INORGANIC CHEMISTRY

PHASE – II

Group-13

Sri Chaitanya IIT Academy.,India.

KAVURI HILLS – MADHAPUR

PREPARED BY : Mr. [Link]

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List of Ores, uses of ‘B’ compounds (from notes)
Synopis:
General characteristic properties:
1) Metallic nature: B-non metal, other elements are metals.
Metallic nature increase from B to Al and then decreases
2*) Atomic radii : B  Ga  Al  In  Tl (Metallic Radius)
(pm): (88) (135) (143) (167) (170)
3*) Ionisation enthalpy ( H1 ) : B  Tl  Ga  Al  In
B  Tl  In  Ga  Al
4) Electro negativity:
(2.0) (1.8) (1.7) (1.6) (1.5)

5) Melting point: B  Al  Tl  In  Ga
Due to B12 units connected each other in boron its m-p is very high

(2453K)
* Ga exist as Ga 2 molecules, hence m.p is low (303 K)

6) Boiling point: B  Al  Ga  In  Tl
* Due to low m.p of Ga, it exists as liquid in summer. Its high bp (2676K) makes it
useful material for measuring high temperatures.
7) density : Tl  In  Ga  Al  B
8) E0M3 /M : Al3 / Al  1.66 , Ga 3 / Ga  0.56 , In 3 / In  0.34 , Tl3 / Tl  1.26

Al is strongest reducing agent among all 13 group elements

9) Oxidation state:
1) ‘B’ forms only covalent compounds because it cannot form B3 ions due high value of
sum of its first three ionization enthalpies.
2) Al can form Al 3 ions in hydrated state/solution state and Al is highly electropositive
element.
In Ga, In, Tl both +1 and +3 O.S are observed.
Stability of +3 O.S: Al>Ga>In>Tl
Stability of +1 O.S: Al <Ga<In <Tl
* In Tl, +1 O. S. is predominant whereas +3 O.S. is highly oxidizing in character.
* The compounds in +1 O.S are more ionic than those of in +3 O.S.
electron aceptor 
Nature of Tl+3 : Tl+1  2e-
 Tl+3  
Stable  unstable  Oxidising
 

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Chemistry of Tl is dominated by +1 state  resembles alkali metals.
Tl3 tends to stabilize by changing to +1 state by gaining electrons  acts as oxidising
agent.

less  Ga +1 2electron donor Ga +3 

¬   +3  morestable
stable  In +1 In 
Ga appears to exhibit +2 in GaX2. But it is proved that exist as Ga I [Ga III X4]. GaX, InX,
TlX mono halides exist but GaX and InX are unstable and disproportionate in aq. solution.
3MX  Ms  M 3  3X   M  Ga, In 
1
T I3 exists as T , I31

10) Reactivity towards air:

* B is unreactive in crystalline form
* Al forms a very thin oxide layer on the surface and become passive.
* Amorphous boron and Al metal on heating in air form B2O3 and Al2 O3 , with N 2 they form

nitride.

2E(s)  3O2 (g)   2E 2O3 (s)

2E(s)  N 2 (g)   2EN(s)

* B2O3 is acidic, reacts with basic (metallic) oxides.

* Al2O3 ,Ga 2O3 are amphoteric and Tl2O3 , In 2O3 are basic.

11) Reaction with acids and alkalis:

* B does not react with acids and alkalis even at moderate temperatures.
* Al dissolved in mineral acids and aqueous alkalis and thus shows amphoteric characters.
2Al  6HCl 
 2AlCl3  3H 2 (g)

 2Na  Al  OH 4   3H 2
2Al  2NaOH  6H 2O 

Sodium tetrahydraxo aluminate (III)

* Conc HNO3 renders Al passive by forming a protective oxide layer on the surface.

12) Reaction with halogens:

* These elements react with halogens to form trihalides (except TlI3 )

Extraction of B:

B- rare element mainly occurs in orthoboric acid  H3BO3  , borax  Na 2B4O7 .10H2O

Kernite  Na 2B4O7 .4H2O

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* Bauxite  Al2O3.2H2O and cryolite  Na 3AlF6  are the important minerals of Al.

Extraction involves two steps : I. Ore to B2O3 II. B2O3 reduction to B

Step – I
Step – II (reduction of B2O3 )

B2 O3 + Mg 
Δ
 B + MgO
(Moissan's Boron)

(Amorphous form)

BBr3 / BCl3  H 2

 
BI3 B  crystalline  B2 H 6
W
 Van arkal 
Al /  **

B2 O 3

Properties of ‘B’
B

O2 S alkali
N2 X2 NH3 M  Except IA 
high at1200C Very high fused
temperature temperature
very high temperature
B2 O 3 B2S3 BN BX 3 Na 3BO3  H 2 BN  H 2
M x By

 Borides 
Non  stoichiometric

Note: Amorphous form of boron is used in the above reactions.

Pure Crystalline boron very unreactive, attacked by mixture of H2SO4 and HNO3 or
Na2O2 at high temperature.
B+C  B4C boron carbide best represented as B12C3

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Compounds of Boron:
1) Diborane ( B2 H 6 ):-

BF3  LiAlH 4
B2 O3  Al3O3  H 2
 LiF, AlCl3


NaBH 4  I 2 B2 H 6 BF3  NaH
H 2 ,  NaI  NaF

Mixture of boranes 

H2O
 Mg 3 B2
2NaBH 4  2H3 PO 4
H3BO3  H 2

H 2O

ROH KOH
B  OR  3  H 2 B2 H 6 KBO 2  H 2

Cl2 CH 3 I
HCl or
 CH3 2 SO4
B2 H 4  CH3 2
BCl3  H 2 B2 H5Cl  H 2


B2 H 6 .2NH 3 (or)  BH 2  NH 3 2   BH 4 


NH 3 ,120C
1: 2 
B2 H 6
NH3 NH 3 (excess)
200  C hight T
1: 2
B3 N 3 H 6  H 2 BN

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Cleavage of diborane:

Symmetrical Unsymmetrical
H H H
H H H
B B
B B
H H H
H H H

 BH 2   BH 4 
 
2BH 3

Soft bulky bases cause symmetrical Compact hard bases like NH3, H  CH3NH2,
breaking of diborane: eg. CO, N(CH3)3,
PR 3 , R 2O, THF,
(CH3)2 NH causes unsymmetrical
R 2S, Pyridine

B2 H6  2N  CH3 3  2BH3 N  CH3 3 E.g. B2 H 6  2NH 3   H 3 NBH 2 NH 3   BH 4 

 

B2 H6  2CO  2BH3  CO B2H6  2Na  H  2Na BH4 

Structure
134 pm

H H
H
B 97
B 120

H
H 119 pm H
* 4 terminal B – H bonds are regular 2c  2e  bonds
* two bridge B – H –B bonds are 3c  2e  bonds
Termind bond is shorter than bridge bond.

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2) Inorganic benzene:
undergoes addition (gives four disubstatuted products)
reactions
0
non polar


BCl3  NH 4 Cl   B3 N 3H 3Cl3 
NaBH 4
 B3 N 3 H 6
less aromatic

H 2O /   slow 

H3BO3  NH3  H 2

2) Halides:
* The trivalent compounds of these elements are electron efficient (eg BF3 ) and act as lewis

acids.
* The Lewis acidic character decreases with increase in size down the group.
BCl3  AlCl3  GaCl3  InCl3  TlCl3

* BCl3 readily accept l.p from NH3

NH 3

BCl3  NH 3 
 B
Cl
Cl
Cl

Lewis acidic nature: BF3  BCl3  BBr3  BI3 ;


B2O3  C  Cl2 
 CO,
 BCl3 
H2O
 H3BO3  HCl

all trihalides of ‘B’ undergo hydrolysis ; BF3 is partially hydrolysed.

BX 3  H 2O  H3 BO3  HX  X  Cl , Br, I  .

B  Me 3 is weaker lewis acid than Al  Me 3 and B  Ph 3 is weaker lewis acid than B  Me 3 .

Lewis acidic nature order

B  Ph 3  B  Me 3  Al  Me 3

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Boron Trihalides :  BX3  :

B  F2 HBF4  H3BO3
H 2O

BF3
conc H 2SO 4 

 / NH 3 , H 2 O PhN 2 BF4
B2O3  CaF2

B2 O3  NH 4 BF4

3) Ortho boric acid:

BCl3 ( ) O
O
Borax  HCl B (acidic nature is increased)
OH OH O O
H 2O

 160C 
H 3 BO3 HBO 2 H 2 B4 O 7 B2 O 3
100C

H 2O

H 2 O  B3 N 3H 6 B2 H 6  H 2 O
BN

1) H3BO3 is white crystalline solid.

2) Sparingly soluble in cold H 2 O but highly soluble in hot water

4) It has layer structure in which 2 – D BO3 units are joined by hydrogen bonds.

Each ring consists of 6 H3BO3 units. Inner ring contains { From quesiotn paper) 6 H-

bonds)
4) Borax:
* Na 2 B4O7 10H2O a white crystalline solid
2
* It contains the tetra nuclear units  B4O5  OH 4 

* Its correct formula is Na 2  B4O5  OH 4   8H 2O

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 HO

B
O
O O O

HO B B OH .8H 2 O
Na 2
O
O
B

OH

CO 2


Ca 2 B6 O11.5H 2 O  Na 2CO3   CaCO3  Na 2 B4O 7  NaBO 2

 2H 3BO3  2B  OH 4
()
Na 2 B4 O7  5H 2 O 
buffer solution
(nuetralised by 2 HCl)
Sodium peroxoborate:

O O OH
HO
 2 N aBO 2 .H 2 O 2
B B

O O OH
HO

(brightner in

 Na 2  B2  O 2 2  OH 4 
washing powder)
NaBO2  H 2O2  H 2O 

Aluminium Chloride:
AlCl3 .6H 2 O
OCH 3

SOCl 2 or CH3  C  CH 3

OCH 3
dry HCl
AlCl3 (an hyd)  Al2 O3  C  Cl2
Al


Al  Cl2 (dry)

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 NH 4OH NH3  
Al  OH 3  AlCl3
LiH
NH 4 OH NaOH
 excess  LiAlH 4

Insoluble Al  OH 3  conc NaOH

dil  excess 
NaOH 3
 Al  OH 6 
(excess)

 Al  OH 4   soluble 
-

* AlCl3 achieves stability by forming a dimer.

The bridge bonds are 3-centre-4-electron bonds.

206pm Cl
Cl
Cl
- -
Al 101 Al 118
790
Cl Cl
Cl 221pm

Anhydrous AlCl3 fumes in moist air

AlCl3  H 2O  Al OH 3  HCl - fumes

Structure AlF3 AlCl3 AlBr3 AlI3

Solid state (or) [Link].‘6’ [Link]. ‘6’ [Link]. ‘4’’ dimeric [Link]. ‘4’ dimeric
low distorted ‘Oh’ Layer structure molecular units molecular units
temperature surrounded by close packed
‘6’ ‘F’ atoms. lattice of Cl 
One ‘F’ shared with Al 3
between two occupying
octahedran octahedral
holes.
At m.p or Ions [Link] : 4 [Link]: 4 molecular [Link] : 4
fused state molecular dimer dimer molecular dimer
Gaseous state At 10000C Monomer + molecular dimer molecular dimer
exist as a dimer upto (Only at high temp,
monomer 1200K, above monomer exists)
1200 K, it is
monomer

*) AlF3 is non volatile and insoluble, AlF3 is ionic and rest are covalent

Thermal stability: AlF3  AlCl3  AlBr3  AlI3

M.P and B.P: AlF3  AlCl3  AlI3  AlBr3

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 Lewis acidity: AlCl3  AlBr3  AlI3 {E.N factor dominates over back bonding}

(negligible/absent)
3
Enthalpy of dimerisation Aq. solution contains  Al  H 2 O 6  ions

ALUMS
Al ions may crystallise from aq solutions, forming double salts. These have form
 M I ( H 2O)6   Al ( H 2O)6  ( SO4 ) 2 .MI is a singly charged cation such as Na+ , K+ and ammonium.

Crystals are usually octahedra and are extremely pure. Potash alum is a mordant in
dyeing. In this application Al+3 cations is precipitated as aluminum hydroxide on cloth and
helps dyes to bind to the clothes. Some M(III) ions other than Al(III) also form alums
 M I ( H 2O)6   M III ( H 2O)6  ( SO4 ) 2 . The most common trivalent ions include Fe+3 and Cr+3 but

others include Ti+3, V+3, Mn+3, In+3, Rh+3, Ir+3 and Ga+3. (But Sc 3 doesn’t form alum
similarly Li  doesn’t form alum)

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