Lewis acids. 2B2 H 6  6NH 3   2B3 N 3 H 6  12H 2
It has a six membered ring of altermating B and N atoms
each is further linked to a H-atom.

Planar Tetrahedral

Borax (Tincal) : Suhaga

It is the most important compound of boron. It is a white
crystalline solid of formula Na2B4O7.10H2O.
In fact it contains the tetranuclear units (B4O5(OH)4)2– and
correct formula; therefore, is Na2[B4O5 (OH)4].8H2O.
Borazole
Borax dissolves in water to give an alkaline solution. 
B3 N 3 H 6  9H 2 O 
 3NH 3  3H 3 BO 3  3H 2
Na2B4O7 + 7H2O  2NaOH + 4H3BO3
Boron nitride (BN)
Orthoboric acid
Colourless, good insulator, diamagnetic and almost
On heating, borax first loses water molecules and swells up.
unreactive solid
On further heating it turns into a transparent liquid, which
solidifies into glass like material known as borax bead. BCl 3  NH 3 
[H 3 N  750 C
 BCl3 ]   BN  3HCl
Excess NH 3
 
Na 2 B4O7 .10H 2O 
 Na 2 B4O 7 
 2NaBO2  BO 2 3
2B  N 2 
Heat
 2BN
Sodium Boric anhydride
metaborate

The metaborates of many transition metals have characteristic The structure of BN is similar to the structure of graphite.
colours and, therefore, borax bead test can be used to identify So it is called Inorganic graphite.
them in the laboratory. For example, when borax is heated in a
Compounds of aluminium
Bunsen burner flame with CoO on a loop of platinum wire, a blue
coloured Co(BO2)2 bead is formed. (A) Ultramarines :
 P- Block Elements Boran Family - 4

Ultramarine is a complex silicate of aluminium and sodium with Ga is soft haevy metal melts at 30°C and is ued in making heat
about 12% of sulphur. It has a blue colour. The blue ultramarine sensitive thermometers.
has the composition Na5Al3Si3S3O12. If this is heated in a stream of
Al burn in air at high temperture with the evolution of much
chlorine a violet coloured variety of ultramarine is obtained. It is
heat.
artificial (lapis-lazuli)
Moisan boron is Amorphous boron of low purity..
Uses :- the blue variety is the most popular and is used in laundry
Excess NH3
for blueing purposes in calico printing and in blue paints. B2H6.2NH3
10 w temp
(B) Alum (120°C)
(i) Introduction :
Excess NH3
(a) Alums are double sulphates with their general formula B2 H 6 (BH)X .boran nitride
High temp.
R2SO4.M2(SO4)3.24H2O
where R = monovalent radical like Na+ , K+, NH4+ and M = Triva- Ratio 2NH3 : 1B2H6
lent radical like Al+3, Cr+3. Fe+3. B3N3H6 borazine
High temp.
(b) The different alums are - H. C Brown won the Noble prize of chemistry in 1979 for
(i) Potash alum - K2SO4.Al2 (SO4)3.24H2O work on these organoborn compounds.
(ii) Chrome alum - K2SO4 Cr2(SO4)3. 24 H2O 2Al + N2  2AlN
(iii) Iron alum - (NH4)2SO4. Fe2(SO4)3. 24H2O Boron fibres are used in making bullet-proof vest and light
composite material for aircraft.
(iv) Ammonium alum - (NH4)2SO4. Al2(SO4)3. 24H2O
(c) In alums each metal ion is surrounded by six water molecules. The boron - 10 (10B) isotope has high ability to absorb neu-
trons and, therefore, metal borides are used in nuclear industry as
(d) Lithium does not form alum because Li ion is too small to have a
protective shield and control rods.
coordination number of six.
The main Industrial application of borax and boric acid is in
(e) Pseudo alums : Double sulphates of divalent ions and triva-
the manufacutre of heat Resistant glass (eg. Pyrex), glasswool
lent ions with 24 water molecules in their crystals are known as
and fibrglass.
pseudo alums.
An aqueous solution of orthoboric acid is generally used as a
Eg. MSO4.X2 (SO4)3.24H2O
mild Antiseptic.
M = divalent or Bivalent ion
Al and its compounds have toxic Nature.
X = Trivalent metal ion
AlCl3 is anydrous and covalent
(ii) Properties :
BF3 in flame give sa characteristic green coloration.
(a) It is a white crystalline solid highly soluble in water.
Aluminum vessel should not be washed with material con-
(b) On heating it undergoes dehydration and swells up. taining washing soda. Since washing soda reacts with aluminium
(c) It is highly acidic in aqueous solution due to the hydrolysis of to form soluble aluminate.
aluminium sulphate to sulphuric acid
(d) It is a double salt and its aqueous solution gives reaction of all the
constituents ions K+, Al+3, SO4–2.
(iii) Uses :
(i) Alum is used to stop bleeding.
(ii) It is used for purification of water.
(iii) It is used as a mordant in dyeing industry.
(iv) Alum is used for tanning of leather.

Some Important Points

Order of Hardness
Diamond > Borazone > Carborundum > Corundum
 P- Block Elements Boran Family - 5
13. The product/s formed when diborane is hydrolysed is/are
Exercise
(a) B2O3 and H3BO3 (b) B2O3 only
01. The type of hybridisation of boron in diborane is
(c) H3BO3 and H2 (d) H3BO3 only
(a) sp-hybridisation (b) sp2-hybridisation
14. Hydrogen as will not reduce
(c) sp3-hybridisation (d) sp2d2-hybridisation
(a) Heated cupric oxide (b) heated ferric oxide
02. In the reaction B2O3 + C + Cl2  A + CO. the A is
(c) Heated stannic oxide (d) Heated aluminium oxide
(a) BCl3 (b) BCl2
15. When Al is added to KOH solution
(c) B2Cl2 (d) CCl2
(a) No action takes place (b) oxgen is evolved
03. Aluminium hydroxide is soluble in excess of sodium
hydoxide forming the ion (c) Water is produced (d) Hydrogen is evolved

(a) AlO2+3 (b) AlO2–3 16. Aluminium is not used

(c) AlO2– (d) AlO3– (a) In silvery paints (b) For making utensils

04. Boron form covalent compound due to (c) As a reducing agent (d) As oxidizer in metallurgy

(a) Higher ionization energy 17. Al2O3 can be converted to anhydrous AlCl3 by heating

(b) Lower ionization energy (a) A mixture of Al2O3 and carbon in dry Cl2 gas

(c) Small size (b) Al2O3 with Cl2 gas

(d) Both (a) and (c) (c) Al2O3 with HCl gas

05. The stability of +1 oxidation state increases in the (d) Al2O3 with NaCl in solid state
sequence 18. Which metal has a greter tendency to form metal oxide
(a) Al < Ga < ln < Tl (b) Tl < In < Ga < Al (a) Al (b) Ca
(c) In < Tl < Ga < Al (d) Ga < In < Al < Tl (c) Cr (d) Fe
06. The liquid field metal expanding on solidification is 19. Which of the following statements is incorrect
(a) Ga (b) Al (a) aluminium reacts with excess NaOH to give Al(OH)3
(c) Zn (d) Cu (b) NaHCO3 on heating gives Na2CO3

07. Aluminium chloride exists as dimer, Al2Cl6 in solid state (c) Pure sodium metal dissolves in liquid ammonia to give
as well as in solution of non-polar solvents such as ben- blue solution
zene. When dissolved in water, it gives (d) NaOH reacts with glass to give sodium silicate
(a) [Al(OH)6] + 3HCl 3–
(b) [Al(H2O)6] + 3Cl 3+ – 20. The number of isomers possible fo redistributed borazine,
(c) Al + 3Cl
3+ –
(d) Al2O3 + 6HCl B3N3H4X2 is

08. Inorganic benzene is (a) 3 (b) 4

(a) B2H6 (b) B3N3H6 (c) 5 (d) 2

(c) B3O3H6 (d) (BH3)3 21. Boron shows single oxidation state due to absence of

09. Which of the folloiwng does not exist in free form (a) inert pair effect (b) Screening effect

(a) BF3 (b) BCl3 (c) Isotope effect (d) None of these

(c) BBr3 (d) BH3 22. The tendency of BF3, BCl3 and BBr3 to behave as Lewis
acid decreases in the sequence
10. Alumina is
(a) BF3 > BCl3 > BBr3 (b) BCl3 > BF3 > BBr3
(a) Acidic (b) Basic
(c) BBr3 > BCl3 < BF3 (d) BBr3 > BF3 > BCl3
(c) Amphoteric (d) None of these
23. The compound which exists as a dimer is
11. An aqueous solution of borax is
(a) LiCl (b) MgCl2
(a) Neutral (b) Acidic
(c) AlCl3 (d) SiCl4
(c) Basic (d) Amphoteric
24. The structure of diborane (B2H6) contains
12. Crystalline metal can be transformed into metallic glass
by (a) Four 2c-2e bonds and two 3c-2e bonds

(a) Alloying (b) Two 2c-2e bonds and four 3c-2e bonds

(b) Pressing into thin plates (c) Two 2c-2e bonds and two 3c-3e bonds

(c) Slow cooling of molten metal (d) Four 2c-2e bonds and four 3c-2e bond

(d) Very rapid cooling of a spray of the molten metal

01. (c) 02. (a) 03. (c) 04. (d) 05. (a) 06. (a) 07. (b) 08. (b) 09. (d) 10. (c) 11. (c) 12. (d) 13. (c) 14. (d) 15. (d)
16. (d) 17. (a) 18. (a) 19. (a) 20. (b) 21. (a) 22. (c) 23. (c) 24. (a)