Key N ot sE

• Elements B, Al, Ga, In and Tl belong to III A Group down the group whereas the stability of +3 oxidation
and p-block of the periodic table. state decreases because of inert pair effect.
• The outer electronic configuration of these elements is • The pair of electrons in ns orbital tend to remain paired
ns2 np1. and are not participating in compound formation. This
• Boron has 2, aluminium has 8, gallium and indium pair of electrons is called inert pair.
have 18 electrons in their penultimate shells. Thallium • In +1 oxidation state, Tl behaves similar to alkali metals.
­

has 18 electrons in the penultimate and 32 electrons in Hence, it is nick named as duck-gilled platypus.
the antipenultimate shells. • In +1 oxidation state, these elements act as reducing
• Owing to the difference in the electronic configuration agents and their reduction power decreases from B (+1)

H
in penultimate shells, there is difference in the proper- to Tl (+1) as the stability of +1 oxidation state increases.
• In +3 oxidation state, they act as oxidizing agents and

AR
ties of these elements, i.e., between B and Al; Al and
Ga; and Ga, In and Tl. the oxidation power increases down the group because
• Aluminium is the third most abundant element and of the decrease in the stability +3 oxidation state be-
cause of inert pair effect.

IG
first most abundant metal in the earth’s crust. Gallium,
Indium and Thallium are less abundant in nature. • B never forms B3+ ion because the sum of three
• Boron is non-metal and others are metals and the ionization energies (I1 + I2 + I3) of B is very large. ‘B’

AL
­

metallic character increases from B to Tl.

­
always form covalent compounds.
• AlF3 and Al2O3 are ionic but other aluminium
p hys c l ro ert es
i a p p i
ES compounds are covalent in solid state, e.g., AlCl3 is
­

covalent in solid state; however, in solution, it ionizes

• Atomic and ionic sizes of Group III A elements do not
because the hydration energy of small Al3+ ion and the
increase regularly. A large increase between B and Al is due
sum of hydration energies and Ea, of three Cl– ions
SS

to the lesser number of electrons in the penultimate shell of

­

exceeds the sum of three ionization energies of Al.

B. Al and Ga have almost equal size because of poor shield-
• Boron is non-metal. Aluminium is the most electro
ing capacity of 3d electrons in Ga. In and Tl are also almost
­

positive metal in the group. The electropositive char-

LA

equal in size because of lanthanide contraction in Tl.

acter of Ga, In and Tl is less than Al and decreases
• Density increases down the group. Ga has unusual
from Ga to Tl. This is again attributed to the increased
expansion during solidification. Solid Ga is less denser
C

effective nuclear charge because of poor shielding ca-

­

than liquid Ga.

pacity of inner d electrons.
• Melting and boiling points of B are very high because
•
L

The tendency to form complexes by these elements

of its giant covalent polymeric structure in both solid
is more than the s-block elements. Boron exhibits a
SA

and liquid state. melting point decreases from B to Ga

maximum covalence 4 because of the absence of
and then increases. Ga has abnormally low Melting
­

d-orbitals in its valence shell but other elements

point because it consists of Ga2 molecules. Ga exist in
N

exhibits a covalence up to 6 because of the availability

liquid state in a wide range of temperatures 30–2000°C
­ ­

of d-orbitals in their valence shells.

BA

and hence used in high temperature thermometers.

­

• Boiling points decrease regularly from B to Tl.

Though melting point of Ga is less, its boiling point is R e ct v ty of grou
a i i p iii A elemen s T

in regular order. • These elements do not react with air in cold condition.
­

• Ionization energies decreases down the group. Large B burns in air forming B2O3. Al does not react with
decrease between B to Al but then onwards the decrease
­
air because of the formation of protective oxide layer.
­

is very little because of the poor shielding effect of d- ­

However, when powdered Al is exposed to liquid oxy-
electrons in Ga and In and d and f-electrons in Tl which gen, it explodes because the reaction between Al and
­ ­

results in the increase of effective nuclear charge. O2 is highly exothermic which takes place instantane-
­

• Electronegativity decreases from B to Al but then ouly because of the availability of large surface area.
onwards there is little increase down the group instead
­
Ga and In are stable in air but Tl forms an oxide layer.
­

of normal decrease which is attributed to the increased • B and Al when burnt in air react with both O2 and N2
effective nuclear charge as said above. in air forming oxides and nitrides.
• Group III A elements exhibit +1 and +3 oxidation • Boron is not affected by water but red hot boron
states. The stability of +1 oxidation state increases decomposes steam. Though the reaction between
­

Chapter_07.indd 34 8/17/2013 4:01:55 PM

 Al and H2O is thermodynamically possible, it does • If Al is amalgamated the, reactivity increases because

­
not react with water because of the presence of oxide of the destruction of oxide layer.
layer. However, it corrodes in salt water because the • B and Al dissolve in alkalis forming borates and
oxide layer will be removed by salts. Owing to this aluminates with the liberation of H2.

­
reason, Al vessels should not be kept with water over • Sodium meta aluminate exists as hydrated tetrahydroxo alu-

­
night. Ga and In are attacked by water only in the pres- minates [Al(OH)4(H2O)2]– and aluminate is [Al(OH)6]3– in
ence of oxygen. which Al exhibits a coordination number 6.
• Boron does not react with non-oxidizing acids but oxi- • Boron can react with highly electro positive metals
dized to boric acid with oxidizing acids such as conc. such as Mg forming borides. Others form alloys with
HNO3. metals.
• The oxide film present on the surface of Al prevents it • With carbon, boron gives B4C whereas aluminium
to react with dil. acids but it readily react with dil. HCl gives Al4C3.

H
and the reaction becomes vigorous with the increase in • Both B and Al react with N2 forming nitrides BN and
concentration of HCl. Dil. H2SO4 and dil. HNO3 react

AR
AlN which on hydrolysis give ammonia.
with Al slowly. Conc. H2SO4 liberates SO2 with Al but • Both B and Al give trihalides with halogens. Tl gives
conc. HNO3 renders the Al passive. both trihalides and mono halides.

IG
Reactions of Boron

AL
Reaction Remark
1. B + O2 → B2O3 At high temperature
2. B + S → B2S3 ES At high temperature
3. B + N2 → BN At high temperature
4. B + X2 → BX3 X = F, Cl, Br, I
5. B + NaOH → Na3BO3 + H2 Fused with alkali
SS

6. B + NH3 → BN + 3H2

7. B + M → MxBy Highly electropositive metals form borides.
LA

Chemical reactivity of Group III A (except boron) elements

Reaction Remark
C

Action of air Al corrodes in air but corrosion is prevented by its oxide

1. M + O2 → M2O3 layer. When burnt in air, they form M2O3. Tl forms some
L

M2O3. Al also form, AlN. Powdered Al explodes in air

SA

because of highly exothermic reaction.

2. M + H2O → M2O3 + H2 Al does not react with pure H2O because of oxide layer but
corrodes easily in salt water. Al decomposes steam.
N

3. M + acid → Al reacts with acids. Al becomes passive with conc. HNO3.
4. M + NaOH → NaMO2 + H2
BA

Only Al and Ga react with alkalis.

Na3MO3 + H2
5. M + X2 → MX3 ( ) −
All form trihalides; Tl I3 is Tl+ I 3

com ounds of grou A elements • Boron hydride and aluminium hydrides form complex
p
p
iii
hydrides such as LiAlH4 NaBH4, in which H– ion acts
ydrides
as donor.
H
• Boron forms a large number of hydrides called boranes
­
with general formula BnHn+4 and BnHn+6. Aluminium
xides
­
forms only one hydride called alane which have
O
polymeric structure in which each Al is surrounded • These elements form sesqui-oxides of the type M2O3.
with six H atoms consisting Al H2 Al bridges. Ga and In form unstable but Tl form most stable
• Gallium and indium hydrides are unstable. monoxides Ga2O, In2O and Tl2O.
­
Chapter_07.indd 35 8/17/2013 4:01:56 PM
 • B2O3 is acidic Al2O3, Ga2O3 and In2O3 are amphoteric
­ • The adduct formation with Lewis bases accompanies
but Tl2O3 is basic. Acidic character decreases and the rehybridization of boron resulting in the loss of
basic character increases for the oxides down the
­ B-X double bond character.
group. Tl2O3 on heating converts into Tl2O. • The enthalpy change in the adduct formation with
trimethyl amine is more for BBr3 and least for BF3
­

H ydroxides indicating the double bond character follows the order

­

BF3 > BCl3 > BBr3.

• The hydroxy compounds of boron and aluminium are
• From the experimental and calculated bond lengths
formed when their oxides react with water.
(sum of the covalent radii of boron and halogen), it
• The acidic character of the hydroxides decreases and
was found that the experimental value is less than
basic character increases down the group.
the calculated value because of double bond char-
• B(OH)3 or H3BO3 is a weak acid, Al(OH)3, Ga(OH)3
acter and the difference between calculated value

H
are amphoteric In(OH)3 is more basic than acidic but
and experimental value is more for BF3 indicating
Tl(OH)3 is completely basic. TlOH behaves almost
­

AR
the effective overlapping of 2p orbitals of both boron
similar to NaOH.
­

and fluorine.
­

• When BF3 forms an adduct such as BF −4 and BF3 . NH3,

halides

IG
the B-F bond length increases because of the change
• Group III A elements form three types of halides from double bond character to single bond character.
• Halides of other Group III A elements are also elec-

AL
viz., monohalides, dihalides and trihalides of which
trihalides are much important.
­
tron deficient and can act as Lewis acids but the Lewis
• All the Group III A elements form trihalides of the acidic character decreases with the increase in the size
type ‘MX3 (X = F, Cl, Br or I)’. of cation down the group.
•
ES • AlF3 is ionic solid having high melting point. Other
TlCl3 and TlBr3 are unstable and tend to lose halogen
forming mono halide because of the oxidizing tenden- halides of Al are low melting volatile solids because
cy of the +3 oxidation state of thallium coupled with AlF3 is ionc but other halides of Al are covalent.
SS

reducing property of Cl– and Br–.

­
• Except fluorides, other halides of Al, Ga, and In exists
­

• In TlI3, thallium exists in +1 oxidation state containing as dimers. This is because boron being small atom
LA

Tl+ and I3– ions. cannot coordinate with four large halogen atoms.
• Stability of different halides for given element is • Though F atom is smaller, BF3 does not dimerize.
fluoride > chloride > bromide > iodide. Owing to dimerization, there will be rehybridization
C

­
­

• All boron halides are covalent. Fluorides of Al, Ga, In of boron results in the loss of resonance stability be-
and Tl are ionic and have high melting points. cause of the loss of B-X double bond character.
L

• Chlorides, bromide and iodides of Al, Ga, In and Tl

Anomalous ehaviour of oron
SA

are covalent when anhydrous, ionic character increases

B B

with the increase in the cation size. • Owing to the absence of d-orbitals in the valence
• Trihalides fumes in air because of hydrolysis. The shell of boron, its coordination number is limited
N

hydrogen halide due to reaction with moisture in air to 4 whereas other elements can have coordination
collects the water molecules, forms as droplets and number of 6.
BA

appears as fumes. • Boron does not exhibit inert pair effect.

• These trihalides are electron-deficient compounds and • Boron can combine with metals to form metal borides
act as Lewis acids. in whereas it exhibit –3 oxidation state.
• The relative strengths of the trihalides of boron as Lewis • Boron is not attacked by non-oxidizing acids such as
acids is BF3 < BCl3 < BBr3. This order is opposite to the HCl whereas others are attacked.
order expected from electronegativities and is due to the • Boron does not decompose water or steam but other
back bonding of electrons from halogen to boron. Group III A elements decompose hot water or steam.
• The back bonding is effective in BF3 and decreases • Boron is non-metal and bad conductor of electricity
rapidly from BCl3 to BBr3 because of the increasing but other elements are metals and good conductors of
difference in the energies of p-orbitals of boron and electricity.
halogen participating in pπ-pπ back bonding. • Boron exhibits, allotropy but other elements do not
• Boron trihalides can form adducts even with weakest ­
exhibit allotropy.
­

bases such as ethers, amines, phosphines, alcohols, • Boron never forms B3+ ion but other elements can
anions and CO by donating a lone pair to boron.
­
form M3+ ions.

Chapter_07.indd 36 8/17/2013 4:01:56 PM

 • Boron forms a large number of volatile hydrides • The electronegativities and ionization energies of both
called boranes which are electron deficient but other B and Si are nearly equal.
­
elements form only one polymeric hydride. Thallium • Oxides of both B and Si, B2O3 and SiO2 are acidic and
­
does not form hydride. with water yield corresponding acids boric acid and
• B2O3 is acidic whereas similar oxides of other ele- silicic acid, which are weak acids.
ments are either amphoteric or basic. • Both B and Si can be prepared by reduction of their
• Boron halides are monomeric whereas halides of other oxides B2O3 and SiO2 with Mg.
elements are dimeric. • Both B and Si form carbides B4C and SiC which are
very hard substances and are used as abrasives.
• Both B and Si react with metals forming borides and
imilarities between oron and Aluminium
silicides which decompose by dilute acids to form
S
B
­
• Both B and Al have same outer electronic configuration. hydrides.

H
­
• Both B and Al exhibit +3 oxidation state. • Both B and Si react with halogen forming halides
•

AR
Both B and Al form covalent compounds. which readily hydrolysed in water.
• Both form similar halides BCl3 and AlCl3 with chlorine • Both B and Si form a number of covalent hydrides
­
and readily hydrolyse in water. which are volatile, spontaneously inflammable and
•

IG
Both form nitrides when heated in nitrogen which readily hydrolyses.
hydrolyses in water liberating ammonia. • Both these elements and their oxides form borates and
­
• Both react with conc. H2SO4 liberating SO2 gas. silicates with alkalis.

AL
• Both react with alkalis liberating H2 gas.
ES oron
B
issimilarities of oron and Aluminium
• Borax on treating with HCl or H2SO4 gives boric acid
D
B
• Boron is non-metal but aluminium is metal. which on heating gives B2O3.
• Boron exhibits allotropy whereas aluminium does not • Colemanite when fused with sodium carbonate forms
SS

exhibit allotropy. calcium carbonate, borax and sodium metaborate,

­
• Crystalline boron is very hard whereas aluminium is sodium metaborate also converts into borax when CO2
­
LA

sufficiently soft. is passed through it.

• Al is good conductor of heat and electricity whereas B • B2O3, obtained by heating boric acid, is reduced to get
is bad conductor. boron with Na, K, Mg etc.
C

• B has very high melting point compared to Al. • The boron obtained by the reduction of B2O3 with Mg
• Maximum covalency of B is 4 whereas that of Al is 6. is about 95–98% pure and is called Moisson boron.
L

• Boron is not attacked even by steam whereas • Reduction of BCl3 with zinc gives crystalline boron.
SA

aluminium decomposes steam liberating H2. • Thermal decomposition of boranes at about 900°C
­
• Boron is not attacked by dilute acids but aluminium gives amorphous boron, but the thermal decomposition
­
evolves H2 from dil. H2SO4 and dil. HCl. Conc. HNO3 of BI3 above 1000°C gives crystalline boron.
N

oxidizes boron to boric acid but renders the aluminium • Crystalline boron contains clusters of boron atoms as
­
passive. B12 unit arranged in a icosahedron structure.
BA

• Borates are stable whereas aluminates are unstable. • Boron steel or boron carbide rods are used to control
• Boron forms a large number of hydrides called boranes nuclear reactions because boron nucleus has a very
­
but aluminium forms only one polymeric hydride high cross section area to capture neutrons.
alane.
• Oxide and hydroxide of boron are acidic whereas
those of aluminium are amphoteric. com ounds of oron
p
B
• Boron reacts with metals forming borides but aluminium oron rioxide 2 3
­
forms alloys.
B
T
B
O
• It is the anhydride of boric acid and can be prepared by
heating boric acid. It can also be prepared by dehydration
iagonal elationship of oron with ilicon
­
of boric acid over P2O5 at about 475K in vaccum.
D
R
B
S
• Both B and Si are non-metals having high melting • It is colourless transparent glassy mass, hygroscopic
points and are bad conductors of electricity. in nature; absorbs moisture from air, becomes opaque
• Both B and Si exhibit allotropy. and finally converts into boric acid.

Chapter_07.indd 37 8/17/2013 4:01:56 PM

 • When heated with transition metal salts, it forms metal • Boric acid is weak monobasic Lewis acid. It does not
metaborate having characteristic colour by which the liberate H+ ion but accepts a pair of electrons from OH–
metal can be detected. For example, CuSO4 gives • With increase in the concentration, acidity increases.
Cu(BO2)2 having blue colour. At low concentration, it is present as meta borate ion
[B(OH)4]–; however, as concentration increases, acid-
ity increases because of the formation of polymeric
oric Acids
­

metaborate ion [B3O3(OH)4]–

B

• Boron forms a large number of oxo acids such as ortho • It is a weak acid and cannot be titrated with NaOH
boric acid (H3BO3), metaboric acid (HBO2), pyroboric
­ solution. However, in the presence of polyhydroxy
­

acid (H6 B4O9) and tetra boric acid (H2B4O7). compounds such as mannitol, sorbitol, glucose, glyc-
­

• Ortho boric acid can be prepared by adding calculated

­ erol and ethylene glycol, boric acid acts as stronger
amount of H2SO4 or HCl to borax. acid and can be titrated with NaOH using phenol-

H
phthalein as indicator.
Na2B4O7 + H2SO4 + 5H2O → Na2SO4 + 4H3BO3
•

AR
When boric acid is heated with ethyl alcohol, it gives
• When SO2 gas is passed through a suspension of ethyl borate vapours which burns with green-edged
colemanite in water, boric acid is formed.
­ flame. This is used for the detection of borate ion.
•

IG
In orthoborate ion, boron atom is involved in sp2
Ca2B6O11 + 4SO2 + 11H2O → 2Ca(HSO3)2 + 6H3BO3
hybridization and is in bond with three OH groups in a
­

• Boric acid is also formed by the action of super heated planar triangular manner.

AL
water on boron nitride or boron sulphide. • Boric acid contains planar triangular B(OH)3 units
• It is white crystalline substance, soft, soapy to touch, which are bonded together through hydrogen bonds in
moderately soluble in cold water. two-dimensional sheets.
• Solubility of boric acid increases with the increase in
ES • Each boric acid molecule can form six hydrogen
temperature.
­ bonds and hydrogen atoms act as bridge between two
• On heating at 375 K, it gives metaboric acid; at 435K, oxygen atoms with a covalent bond on one side and
SS

3−
it gives tetraboric acid; and at red hot condition, it a hydrogen bond on the other side of different BO 3
­

forms boron trioxide. units.

•
LA

Borate ions are arranged in hexagonal rings and the

Summary of the reactions of Boric acid. number of hydrogen bonds in that hexagonal ring are six.
NaBO2
C
L

∆ NaOH
160oC
SA

HBO2 H2B4O7
Na2B4O7
N

100° Red
HC 2SO

Borate peroxo hydrates hot

H
BA

lo 4

and peroxo borates

r

H
2O
Na 2
2O
2
NH4BF4 Fusion with NH4 HF2 Red hot Na or K or
H3BO3 B2O3 B
Mg or Fe
or ols
∆ B2O3 d iols lcoh H
2O
C + Halogen
Cis dric a
ion es

y
(R

yh
fus oxid

pol
C
RCOCl

O)

Acidic
l

2
eta

BF3 BX3
O
M

chelate
complexes
Borates B2O (RCOO)4
B (RCOO)3

Acyl borates

Chapter_07.indd 38 8/17/2013 4:01:56 PM

 etaboric Acid gives characteristic coloured bead when heated with a
M
transition metal ion because of the formation of me-
• It is prepared by heating orthoboric acid.
taborate.
• Metaboric acid when dissoved in water forms orthoboric • In borax, two B atoms are in sp3 and other two B atoms

­
acid.
are in sp2 hybridization having tetrahedral and planar
• Metaborates are stable even at high temperatures.
triangular structures, respectively.
• Metaboric acid on reaction with sodium hydroxide • The borax ion is [B4O5(OH)4]2–, the remaining eight
forms either sodium metaborate or borax.
water molecules are associated with the two sodium ions.

­
• The formula of borax is written as Na2 [B4O5 (OH)4] .
orax a2 4 7
. 10
2 8H2O. It contain two six-membered heterocyclic rings,
B
N
B
O
H
O
• Borax occurs naturally as tincol. five B-O-B bridge bonds, 10 B-O bonds and four OH
• It can be prepared from the mineral colemanite by groups on four boron atoms.

H
boiling with concentrated solution of sodium carbonate. Borax is metaborate
­
­
AR
Ca2B6O11 + 2Na2CO3 → 2CaCO3 + Na2B4O7 +
oron alides
2NaBO2

B
H
• • BF3 is prepared by the action of conc. H2SO4 on B2O3

IG
The NaBO2 also converts into borax by passing CO2
into metaborate solution after separating CaCO3 and and CaF2
Na2B4O7.

AL
3CaF2 + B2O3 + 3H2SO4 → 2BF3 + 3CaSO4 + 3H2O
4NaBO2 + CO2 → Na2B4O7 + Na2CO3
• Other boron trihalides can be prepared by heating
• Naturally occuring tincol is dissolved in water, filtered, ES B2O3 with carbon in the presence of halogen.
concentrated and crystallized to get borax. • BF3 is gas, BCl3 is a liquid, BBr3 is viscous liquid and
• Small quantities of borax can be obtained by
BI3 is crystalline solid. Therefore, their melting points
neutralizing boric acid with NaOH.
SS

and boiling points also increase with them increase in

­
• Borax is sparingly soluble in cold water but highly
the atomic number of halogen.
soluble in hot water.

­
• All the trihalides of boron hydrolyse in water giving
• Crystallization of borax from saturated solution
LA

boric acid and hydrogen halide (HCl, HBr and HI).

at ordinary temperature gives prismatic borax • BF3 on hydrolysis forms H3BO3, BF4−, [BF3OH]–, HF
Na2B4O7 . 10H2O.
and H+ ions because of incomplete hydrolysis and the
•
C

Crystallization at 62°C from saturated solution gives

reaction of H3BO3 with HF formed initially.
octahedral or Jeweller’s borax Na2B4O7 . 5H2O.
• 4BF3 + 3H2O → H3BO3 + 3H+ + 3[BF4]–
L

At red hot condition, it forms borax glass which is

SA

anhydrous and absorbs moisture converting into

BF4− + H2O → [BF3OH]– + HF
­
decahydrate.
•
­
• Borax on heating with ammonium chloride gives a The degree of hydrolysis increases from BCl3 to BI3 which
N

mixture of boron nitride and oxide. supports the other evidences for increasing Lewis acid char-
acter from BF3 to BI3.
BA

Na2B4O7 + 2NH4Cl → 2BN + B2O3 + 2NaCl + 4H2O

• When boric acid is dissolved in aqueous HF forms fluo-
• When heated, it swells into white mass finally to a boric acid HBF4 which is tetrahedral and has least ten-
transparent glassy mass called borax bead. This bead dency to act as a ligand.
­
Reactions of Boron Halides
Reaction boron trifluoride Remark
−
1. BF3 + H2O → H3BO3 + HF + BF 4
+ [BF3OH] –

2. BF3 + NH4F ∆ → NH4 BF4

3. BF3 + RMg Br → RBF2, R2BF, R3B
4. BF3 + NH3 . NR3 → F3B . NH3, F3B . NR3
5. BF3 + Ether → BF3 . OR2
6. BF3 + NaBH4 Ether
 → B2H6

Chapter_07.indd 39 8/17/2013 4:01:57 PM

 Remark
7. BF3 + CH3 CN → F3B . NC CH3
8. BF3 Al
2 Cl6 or Al 2 Br6
→ BCl3 or BBr3
9. BF3 → B2H6
NaH or BF4

Reactions of BCl3 and BBr3 (BX3; X = Cl or Br)

1. BX3 + H2 Heat
→B
2. BX3 + H2O → H3BO3
3. BX3 + alcohol → B (OR)3
4. BX3 + liquid NH3 → B (NH2)3
5. BX3 + C6H5NH2 Benzene
 ∆
→ B (NHC6H5)3 HCl
→ B3N3Cl3 (C6H5)3

H
6. BX3 + R3N → X3B . NR3
BX3 + NH4Cl C 6 H 5 Cl
→ B3N3H3Cl3

AR
7. 150°
8. BX3 + CH3 NH2 → B3N3H3(CH3)3

IG
oron ydrides • The reactivity of diborane with hydrogen halides increases

AL
B H
­

• from HCl to HI and forms halogen substituted diborane in

Boron forms two series of hydrides having general
the presence of corresponding aluminium halide, which
formula BnHn+4 known as boranes and BnHn+6 known
will be converted into trihalides after some time.
­

as hydroboranes.
ES • The reactivity of halogens with diborane decreases from
• Boranes are named by the number of boron atoms
Cl2 to I2. With Cl2, it forms BCl3; with Br2, it forms
in the molecule by Greek prefix and the number of
B2H5Br at 100°C; and I2 does not react with B2H6.
SS

hydrogen atoms with arabic numbers in parentheses, • With ammonia diborane forms diammoniate of diborane
­

e.g., pentaborane (9) for B5H9.

­

(B2H6 . 2NH3) at 120°C, borazole at 200°C and boron

• Diborane is the simplest borane.
LA

nitride above 200°C.

• Diborane is prepared by treating BF3 or BCl3 with • As diborane is electron deficient, it reacts with several
­

LiAlH4 in diethyl ether.

­

molecules to form complexes. During the addition

C

• Sodium borohydride on oxidation with I2 gives of smaller sterically uncrowded Lewis bases such as
diborane.
­
NH3, primary amine and secondary amine assymmet-
L

ric cleavages take place.

­

2NaBH4 + I2 → B2H6 + 2NaI + H2

SA

B2H6 + 2NH3 → [BH2(NH3)2]+ [BH4]–

• On large scale, it is manufactured by the reaction of • With bulky Lewis bases, symmetric cleavage takes place
N

BF3 with NaH or LiH. forming two equal BH3 fragments each of which form
• It can also be prepared subjecting a mixture of boron complex with Lewis base.
BA

trichloride and hydrogen to silent electric discharge.

­

B2H6 + 2(CH3)3N → 2(CH3)3N: → BH3

• It is a colourless, highly toxic gas, slowly changes into
• With CO, ether, thioether, tertiary amines and pyridine,
higher boranes.
it forms adducts with diborane by symmetric cleavage
• It burns or explodes in air with evolution of much heat. such as BH3 . CO, H3B . O(CH3)2 , H3B . S(CH3)2 and
H3B . NR3.
B2H6 + 3O2 → B2O3 + 3H2O
• With sodium amalgam diborane, it forms an addition
• With water, it forms boric acid (H3BO3) and hydrogen. compound B2H6 . Na2Hg.
• With alkalis, it forms borates with the evolution of
• In diborane, two hydrogens are one type and the other ­

four hydrogen atoms are another type which is confirmed

hydrogen.
­

by specific heat measurements, NMR and Raman spectra

­

B2H6 + 6KOH → 2K3BO3 + 6H2 and methylation.

• Diborane on methylation yields only Me4B2H2 which
B2H6 + 2KOH + 2H2O → 2KBO2 + 6H2 indicates that the two hydrogens which cannot be

Chapter_07.indd 40 8/17/2013 4:01:58 PM

 replaced by CH3 groups have been different from the
­
orazole

B
other which are replaced.
• Borazole formed by the reaction of diborane with
• Diborane contain two hydrogen bridge bonds.
ammonia has the structure similar to benzene. There-
• In each hydrogen bridge bond in diborane, two

­
fore, it is also called inorganic benzene.
electrons are delocalized on three atoms and hence it • The difference in the structures of benzene and
­
is known as three-centred two-electron (3c-2e) bond borazole is that in benzene, the π bonds are covalent;

­
or (B-H-B) hydrogen bridge bond or protonated

­
­
however, in borazole, the π bonds are dative bonds by

­
bond. donation of lone pair on nitrogen.
•

­
The two hydrogen bridge bonds in diborane are present • Benzene and borazole both are isoelectronic, non-
one above and the other below the plane of molecule polar. Though the B-N bonds in borazole are polar, the

­
whereas the other four hydrogen atoms and two boron molecule is non-polar.
atoms (Total 6) are in the same plane. •

H
Owing to the polarity of B-N bonds, borazole is more
• In diborane, each boron is in sp3 hybridization. In the reactive than benzene. Generally, electrophile will be

AR
B-H-B bridge bond one ‘sp3’ orbital of one boron atom added to the more negative nitrogen whereas nucle-
containing one electron, one ‘s’ orbital of H atom and ophile will be added to the less electronegative boron
one vacant sp3 hybrid orbital of another boron atom during addition reactions.

IG
overlap forming molecular orbital which appear like • With two similar substituents, benzene gives three
banana. Therefore, these bonds are also called banana isomers ortho, meta and para; however, borazole gives

AL
­
bonds or sometimes as Tau bonds. four isomers one ortho, two meta and one para isomers.
• The angle HtBHt in diborane is 120 in the plane of In meta isomer, both similar substitutes may be either
molecule but 97.5° in the case of HbBHb. ES on boron or on nitrogen.

Reaction of Diborane
SS

Reaction Remark
1. B2H6 + O2 combustion
→ B2O3 + H2O
2. B2H6 + H2O → H3BO3 + H2
LA

3. B2H6 + KOH → KBO2 + H2 or K3 BO3 + H2

4. B2H6 ∆ → Higher boranes
C

5. B2H6 + Cl2 → BCl3 + HCl

B2H6 + Br2 → B2H5Br + HBr
B2H6 + I2 → No reaction
L

6. B2H6 + NH3 → [H2B(NH3)2]+ [BH4]– ∆ → B3N3H6 (borazole)

SA

B2H6 + CH3NH2 → [H2B(CH3NH2)2]+ [ BH 4− ]

B2H6 + (CH3)2NH 
−42° C
→ H3B – +NH(CH3)2 ∆
→ (CH3)2NBH2
+
N

B2H6 + (CH3)3 N →(CH3)3 N − BH 3

7. B2H6 + CH3OH → BH(OCH3)2 + B(OCH3) 3 + H2
BA

8. B2H6 + ROR → R2O → BH3

B2H6 + RSR → R2S → BH3
B2H6 + HCl  → B2H5Cl
AlCl3
9.
10. B2H6 
BCl3 or BBr3
→ B2H5Cl or B2H5Br
B2H6  → H3B ← CO or H3B ← PF3
CO or PF3
11.
12. B2H6 + LiR → LiBH4 + BR3
13. B2H6 + (CH3)2PH → (CH3)2 PH . BH3

Borohydrides in which one or more ‘H’ atoms of [BH4]– group act as

• Metal borohydrides contain tetrahedral [BH4] unit. – bridge between B and metal atoms forming 3c-2e bonds.
• The Be, Al and transition metal borohydrides are more • In Be(BH4)2, the Be and B atoms are involved in sp3
covalent and volatile. In these, the [BH4]– group acts as hybridization and have tetrahedral structure. Three
ligand and forms covalent compounds with metal ions ­tetrahedrons are joined through hydrogen bridges.

Chapter_07.indd 41 8/17/2013 4:01:59 PM

 • From each BH 4− , two hydrogen atoms are involved in • It hydrolyses in water forming Al(OH)3 liberating H2.
3c-2e hydrogen bridge bonds, one with another boron • It is polymeric giant molecule containing AlH2Al
and the other with beryllium atom thus making total bridges (Fig. 7.15).
four bridge bonds two B-H-B and two B-H-Be bonds.
• Al(BH4)3 contain six B-H-Al bridge bonds but no Aluminium O xide Al2 O
3
B-H-B bridge bonds (Fig. 7.13).
• It is prepared by thermal decomposition of Al2(SO4)3,
­

Al(NO3)3, Al(OH)3 etc.

B oron N itride • It is white amorphous powder, amphoteric in nature
• In the laboratory, boron nitride is formed by fusing and very stable compound.
borax with ammonium chloride.
• Alumina when heated with carbon or calcium carbide
forms aluminium carbide which on hydrolysis liberate
­

H
Na2B4O7 + 2NH4Cl → 2BN + 2NaCl + B2O3 + 4H2O methane.
• It is used as refractory material and adsorbent in

AR
• On large scale, it is prepared by fusing urea with boric
acid. chromatography.
­

• It is also formed by heating diborane with ammonia or

• Fused alumina at 3275k is called alundum used as
abrasive.

IG
boron in nitrogen or boron with ammonia.
• Boron nitride is formed by the action of ammonia on
• Fused mixture of alumina and lime is called bauxite cement.
• Rubies, saphires, topazs and emeralds are naturally

AL
BCl3.
occuring corrundum stones containing metal oxides as
BCl3 + 6NH3 ∆
­

→ B(NH2)3 + 3NH4Cl impurities.

2B(NH2)3 ∆
• Artificial rubies and saphires can be prepared by
→ B2(NH)3 + 3NH3
ES dropping finely powdered mixture of alumina,
B2(NH)3 ∆
­

→ 2BN + NH3 fluorspar and little colouring matter (metal oxides)

­

• through the centre of an oxyhydrogen flame.

SS

It decomposes when heated with steam under pressure

to yield ammonia.
• In the precious stones, Al3+ ions are replaced by
• With fluorine gives BF3 but when dissolved in HF transition metal ions which are coordinated by six oxy-
­

gen atoms octahedrally because of which splitting of

LA

forms NH4BF4.
• Structure of boron nitride is similar to graphite having d orbitals takes place and because of d-d transition of
­

layered lattice structure. It is slippery in nature used as electrons in the presence of light, they get the colour.
­
C

lubricant.
• Unlike graphite, it is colourless, electrical insulator as Aluminium H ydroxide
L

there is large gap between filled and vacant bands. • It is obtained as white gelatinous precipitate by the action
SA

•
­

The bond order in boron nitride is 1.33 where as in of hydroxide solution with aluminium salt solution.
borazole is 1.5. • It is amphoteric in nature, dissolves in sodium
• Layered boron nitride changes into denser cubic hydroxide to form hydroxy aluminate ions [Al(OH)4]–
N

phase at high pressure and temperatures which is hard or [Al(OH)6]3–.

analogous to diamond. •
BA

It is a polynuclear complex having layer structure

such that each aluminium atom is associated with six
C om ounds of Alum n um
p i i
OH groups and each OH group is associated with two
aluminium atoms.
Aluminium H ydride • Partly dehydrated aluminium hydroxide is called
• It is prepared by the reaction of LiH with AlCl3 in dry alumina gel which adsorbs moisture rapidly. There-
­

ether. fore, it is used as drying agent and adsorbent in chro-

3LiH + AlCl3 → 3LiCl + AlH3 matography.
• Stable up to 373K but decomposes into elements
• It is used in making water proof cloth, as mordant in
above 373K. mordant dyeing.
• It forms LiAlH4 with LiH, a useful reducing agent.
• It is an electron-deficient compound, acts as Lewis Aluminium C hloride
acid and forms addition compounds with Lewis bases • Hydrated AlCl3 . 6H2O can be prepared by dissolving
such as AlH3 . NH3 and AlH3 . N(CH3)3. aluminium or Al2O3 or Al(OH)3 in dilute HCl.

Chapter_07.indd 42 8/17/2013 4:02:00 PM

 • Anhydrous aluminium chloride cannot be prepared • It is a white crystalline solid soluble in water; the
by heating hydrated salt because it hydrolyses with its solution is acidic because of hydrolysis.

­
own water of crystallization forming Al(OH)3 or Al2O3 • On heating, it decomposes to Al2O3 and SO3.
depending on temperature. • It is a white crystalline solid soluble in water, dyeing,
• Anhydrous AlCl3 can be prepared by heating aluminium calico printing, foamite fire extinguishers, tanning of
with chlorine or HCl. leather, water proof cloth and sizing of paper.
• In Mac Affe method, anhydrous AlCl3 is prepared by
heating a mixture of Al2O3 and coke in a current of dry
Cl2 gas. Alums
• Anhydrous AlCl3 can be prepared by the dehydration of • Alums are double salts with general formula M2SO4 .

­
hydrated AlCl3 . 6H2O with SOCl2 or 2,2-dimethoxy M′2(SO4)3 . 24H2O or MM′(SO4)2 . 12 H2O where M is
propane. monovalent cation such as Na+, K+, Rb+, Cs+, Tl+ and

H
AlCl3 . 6H2O + 6SOCl2 → AlCl3 + 6SO2 + 12HCl NH4+ and M′ is trivalent cation such as Al3+, Cr3+, Fe3+,

AR
Mn3+, CO3+, V3+and Ti3+ etc.
AlCl3 . 6H2O + 6(CH3)2 C(OCH3)2 → • All alums are isomorphous. In alums, every cation is
AlCl3 + 12CH3OH + 6CH3COCH3 surrounded by six water molecules octahedrally.

IG
• Lithium cannot form alum; because of its small size, it
• It is deliquescent in nature when exposed to moist cannot be coordinated with six water molecules.
air gives fumes owing to the formation of HCl which

AL
• The common alum is potash alum K2SO4 . Al2(SO4)3 .
collects the water molecules forming droplets which 24H2O.
­
appear as fumes.
• It is prepared by mixing equimolar solutions of
• It sublimes at 180°. Below 350°C, its vapour contains
ES K2SO4 and Al2(SO4)3 followed by evaporating and
dimers Al2Cl6. Above 350°C, it converts into monomer.
crystallizaton gives alum.
• It is covalent when anhydrous does not conduct elec-
­
tric current in fused state. Soluble in organic solvents.
• It is manufactured from the mineral alum stone or
SS

alunite or by dissolving in sulphuric acid and then

The dimeric formula is retained in non-polar solvents
­
adding required amount of K2SO4.
but ionizes in water and exists as [Al (H2O)6]3+ and
­
K2SO4 . Al2(SO4)3 . 4Al(OH)3 + 6H2SO4 →
LA

Cl– ions because of heat of hydration.

• With NH4OH, forms white gelatinous precipitate
K2SO4 + 3Al2(SO4)3 + 12H2O
insoluble in excess of NH4OH; however, with NaOH,
C
­
the white gelatinous precipitate formed dissolves in • Alum shale (Al2O3 . xSiO2 . FeS2) is also used in the
excess of NaOH. preparation of alum.
L
­
• It is used as Friedel crafts catalyst and in manufacture • Alum shale on roasting converts into ferrous sulphate
SA

of dyes, drugs etc. and sulphuric acid which converts Al2O3 to Al2(SO4)3
• Anhydrous AlCl3 has six-coordinated layer structure
in the solid phase and converts into four coordinate 2FeS2 + 2H2O + 7O2 → 2FeSO4 + 2H2SO4
N

molecular dimers at its melting point and above 850°C, Al2O3 . xSiO2 + 3H2SO4 → Al2(SO4)3 + xSiO2 +
­
it converts into tri-coordinate monomer AlCl3.
BA

3H2O
• Except AlF3, other trihalides of aluminium exist as
dimers. • After the separation of FeSO4, required amount of
• In the dimer Al2Cl6 the bridge Al-Cl bonds are longer K2SO4 is added to get alum.
than terminal Al-Cl bonds. • It is white crystalline substance soluble in water; solu-
tion is acidic because of hydrolysis of aluminium sul-
phate.
Aluminium ulphate • On heating, it swells up because of the removal of water
S
• of crystallization and on further heating, it gives alumina.
It can be prepared by the reaction of aluminium or its
oxide or hydroxide with dil H2SO4.
• Alum is used in the purification of drinking water, as a
• styptic in bleeding, as mordant in dyeing and in tanning
It can be manufactured by treatment of bauxite or
­
of leather and sizing of paper.
china clay with boiling H2SO4.
• The double salts of sulphate of divalent and trivalent cati-
­
Al2O3 . 2SiO2 . 2H2O + H2SO4 → ons with 24 water molecules are called pseudo alums,
Al2(SO4)3 + 2SiO2 + 5H2O e.g., MnSO4 · Al2(SO4)3 · 24H2O.

Chapter_07.indd 43 8/17/2013 4:02:00 PM

 U ltramarines
• These are double silicates of sodium and aluminium
with sulphur.
• White ultramarine Na5Al3Si3SO12 is obtained by
fusing kaolin, soda ash, sulphur and some resin.
­
It changes to green ultramarine Na5Al3Si3S2O12 in the
presence of air.
• Blue ultramarine Na5Al3Si3S3O12 is obtained from
green ultramarine by heating with sulphur and air. ­
• Violet form is obtained by heating blue ultramarine in
a current of chlorine. ­
• Ultramarines are used in paints and laundry. ­

H
• Lapis Lazuli is one of the rare minerals of beautiful

AR
blue colour which is sodium aluminium silicate with
some sulphur and is used as a precious gem.

IG
AL
­
­ ­ ES
SS

­ ­

­
LA
C
L

­
SA

­ ­
N
BA

Chapter_07.indd 44 8/17/2013 4:02:00 PM