INORGANIC CHEMISTRY

PHASE – II

Group-13

Sri Chaitanya IIT Academy.,India.

KAVURI HILLS – MADHAPUR

PREPARED BY : Mr. T.SRINIVAS

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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) C.No.‘6’ C.No. ‘6’ C.No. ‘4’’ dimeric C.No. ‘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 C.No : 4 C.No: 4 molecular C.No : 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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