Group IIIA

Boron and Its

Compound
Group IIIA
Introduction

Existence

• Kernite: Na2B4O7.4H2O
• Borax: Na2B4O7.10H2O
• Colmanite: Ca2B4O11.5H2O
Boron

• 10B - % natural abundant 19.6 %

• 11B - 80.4 %

Crystal structure
of Boron
Group IIIA
Preparation

Preparation of Boron

1) Reaction of borax in HCl

Na2B4O7 + 2HCl + 5H2O → 4H3BO3 + 2NaCl
H3BO3 → B2O3 + 3H2O
B2O3 + 3Mg → 2B +3MgO
(brown/amorphous/90-98 % pure)

2) Electrolysis KBF4 compound in a mixture of fused

KCl and KF at 800 °C.
- Boron is deposited at anode as 95 % pure.

3) Thermal decomposition (Pyrolysis) BI3 at 1327 oC by

using tantalum (Ta) filament. Boron was isolated as
crystals
2BI3 → 2B(s) + 3I2
 Group IIIA
Preparation

Cont. preparation

4) Heating diborane, B2H6 at 1000 °C

- Pure boron can be obtained by this method as thin film.

Properties
• Black non-metal element but shining likes metal.
• Semiconductor properties
• High melting point (2297oC)
• Crystal form – Icosahedron B12,
- very stable (extremely inert chemically)
- only slowly oxidized by hot concentrated HNO3
when finely powdered.
 Group IIIA
Properties

Cont. properties

• Boron powder – extremely reactive, reacted with O2, S, N2

and X2.
e.g: 4B(s) + 3O2(g) → 2B2O3(s)
4B(s) + 6S(s) → 2B2S3(s)
2B(s) + N2(g) → 2BN(s)
2B(s) + 3Cl2(g) →BCl3(g)
• At red-hot, it reduced water vapour to hydrogen.
2B(s) + H2O(g) → B2O3 + 3H2
 Group IIIA
Application

Application

• Neutron absorber (boron alloy or B4C)

10B + 1n → 7Li + 4He
5 0 3 2

• Cancer treatment- BNCT (Na2B12H11SH &

Na2B12H12)
10B
5 + 1n
0 → 7Li3 + 4He2(alpha particle) , E=2.4 MeV

• High bombardment steel in construction material.

• High purity boron is used as high temperature

semiconductor compared to Ge(37 K); Si(570 K).
 Group IIIA
Cpds - Hydrides

Compounds of Boron
Boron Hydrides

• Known as borane;
BnHn+4 (B2H6, B5H9, B6H10) and BnHn+6 (B4H10, B5H11)
BnHn2- (polyhedra)

Preparation:
1. Reduction of boron trichloride
4BCl3 + 3LiAlH4 → 2B2H6 + 3LiCl + AlCl3

2. Hydrogenation of BCl3
2BCl3 + 6H2 →B2H6 + 6HCl
diborane
Group IIIA
Cpds - Hydrides

Physical properties based on diborane, B2H6:

• Exist as gas ( m/p: = -164.9oC, b/p = -92.6oC
• Toxic

Structure of diborane (special)

• Electron deficient structure : bridging-H

• 2 B atoms bonded to 4 terminal hydrogen atoms, B−H
• Both B are connected each other by bridging hydrogen,
B−H−B
• 2 B and 4 terminal H atoms in one plane and B and 2-
bridged atom in another plane perpendicular to the first one
• B has sp3 hybridization
Group IIIA
Cpds - Hydrides

H H H
119 pm
B B
H H H
133 pm
 Group IIIA
Cpds - Hydrides
Reactions
1. Extremely reactive, flammable in air with green flame
and large energy evolved.
B2H6(g) + 3O2(g) →B2O3(s) + 3H2O(l); H= − 2040 kJ
2. Fast hydrolysis in water /alcohol
B2H6(g) + 6H2O(l) →2 B(OH)3 + 6H2
B2H6(g) + 6ROH → 2B(OR)3 + 6H2

3. React vigorously in acid and Cl2

B2H6(g) + 6HCl(l) → B2H5Cl + H2
B2H6 + Cl2 →2BCl3 + 6HCl
4. React with Lewis base to form adduct
B2H6(g) + 2L → 2(L-BH3)
e.g.: B2H6(g) + PF3 → 2(F3P-BH3)
Stability of the adduct
PF3 < CO < Et2O < Me2O < C4H8O <<< H−
Group IIIA
Cpds - Hydrides

Applications

• NaBH4 (BH4- ion) is reducing agent for aldehide /keton

to alcohol
e.g.: CH=CHCHO → CH=CHCH2OH
(*selective reducing agent because does not reduce
double bond).

• Supply of H2 gas
 Group IIIA
Cpds - Oxides

Boron Oxide (B2O3)

Preparation:
1. Burning B in oxygen/air
4B + 3O2 → 2B2O3

2. Fusing solid boric acid

2H3BO3(s) → B2O3(s) + 3H2O(l)

Structure:
Empirical formula = (BO3/2) = B2O3
Each oxygen bonded to 2 B B
O

B B B
O O
 Group IIIA
Cpds - Oxides

Properties:
• Acidic oxide
• React slowly in water → boric acid
B2O3(s) + 3H2O(l) → 2H3BO3(s)
• If boron oxide is fused with other metal oxides →
coloured borate glass is produced.

Application:
• Produced borosilicate glass (trade name such as pyrex
etc)
 Group IIIA
Cpds - Hydroxide

Boron Hydroxide

• Known as Boric Acid, B(OH)3 or H3BO3

Preparation:
1. Hydrolysis of boron trihalide, e.g. BCl3(g)
BCl3(g) + 3H2O(l) → H3BO3(aq) + 3HCl(aq)

2. Reaction between dilute HCl and Borax

Na2B4O7 (s) + HCl(aq) + 5H2O(l)
→ 4H3BO3(aq) + 2NaCl(aq)
 Group IIIA
Cpds - Hydroxide

Properties:
• White needle crystal
• Soluble in hot water (slightly in cold water)
• Easily vapourized
• Weak monobasic acid
• Acting as Lewis acid – can accept OH−
or dissociation in water
B(OH)3 + 2H2O → B(OH)4− + H3O+
• React with alcohol to form borate ester. H2SO4 as catalyst.
B(OH)3 + 3ROH → B(OR)3 + 3H2O
• Boric acid act as antibacterial, additive → in soap,
detergent, washing powder, hand cream, Eye-Mo noodle,
soy-sauce etc
Group IIIA
Cpds - Hydroxide

• Weak acid in aqueous solution but becomes stronger

acid in diol (glycol, mannitols, glucose)

B(OH)3 + H2C-OH H2CO OH

B- + H 3 O+
H2C-OH H2CO OH
glycol glycol
The reaction is used to determine
the concentration of boric acid by
H2CO OCH2
titration with NaOH −
B + 2H2O
NaOH + H3O+ → H2O + Na+ H2CO OCH2
1 mol B(OH)3  1 mol H3O+
 Group IIIA
Cpds - Hydroxide

• Thermal dissociation of H3BO3 formed metaboric acid;

HBO2
H3BO3 → HBO2 + H2O

• Complete fusion of boric acid gives B2O3 in glass form.

Dissolved
in other metal oxide → borate glass
in silica (SiO2)→ borosilicate (tradename Pyrex)
Group IIIA
Cpds - Oxides

Structure:
• Based on B(OH)3 planar unit, each unit is connected by H-
bond.
• Each layer- 2 dimension – as hexagon (like graphite)
• Each layer is hold by van der Waals forces, →→ slippery,
easily cleaves into flakes and vaporize/chip.
•
•
 • •
 

 • 
•

•
   = oxygen

• • • •=
•
 •  • hydrogen
 •  =
 y
•  •  boron
•
  x
•
 Group IIIA
Cpds - Borate

Borate
• Prepared by fusing boric acid and metal oxide.
• Polyoxyborate anion can exists as a ring or chain, by
sharing oxygen with one neighbouring boron, e.g.: [B3O6]3-

• Borax
– Borate species.
– Fusing with transition metal → coloured glass
e.g: Co(BO2)2 and Cu(BO2)2 – blue
(drastic cooling → metaborate anion do not align to form
crystals)
• Uses
1. Coloured glass – decoration materials
2. Pyrex glass (borosilicate) – laboratories equipments
(thermal expansion low – not easily breakable)
Group IIIA
Cpds - Halide

Boron Halide, BX3

Preparation:
1. BX3, X = Cl → I
• Direct halogenation of boron with halogen at high
temperature
2B + 3X2 → 2BX3 (X = Cl →I)

2. BF3
• Heating B2O3 with CaF2
• Heating B2O3 with NH4BF4 and sulphuric acid
B2O3 + 6NH4BF4 + H2SO4 → 3(NH4)2SO4 + 8BF3 + 3H2O
Group IIIA
Cpds - Halide

Structure:
• Trigonal planar with B having sp2 hybridization

 _ __ __ _ _ _ __
2s 2p hybrid sp2 p
B: (ground state) *B (Excited state)
 Group IIIA
Cpds - Halide

Properties:
• Covalent and easily vaporize (inversely proportional) to MW.
E.g: BF3 > BCl3 > BBr3 > BI3
Gas ------- liquid solid

• Strong Lewis acid

Easily accept a pair of electron from Lewis bases such as
amine (RNH2) or alcohol (ROH) +
:F F
Trend of Lewis acid strength:
*BF3 < BCl3 < BBr3 > BI3# B B
−
F F F F

*Electronegativity of F very high, lone pair electron from F is donated

back to B → forming p - p bond between B – F bond resulting in
the increases of electron density on the B → weak Lewis acid

#Steric effect – due to large size of Iodin – poor overlapping of the np

orbital with 2p orbitals of B
Group IIIA
Cpds - Halide

Cont. Properties:

• Vigorous reaction with water to give halogen

hydride (Except BF3 →HBF4, fluoroboric acid).
e.g:
BCl3(g) + H2O(l) →H3BO3(aq) + 3HCl(g)
3BF3(g) + 3H2O(l) →3HBF4(aq) + H3BO3(aq)
or
BF3(g) + H2O(l) →H3BO3(aq) + 3HF(g)
HF(aq) + BF3(g) →HBF4(aq) )

• Complete hydrolysis of BCl3 and BBr3 → stronger

acid than BF3
Group IIIA
Cpds - Halide

Application

• BF3 is used as Friedel Crafts catalysts (as

Lewis Acid) in olefin polymerization or alkylation
of aromatic-HC

+ −
C2H5F + BF3 [C2H5----F----BF3]
C6H6 (benzene)

H +
HBF4 + C 2H 5 C 2H 5 + BF4−
 Group IIIA
Cpds - Nitride

Boron Nitride
Preparation:
1. Heating B2O3 in ammonia at 1200oC
B2O3 + 2NH3(g) → 2BN(s) + 3H2O(g)
• Form 2 stable polymorphs,
Graphite type and the diamond type (sphalerite).
Graphite type is more stable

Properties:
• Graphite type: form planar hexagon layer
• Slippery (easily slipping away) therefore is used as lubricant.
• Electric insulator (no delocalized e− due to the charge
separation on adjacent atoms, −B=N+)
• White refectory solid,
• BN layer changes to sphalerite cube
at high T and P and becoming as hard as diamond
 Group IIIA
Cpds - Nitride

Borazine, B3N3H6
Resonance hybrid structure similar to benzene
Preparation:
1. Reaction between diborane and ammonia
3B2H6 + 6NH3 → 2B3N3H6 + 12H2 H H

H N H H N H
..
B B B B

Properties: H
N
B
N
H H
N:
B
:N
H

• Similar structure like benzene but different properties.

H H

e.g: Borazine reactive towards HCl but benzene is

inert.
B3N3H6 + HCl → Cl3B3N3H9
e.g. React as reducing agent and sensitive towards
moisture and water (H+ and OH-).
B3N3H6 → (HO)3B3N3H9
 Group IIIA
Cpds - Nitride

Cont. Properties:
• Different properties is due to  electron in borazine is
localized but in benzene is delocalized →
electronegativity difference between B – N is large
→→charge separation
• Liquid at room temperature (b.p=55oC)
 Group IIIA
Uses

Summary of the Uses of Boron and its cpds

The following uses for boron are gathered from a number of
sources as well as from anecdotal comments.
• amorphous boron is used in pyrotechnic flares (distinctive
green colour), and rockets (as an igniter)
• boric acid, is used as a mild antiseptic
• borax, Na2B4O7.10H2O, is a cleansing flux in welding
• borax, Na2B4O7.10H2O is a water softener in washing
powders
• boron compounds are used in production of enamels for
covering steel of refrigerators, washing machines, etc.
• boron compounds are extensively used in the manufacture
of enamels and borosilicate glasses
 Group IIIA
Uses

• boron compounds show promise in treating arthritis

• 10B is used as a control for nuclear reactors, as a shield
for nuclear radiation, and in instruments used for
detecting neutrons
• boron nitride is as hard as diamond. It behaves like an
electrical insulator, but conducts heat like a metal. It
also has lubricating properties similar to graphite
• the hydrides are sometimes used as rocket fuels
• boron filaments, a high-strength, lightweight material, are
used for advanced aerospace structures, .
• lightweight compounds used for aerospace structures
• boron filaments used in fibre optics research
• Boric Acid is also used in North America for the control of
cockroaches, silverfish, ants, fleas, and other insects
Group IIIA
Uses

Anomaly of Boron
• Boron – non metal, formed icosahedron, B12. Other element – metallic
- with metallic character.
Boron oxide, B2O3 - an acidic
Al2O3 & Ga2O3 - amphoteric
In2O3 & Tl2O3 - basic

Boron hydroxide, B(OH)3 – an acid

Al(OH)3 - amphoteric
Others - amphoteric, but showed > basic character.

• Boron chloride, BX3 – monomer, covalent.

Others – covalent dimer, M2X6, (except MF3 (M = Al→In), ionic)

• Boron does not replaced H from non oxidizing acid (HCl/H2SO4)

but others do.
B + 4HCl →
Al + 4HCl → [AlCl4]− + 2H2
 Group IIIA
Uses

Diagonal Relationship (B & Si)

1. The hydrides are easily vaporized, covalent, reactive, easily hydrolyzed by water or
acid.
BH3 + 3H2O → B(OH)3 + 3H2
SiH4 + 4H2O → Si(OH)4 + 4H2
2. Halides – covalent
- easily hydrolysed by water.
BX3 + H2O → B(OH)3 + 3HX
SiX4 + 4H2O→ Si(OH)4 + 4HX
3. Boric/silicic acids – weak acid.
Borate and silicate salt – polyanionic formed → solid solution
The bond strength : B⎯O = Si⎯O
4. Non- metal elements
→ Crystal and amorphous formed.
→ Size, electronegativity, density, etc, are similar.
Dissolved in alkali – H2
Strong reducing agents in alkaline solution.
5. B2O3/SiO2 (oxides) – covalent acid, polymeric macromolecules.
Dissolved molten metal oxide to form borate/silicate, dissolved in each other →
glass