Hydrides And Oxides of Boron Family

Hydrides Boranes are electron deficient compounds. It is important to note that although BX 3 are well known, BH3is not known. This is due of the fact that hydrogen atoms in BH 3 have no free electrons to form pp back bonding and thus boron has incomplete octet and hence BH3 molecules dimerise to form B 6H6 having covalent and three centre bonds. Al forms only one polymeric hydride (AlH3)n commonly known as alane It contains Al..HAl bridges. ether 4LiH + AlCl3 Li[AlH4] + 3 LiCl Oxides B(OH)3 or H3BO3 is weak monobasic Lewis acid. 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 are insoluble in water and form a gelatinous precipitate. B(OH)3 + H2O B(OH)41+H+ Al2O3 being amphoteric dissolves in acid and alkalies both. Al2O3 + 3H2SO4 Al2 (SO4)3 + 3H2O fuse Al2O3 + 2NaOH 2NaAlO3 + H2O
Sodium meta aluminate

One of the crystalline form of alumina (Al 2O3) is called corrundum. It is very hard and used as abrasive. It is prepared by heating amorphous form of Al2O3 to 2000 K.

Action of Acids and Alkalies on Boron Family

Action of Acids Boron does not react with non oxidizing acids, however, it dissolves in nitric acid to form boric acids. Action of Alkalies Boron dissolves only in fused alkalies, 2B + 6NaOH (fused) 2Na3BO3 + 3H2 Al and Ga dissolves in fused as well as in aqueous alkalies, 2Al + 2 NaOH + 2H2O 2NaAl O2 + 3H2

Diagonal relationship between Boron and Silicon

The chlorides of both are liquid, fume in most air and readily hydrolysed by water. BCl3 + 3H2O B(OH)3 + 3HCl SiCl4 + H2O Si(OH)4 + 4HCl Both form weak acids like H3BO3 and H2SiO3. Both form binary compounds with several metals to give borides and silicide. These borides and silicide react with H3PO4 to give mixture of boranes and silanes. 3Mg+2B Mg3B2; Mg3B2 + H3PO4 Mixture of boranes
(Magnesium boride)

2Mg + Si Mg2Si ; Mg2Si + H3PO4 Mixture of silanes

(magnesium silicide)

The carbides of both Boron and silicon (B4C and SiC) are very hard and used as abrasive. Oxides of both are acidic and can be reduced by limited amount of Mg In excess of Mg boride and silicide are formed. B2O3 + 3Mg 3MgO + 2B ; SiO2 + 2Mg 2MgO + Si Both the metals and their oxides are readily soluble in alkalies. 2B + 6NaOH 2Na3BO3 + 3H2
(borate)

Si + 2NaOH + H2O Na2SiO3 + 2H2

(silicate)

B2O3 + 6NaOH 2Na3BO3 + 3H2O SiO2 + 2NaOH Na2SiO3 + H2O

Acids of both these elements form volatile esters on heating with alcohol in presence of conc. H 2SO4. B(OH)3 + 3ROH B(OR)3 + 3H2O Si(OH)4 + 4ROH Si(OR)4 + 4H2O

Boron Hydrides
Boron forms hydrides of the types BnHn+14 and BnHn+6 called boranes. Diborane is the simplest boron hydride which is a dimer of BH3 . Preparation 450K (a) 8BF3 + 6LiH B2H6 + 6LiBF4 (b) 4BCI3 + LiAIH4 2B2H6 + 3ACI3 + 3LiCI (c) In the laboratory, it is prepared by the oxidation of sod. Borohydride with I 2 . Polyther 2NaBH4 + I2 B2H6 + 2NaI + H2 Properties : (a) Since Boron in boranes never complete its octet of electrons hence all boranes are called as electron-deficient compounds or Lewis acids. (b) All boranes catch fire in the presence of oxygen to liberated a lot of heat energy. Thus, they can also be used as high energy fuels. B2H6 + 3O2 2B2O3 + 3H2O; H = - 1976 KJ / mole (c) Boranes are readily hydrolysed by water. B2H6 + 6H2O 2H3BO3 + 6H2 (d) With carbon monoxide B2H6 + 2CO ( BH3 CO)2 (e) Boranes are used for formation of hydroborates or borohydrides such as LiBH 4 or NaBH4 , which are extensively used as reducing agents in organic synthesis. Diethyl ether 2LiH + B2H6 2Li+[BH4]Diethyl ether 2NaH + B2H6 2Na+[BH4]Structure of diborane : B2H6 has a three centre electron pair bond also called a banana shape bond. (a) B - Ht : It is a normal covalent bond (two centre electron pair bond i.e., 2c - 2e ) (b) B - Hb : This is a bond between three atoms, (three centre electron pair bond i.e., 3c - 2e )

or Structure of diborane ( B2H6 )

Borax ( Na2B4O7. 10 H2O )

Ca2B6O11 + 2Na2CO3 Na2B4O7 + 2CaCO3 + 2NaBO2
Colemanite Borax

Properties : (a) Its aqueous solution is alkaline due to hydrolysis, Na2 B4O7 + 7H2O 2NaOH+4 H3BO3 . (b) On heating borax loses its water of crystallization and swells up to form a fluffy mass. On further heating, it melts to give a clear liquid which solidifies to a transparent glassy bead consisting of sodium metaborate (NaBO2 ) and boric anhydride ( B2O3 ), Na2B4O7. 10H2O Na2B4O7 2NaBO2 + B2O3
-10H2O Boraxbed

Borax bead test

It is used for the detection of coloured basic radicals under the name borax bead test. Borax bead test : Borax bead is a mixture of NaBO 2 and B2O3. B2O3 on heating combines readily with a number of coloured transition metal oxides such as Co, Ni, Cr, Cu, Mn, etc. to form the corresponding metaborates which possess characteristic colours, CoSO4 CoO + SO3 ; CoO + B2O3 Co (BO2)2
Cobalt meta borate ( Blue)

Colours of some important metaborates are : Cupric metaborate, Cu (BO2)2 is dark blue, chromium metaborate, Cr (BO2)2 is green, nickel metaborate, Ni(BO 2)2 is brown and manganese metaborate,Mn(BO2)2 is pink violet. When heated with C2H5OH and conc. H2SO4 it gives volatile vapours of triethyl borate which burns with a green edged flame. Na2B4O7 + H2SO4 + 5H2O Na2SO4 + 4H3BO3 H3BO3 + 3C2H5OH B ( OC2H5)3 + 3H2O
Triethyl borate

This reaction is used as a test for borate radical in qualitative analysis. Uses : (a) In making optical and hard glasses. (b) In the laboratory for borax bead test. (c) In softening of water. (d) In the preparation of medicinal soaps due to its antiseptic character.

Boric acid or orthoboric acid (H3BO3)

It is obtained from borax by treating with dil. HCl or dil.H 2SO4 , Na2B4O7 + 2HCI + 5H2O 2NaCI + 4H3BO3 It can also be obtained from the mineral colemanite by passing SO 2 through a mixture of powdered mineral in boiling water, Ca2B6 O11 + 4SO2 + 11H2O 2Ca ( HSO3)2 + 6H3BO3 Properties : (a) It is a very weak monobasic acid, does not act as a proton doner but behaves as a Lewis acid i.e. it accepts a pair of electrons from OH- ion of H2O , H3BO3 + H2O [B (OH )4 ]- + H+ It acts as a strong acid in presence of polyhydroxy compounds such as glycerol, mannitol etc. and can be titrated against strong alkali . (b) With NaOH it forms, sodium metaborate, H3BO3 + NaOH NaBO2 + 2H2O (c) With C2H5OH and conc. H2SO4 , it gives triethyl borate
Conc. H2SO4

H3BO3 + 3C2H5OH B ( OC2H5 )3 + 3 H2O

Borazine or Borasole or Triborine triamine ( B3N3H6 )

It is a compound of B, N and H. It is a colourless liquid and is also called inorganic benzene.
180oC

2B2H6 + 6NH3 2B3N3H6 + 12H2. It has a six membered ring of alternating B and N atoms, each is further linked to a H- atom.

(vi) Boron nitride (BN) It is prepared by treating BCI3 with an excess of NH3 and pyrolysing the resulting mixture in an atmosphere of NH3 at 750C,
750oC

BCI3 + NH3 [ H3N BCI3 ] BN + 3HCI.

Excess NH3

It is a colourless, good insulator, diamagnetic and almost unreactive solid

Aluminum
(1) Ores of Aluminum : Bauxite ( AI2O3.2H2O) Cryolite ( Na3AIF6, Felspar (KAISi3O8 ), Kaolinite (AI2O3. 2SiO2.2H2O ), Mica ( K2O.3AI2O3.6SiO2.2H2O), Corundum ( AI2O3) , Diaspore (AI2O3.H2O) Alunite or alum stone [ K2SO4. AI2(SO4)3. 4AI(OH)3] (2) Extraction : Aluminum is obtained by the electrolysis of the oxide (alumina) dissolved in fused cryolite. This involves following steps, Purification of ore (i) Baeyer's process
Roasted Finely powdered (red) FeOFe2o3 + Caustic soda solution high pressure (150oc, 80atm) filtered, Fe2O3 asresidue Heat

Bauxite Roasted ore

Filtered (Sod. Aluminate) CO2

FiItrate Pure AI2O3 AI(OH)3 (ii) Hall's process

+Na2CO3 CO2 50 - 60oC and filtered. Filtrate (Na2CO3)

Bauxite

Solution

(Finely powdered) Fused, extracted with (red) water.Residue Fe2O3

Heat

Precipitate Al (OH)3 Pure Al2O3 (iii) Serpek's process

+ Coke +N2

Bauxite
(Finely powdered) (white) Hydrolysis Heated to 1800oC

Silicareduced to +
Si which volatalises

Alumina
aluminium

form

AIN

nitride

Heated

Pure AI2O3 AI(OH)3

Compounds Of Aluminum

(i) Aluminum oxide or Alumina ( AI2O3) It occurs in nature as colorless corundum and several colored minerals like ruby (red), topaz (yellow), Sapphire (blue), amethyst (violet) and emerald (green). These minerals are used as precious stones (gems). (ii) Aluminum chloride ( AI2CI6 ) : It is prepared by passing dry chlorine over aluminum powder. AI2O3 +3C+3CI2 2AICI3 +3CO(g)
(anhydrous)

It exists as dimer AI2CI6 in inert organic solvents and in vapor state. It sublimes at 100 oc under vacuum. Dimeric structure disappears when AICI 3 is dissolved in water. It is hygroscopic in nature and absorbs moisture when exposed to air. (iii) Thermite : A mixture of aluminum powder and Fe 2O3 in the ratio 1:3. It is used for welding of iron. The reaction between AI and Fe2O3 is highly exothermic, AI + Fe2O3 AI2O3 + Fe Heat (iv) Aluminium sulphate [Al2(SO4)3] : It is used for the preparation of alums e.g., potash alum AI2 ( SO4 )3 . K2SO4 . 24H2O . It is also used for making fire proof clothes.

Alums
In general, the term alum is given to double sulphates of the type M2SO4.M'2 ( SO4 )3 . 24H2O where M is a univalent cation like Na+, K+ and NH4+, M' is a trivalent cation like AI3+, Fe3+ and Cr3+ . Some important points to be noted about the alums are (a) General formula is M2SO4 .M'2 ( SO4 )3 . 24H2O M = Monovalent metal; M' = Trivalent metal In alum crystals, 6 water molecules are held by monovalent ion, 6 water molecules are held by trivalent ion, 12 water molecules are held in the crystal structure. (b) All alums are isomorphous. Aqueous solutions of alums are acidic due to cationic hydrolysis of trivalent cation. (c) Double sulphates of divalent ions and trivalent ions with 24 water molecules in their crystals are known as Pseudoalums. General formula is MSO4 .M'2 ( SO4 )3 .24H2O M = Bivalent metal; M' = Trivalent metal (d) Pseudoalums are not isomorphous with alums. (e) Feather alum or Hair-salt AI2SO4 .18H2O is a native form of aluminium sulphate. (f) Potash alum is used for tanning of leather, as mordant in dyeing and calico printing, for sizing paper, as a syptic to stop bleeding and purification of water. Some important alums are Potash alum K2SO4 .AI2 (SO4)3 .24H2O Sodium alum Na2SO4 .AI2 ( SO4 )3 .24H2O Ammonium alum (NH4 ) SO4 .AI2 ( SO4 )3 .24H2O Chrome alum K2SO4 .Cr2 ( SO4 )3 .24H2O