-*

PBLOCK ELEMENTS

THE GROUP 13 ELEMENTS (BORON GROUP)

GENERAL PROPERTIES
Electronic configuration
Element Electronic configuration ( ns2 np1 )

5B 1s2 ,2s2 2p1 or [He] 2s2 2p1

13 Al 1s2 ,2s2 2p6 ,3s2 3p1 or [Ne] 3s2 3p1

31Ga 1s2,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p1 or [Ar]3d10 4s2 4 p1

49 In 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p6 4d10,5s2 5p1 or [Kr]4d105s2 5p1

81Tl 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p6 4d10 4 f 14,5s2 5p6 5d10,6s2 6p1 or [Xe]4 f 14 5d10 6s2 6p1

Physical properties
(1) A regular increasing trend in density down the group is due to increase in size.
(2) Melting points do not vary regularly and decrease from B to Ga and then increase.
(3) Boron has very high m.pt because it exist as giant covalent polymer in both solid and liquid
state.
(4) Low m.pt of Ga (29.80C) is due to the fact that consists of only Ga 2 molecule; it exist as liquid
upto 20000C and hence used in high temperature thermometry.
(5) Boiling point of these elements however show a regular decrease down the group.
(6) The abrupt increase in the atomic radius of Al is due to greater screening effect in Al (it has 8
electrons in its penultimate shell ) than in B (it has 2 electrons in its penultimate shell)
(7) The atomic radii of group 13 elements are smaller than the corresponding s-block elements.
This is due to the fact that when we move along the period, the new incoming electron occupy
the same shell whereas the nuclear charge increases regularly showing more effective pull of
nucleus towards shell electrons. This ultimately reduces the atomic size.
(8) The atomic radius of Ga is slightly lesser than of Al because in going from Al to Ga, the
electrons have already occupied 3d sub shell in Ga. The screening effect of these intervening
electrons being poor and has less influence to decrease the effective nuclear charge, therefore
the electrons in Ga experience more forces of attractions towards nucleus to result in lower size
of Ga than Al
(9) Oxidation state
(i) All exhibit +3 oxidation state and thus complete their octet either by covalent or ionic union.
(ii) Boron being smaller in size cannot lose its valence electrons to form B 3+ ion and it usually
show +3 oxidation no. The tendency to show +3 oxidation no. however decreases down the
group Even Al shows +3 oxidation no. in most of its compounds.
(iii) Lower elements also show +1 ionic state e.g Tl +, Ga+. This is due to inert pair effect. The
phenomenon in which outer shell ‘s’ electrons (ns2) penetrate to (n-1) d electrons and thus
become closer to nucleus and are more effectively pulled the nucleus. This results in less
availability of ns2 electrons pair for bonding or ns 2 electron pair becomes inert. The inert pair
effect begins after n  4 and increases with increasing value of n.

1
 (iv) The tendency to form M+ ion increases down the gp. Ga+1 < Tl+1
(10) Hydrated ions : All metal ions exist in hydrated state.
(11) Ionisation energy
(i) Inspite of the more charge in nucleus and small size, the first ionisation energies of this
group elements are lesser than the corresponding elements of s block. This is due to the fact
that removal of electron from a p-orbitals (being far away from nucleus and thus less
effectively held than s-orbitals) is relatively easier than s-orbitals.
(ii) The ionisation energy of this group element decrease down the group due to increases in
size like other group elements.
(iii) However, ionisation energy of Ga are higher than that of Al because of smaller atomic
size of Ga due to less effective shielding of 3d electrons in Ga. Thus valence shell exert
more effective nuclear charge in Ga to show higher ionisation energies.
(12) Electropositive character
(i) Electropositive character increases from B to Tl.
(ii) Boron is semi metal, more closer to non-metallic nature whereas rest all members are
pure metals.
(iii) Furthermore, these elements are less electropositive than s-block elements because of
smaller size and higher ionisation energies.
(13) Oxidation potential
(i) The standard oxidation potentials of these element are quite high and are given below,
B Al Ga In Tl
E0op for M  M3++ 3e – +1.66 +0.56 +0.34 +1.26
E op for M  M + e
0 +
– +0.55 – +0.18 +0.34
(ii) However Boron does not form positive ions in aqueous solution and has very low
oxidation potential.
(iii) The higher values of standard oxidation potentials are due to higher heats of hydration on
account of smaller size of trivalent cations.
(iv) Aluminium is a strong reducing agent and can reduce oxides which are not reduced even
by carbon. This is due to lower ionisation energy of aluminium than carbon. The reducing
character of these elements is Al > Ga > In > Tl.
(14) Complex formation : On account of their smaller size and more effective nuclear charge as
well as vacant orbitals to accept elements, these elements have more tendency to form
complexes than-s block elements.

Chemical Properties

(1) Occurrence: The important of this group elements are given below,

Boron : Borax (Tincal) (Na2B4O7.10H2O), Colemanite(Ca2B6O115H2O)

Boracite (2Mg3B8O15.MgCl2), Boronatro calcite(CaB4O7.NaBO2.8H2 O),
Kernite (Na2B4O7.4H2O), Boric acid (H3BO3)
Aluminium : Corundum (Al2O3), Diaspore (Al2O3.H2O), Bauxite (Al2O3. 2H2O), and Cryolite
(Na3AlF6).
(2) Hydrides
(i) Elements of gp 13 do not react directly with hydrogen but a number of polymeric
hydrides are known to exist.
2
(ii) Boron forms a large no. of volatile covalent hydrides, known as boranes e.g. B2
H6,B4H10,B5H11 ,B6H10 Two series of boranes with general formula B nHn + 4 and BnHn + 6
are more important.
(iii) Boranes are electron deficient compounds. It is important to note that although BX 3 are
well known, BH3 is not known. This is due of the fact that hydrogen atoms in BH 3 have no
free electrons to form p-p back bonding and thus boron has incomplete octet and hence
BH3 molecules dimerise to form B6H6 having covalent and three centre bonds.
(iv) Al forms only one polymeric hydride (AlH3)n commonly known as alane It contains
A1…..H……Al bridges.
(v) Al and Ga forms anionic hydrides e.g. LiAlH4 and Li Ga H4 ,
ether
4LiH  AlCl3   Li[AlH 4 ]  3LiCl

(3) Reactivity towards air

(i) Pure boron is almost unreactive at ordinary temperature. It reacts with air to form B 2O3
when heated It does react with water. Al burns in air with evolution of heat give Al2O3.
(ii) Ga and In are not effected by air even when heated whereas Tl is little more reactive and
also form an oxide film at surface. In moist air , a layer of Tl (OH) is formed.
(iii) Al decomposes H2O and reacts readily in air at ordinary temperature to form a protective
film of its oxides which protects it from further action.

(4) Oxides and hydroxides

(i) The members of boron family form oxide and hydroxides of the general formula M 2O3 and
M (OH)3 respectively.
(ii) The acidic nature of oxides and hydroxides changes from acidic to basic through
amphoteric from B to Tl.
B2O3 and B(OH)3> Al2O3 and Al(OH)3 >Ga2O3 and Ga(OH)3> In2O3 In (OH)3> Tl2O3 Tl(OH)3
(acidic) (amphoteric) (amphoteric) (basic) (strong basic)

Note : B(OH)3 or H3BO3 is weak monobasic Lewis acid.

(iii) Boric acid, B(OH)3 is soluble in water as it accepts 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+
(iv) Al2O3 being amphoteric dissolves in acid and alkali both.
fuse
Al2O3 + 3H2SO4 Al2 (SO4)3 + 3H2O ; Al2O3  2NaOH  2NaAlO3  H 2O
Sodiummetaaluminate

(v) One of the crystalline form of alumina (Al 2O3) is called corundum. It is very hard and used
as abrasive. It is prepared by heating amorphous form of Al2O3 to 2000 K.
(5) Action of Acids
(i) Boron does not react with non oxidizing acids, however, it dissolves in nitric acid to form
boric acids.
(ii) Al, Ga and In dissolve in acids forming their trivalent cations; however, Al and Ga become
passive due to the formation of protective film of oxides.
(iii) Thallium dissolves in acids forming univalent cation and becomes passive in HCl due to
the formation of water insoluble TICl.
(6) Action of Alkalies
3
(i) Boron dissolves only in fused alkalis, 2B + 6NaOH (fused)2Na3BO3 + 3H2
(ii) Al and Ga dissolves in fused as well as in aqueous alkalis,
2Al + 2 NaOH + 2H2O 2NAl O2 + 3H2
(iii) Indium remains unaffected in alkalies even on heating.

(7) Halides
(i) All the group 13 elements from the trihalides, MX3 on directly combining with halogens.
M + X2  MX3
(ii) All the trihalides of group 13 elements are known except Tl (III) iodide.
(iii) Due to small size and high electronegativity of boron, all boron halides are covalent and
Lewis acids. These exist as monomeric molecules having plane triangular geometry (sp 2
hybridization).
(iv) All Boron trihalides except BF3 are hydrolysed to boric acid.
BX3+ 3H2O B(OH)3 + 3HX; [X=Cl,Br,I]
However, BF3 forms as addition product with water, BF3 + H2O  H+ [BF3OH]-
BF3 having less tendency for hydrolysis as well as Lewis acid nature, is extensively used as a
catalyst in organic reactions e.g. Friedel- Crafts reaction.
(v) Boron atom, in BX3, has six electrons in the outermost orbit and thus it can accept a pair of
electrons form a donor molecule like NH 3 to complete its octet. Hence boron halides act as
very efficient Lewis acids. The relative Lewis acid character of boron trihalides is found to
obey the order ;
BI3 > BBr 3 > BCl3 > BF3.
However, the above order is just the reverse of normally expected order on the basis
relative electronegativities of the halogens. Fluorine, being the most electronegative, should
create the greatest electron deficiency on boron and thus B in BF 3 should accept electron
pair from a donor very rapidly than in other boron trihalides. But this is not true.
This anomalous behaviour has been explained on the basis of the relative tendency of the
halogen atom to back-donate its unutilised electrons to the vacant p orbitals of boron atom.
In boron trifluoride, each fluorine has completely filled unutilised 2p orbitals while boron
has a vacant 2p orbital. Now since both of these orbitals belong to same energy level (2p)
they can overlap effectively as a result of which fluorine electrons are transferred into the
vacant 2p orbital of boron resulting in the formation of an additional p – p bond. This
type of bond formation is known as back bonding or back donation. Thus the B- F bond
has some double bond character. Back bonding may take place between boron and of the
three fluorine atoms and thus boron trifluoride is regarded as a resonance hybrid of some
structures.
Resonance in boron trifluoride is also evidenced by the fact that the three boron-fluorine
bonds are indentical and are shorter than the usual single boron-fluorine bond As a result of
back bonding, the electron deficiency of boron is reduced and hence Lewis acid nature is
decreased. The tendency for the formation of back bonding (p- p bond) is maximum
in BF3 and decreases very rapidly from BF 3 to BI3 This is probably due to the fact that
overlapping of the vacant 2p orbitals of boron cannot take place easily with the p-orbitals
of high energy levels (3p in Cl, 4p in Br and 5p in iodine). Thus BI 3 Br3 and BCl3 are
stronger Lewis acids than the BF3.
(vi) Lewis acid character of halides of the group 13 elements decreases in the order,B > Al >
Ga > In

4
 (vii) Boron halides form complex halides of the type, [BF4-], in which boron atom extends its
coordination number to four by utilising empty p-orbital. It cannot extend its coordination
number beyond four due to non availability of d-orbitals. However, the other trihalides of
this group form complex halides of the type (AlF6)3-, (GaCl6)3- and (InCl6)3-, etc where the
central atom extends its coordination number to 6 by the use of d-orbitals.
(viii) The fluorides of Al, Ga In and Tl are ionic and have high melting points. The high melting
points of metal fluorides can be explained on the basis that their cations are sufficiently
large and have vacant d-orbitals for attaining a coordination number of six towards the
relatively small fluorine atom.
(ix) Other halides of Al, Ga, In and Tl are largely covalent in anhydrous state and possess low
m.pt. These halides do not show backbonding because of increases in the size of the
element. However, the make use of vacant p-orbitals by co-ordinate bond i.e. metal atoms
complete their octet by forming dimers. Thus aluminium chloride, aluminium bromide and
indium iodide exist as dimers, both in the vapour state and in non-polar solvents.
Note : The dimer structure for Al2Cl6 is evidenced by the following facts,
(a) Vapour density of aluminium chloride measured at 4000C corresponds to the formula Al2 Cl6.
(b) Bond distance between aluminium chlorine bond forming bridge is greater (2.21A 0) than the
distance between aluminum-chlorine bond present in the end (2.06 A0). The dimeric structure
disappears when the halides are dissolved in water This is due to high heat of hydration which split
the dimeric structure into [M(H2O)6]3+ and 3X- ions and the solution becomes good conductor of
electricity.
Al2Cl6 + 2H2O 2[Al(H2O)6]3++6Cl- ; Therefore Al2Cl6 is ionic in water.
The dimeric structure may also split by reaction with donor molecules e.g. R 3N. This is due to the
formation of complexes of the type R3NAl Cl3 The dimeric structure of Al2 Cl6 exist in vapour state
below 473 K and at higher temperature it dissociates to trigonal planar AlCl3 molecule.

Note:- Boron halides do not exist as dimer due to small size of boron atom which makes it unable
to co-ordinate four large-sized halide ions.
(x) BF3 and AlCl3 acts as catalyst and Lewis acid in many of the industrial process.

2.1.4 Some dissimilarities of boron with other elements of this group

(i) Boron is a nonmetal, while all other elements of this group are metals.

(ii) Boron forms only covalent compounds, while other elements of this group form both covalent and
ionic compounds.

(iii) Boron shows a maximum covalency of four, while other elements of this group show
a maximum valency of six, absorbs neutron and is steel grey in colour. Its density is
2.34 gm/cc.

2.2. BORON
2.2.1. Isolation of Boron
Ores of boron
(i) Borax or tincal : Na2 B4O7 . 10 H2O (iv) Orthoboric acid : H3BO3
(i) Reduction of boric oxide with highly electropositive metals like Na, K and Mg in the absence of
air.

B2O3 (s) + 6K(s) 
 2B(s) + 3K2O(s)

5
 
B2O3 (s) + 3Mg(s) 
 2B(s) + 3MgO(s)

The product thus obtained is boiled with HCl and filtered when K 2O and MgO dissolves, leaving
behind elemental B. The powdered B thus obtained is thoroughly washed with water to free it from
HCl and is finally dried
(ii) Modern Method

B is obtained these days by the electrolysis of a fused mixture containing boric anhydride, MgO
and MgF2 at 1100C. The electrolysis is done in a carbon crucible, which acts as anode and Fe rod
is used as cathode. The Mg discharged at cathode reduces B2O3 to B.

2MgO  2Mg + O2

B2O3 + 3Mg  2B + 3MgO

B thus obtained is heated electrically in vacuum at 1100C, when the impurities are volatilised off
and pure boron is obtained.
(iii) By thermal decomposition of BI3 over red hot tungsten filament (Van Arkel method)
W
2BI3    2B(s) + 3I2(g)
1173 K

2.2.2. Chemical properties of boron

Crystalline B is not active while amorphous B reacts. The reactions are

as follows.

(a) Reaction with air

700°C
4B + 3O2 2B2O3
700°C
2B + N2 2BN

The above reaction accompanies red flame.

High temp. & press.
BN + 3H2O      H3BO3 + NH3

(b) Action of alkali and acid

2B + 2NaOH + 2H2O  2NaBO2 + 3H2

High temp.
2B + 3H2O    B2O3 + 3H2
oxidation
2B + 3H2SO4 2H3BO3 + 3SO2
oxidation
2B + 6HNO3 2H3BO3 + 6NO2

(c) Boron reacts with Mg and consequent hydrolysis gives diborane.

3Mg + 2B  Mg3B2

3Ca + 2B  Ca3B2

6
 Mg3B2 + 6HCl  3MgCl2 + B2H6

B2H6 + 6H2O  2H3BO3 + 6H2

(d) Boron reduces SiO2, CO2

3SiO2 + 4B  2B2O3 + 3Si

3CO2 + 4B  2B2O3 + 3C

2.3 COMPOUNDS OF BORON

2.3.1. Boron halides

Let us discuss the acidic character of boron trihalides.

The shape of the BF3 molecule is a planar triangle with bond angles of 120°. This is predicted by
VSEPR theory as the most stable shape for three outer electron pairs around B. The valence bond
theory also predicts a planar triangle with hybridisation of one s and two p orbitals used for
bonding. However, the B atom only has six electrons in its outer shell and this is termed electron
deficient.
1s
Electronic structure of
boron atom excited state

three singly occupied orbitals form bonds with

unpaired electrons from three halogen atoms
2
shape: triangular planar (sp hybridization)

The bond lengths in BF3 are 1.30 Å each and are significantly shorter than the sum of the covalent
radii (B = 0.80 Å, F = 0.72 Å). The bond energy is very high: 646 kJ mol 1, which is higher than
for any single bond. The shortness and strength of the bonds is interpreted in terms of a pp
interaction, that is the bonds possess some double bond character. The empty 2p z atomic orbital on
B which is not involved in hybridisation is perpendicular to the triangle containing the sp 2 hybrid
orbitals. This pz orbital may accept an electron pair from a full pz orbital on any one of
the three fluorine atoms. Thus, a dative  bond is formed and the B atom attains an octet of
electrons. If one localized double bond existed, then there would be one short bond and two longer
ones. However, all measurements show that the three bond lengths are identical. The old valence
bond explanation of this was resonance between three structures with the double bond in different
positions. The modern explanation is that the double bond is delocalised. The p z atomic orbitals
from B and the three F atoms form a fourcentre  molecular orbital covering all four atoms which
contains two bonding electrons.
2p
2p
F
F B
F

The acidic strength of the trihalides is in order

BBr3 > BCl3 > BF3

The order is the reverse of what would be normally expected on the basis of electronegativity of
halogen and also on the basis of steric grounds.
7
 This is explained on the basis of BX bonding. The tendency to form the pp double
bond is maximum in BF3 and decreases very rapidly as we move to BCl3 and BBr3.

2.3.2. Orthoboric acid (H3BO3)

Structure of orthoboric acid

Orthoboric acid contains triangular BO 33  units. In the solid, the B(OH)3 units are hydrogen bonded
together into twodimensional sheets with almost hexagonal symmetry. The layers are quite a
large distance apart and thus the crystal breaks quite easily into very fine particles.
H H

H H H H
B

H B H H B H

H H H H

H B H H B H

H B H
H H

H H
Hydrogen bonded structure of orthoboric acid

Preparation

Na2B4O7 + 2HCl + 5H2O  2NaCl + 4H3BO3

2CaO + 3B2O3 + 2SO2 + 9 H2O  2CaSO3 + 6H3BO3

2CaSO3 + 2H2O + 2SO2  2Ca (HSO3)2

Properties

H3BO3 + H2O  [B(OH4)] + H+ (aq)

Acidic properties of H3BO3 or B(OH)3

Since B(OH)3 only partially reacts with water to form H 3O+ and [B(OH)4], it behaves as a weak acid.
Thus H3BO3 or [B(OH)3] cannot be titrated satisfactorily with NaOH, as a sharp end point is not obtained.
If certain organic polyhydroxy compounds such as glycerol, mannitol or sugars are added to the titration
mixture, then B(OH)3 behaves as a strong monobasic acid. It can now be titrated with NaOH and the end
point is detected using phenolphthalein as indicator (indicator changes at pH 8.3  10.0).

B(OH)3 + NaOH Na[B(OH)4]  NaBO2 + 2H2O

Sodium metaborate

100°C 140°C strong heating

H3BO3 –H2O
HBO2 –H2O
H2B4O7 2B2O3
–H2O

meta boric acid Boron sesquioxide

Again B2O3 + H2O  H3BO3

BF3 is a strong Lewis acid and forms adduct with NH3

8
Uses of Boric acid

(i) Boric acid is used in the manufacture of enamels and pottery glazes.

(ii) Boric acid is used in medicines as an eye wash.

(iii) Boric acid is used for making borosilicate glass.

Boric acid on heating gradually loses its water of crystallisation to finally give borontrioxide.
375 K 435 K red heat
4H3BO3  
4H2O
4HBO2  
H2O
H2B4O7  
H2O
2B2O3(s)

boric acid metaboric acid tetraboric acid boron trioxide

2.3.4 Borax (Na2B4O7.10H2O)

Structure of Borax

In borax, two boron atoms are in triangular geometry and two boron atoms are in tetrahedral
geometry. The ion is [B4O5(OH)4]2 and the remaining eight water molecules are associated with
the two sodium ions. Hence, the borax contains tetranuclear units [B 4O5(OH)4]2 and therefore is
formulated as Na2[B4O5(OH)4].8H2O.

OH
B
O O
HOB O BOH
O O
B
OH
Structure of borax anion

Borax occurs naturally as tincal (contains about 55% borax) in certain inland lakes of India, Tibet
and California (U.S.A.).

Borax can also be prepared from certain other minerals such as boracite, colemanite and
boranatrocalcite. The minerals are powdered and boiled with sodium carbonate solution.

Ca2B6O11 + 2Na2CO3  2CaCO3 + Na2B4O7 + 2NaBO2

Borax is crystallised from the filtrate. Sodium metaborate, present in the mother liquor, is
converted into borax by passing carbon dioxide through it

4NaBO2 + CO2  Na2B4O7 + Na2CO3

Properties of Borax

(i) Borax is a colourless, crystalline solid sparingly soluble in cold water but dissolves readily in hot
water. It forms two important hydrates: octahedral borax Na2B4O7.5H2O and monoclinic borax
Na2B4O7.10H2O.

(ii) Basic nature

Borax is slightly hydrolysed in solution. As boric acid is a weak acid, the solution is alkaline in nature.

9
 B 4 O 72 + 7H2O 2OH + 4H3BO3

(iii) Action of acids

Borax reacts with HCl or H2SO4 to form boric acid. On cooling, the white flakes of boric acid are
obtained

Na2B4O7 + 2HCl + 5H2O  2NaCl + 4H3BO3

boric acid

(iv)Action of heat
When powdered borax is heated strongly in a bunsenflame, it loses water of crystallization and
forms colourless, transparent glasslike bead which is made up of sodium metaborate and boric
anhydride.
 
Na2B4O7.10H2O  Na2B4O7  2NaBO2 + B2O3
borax sod. Metaborate boron oxide

transparent bead
Uses of Borax

Borax is used,

(i) for manufacturing enamels, glazes and optical glass.

(ii) as a flux for soldering and welding.

(iii) as an analytical reagent, e.g. in borax bead test.

2.3.5 Boron Nitride (Inorganic Graphite)

1200°C
Na2B4O7 + 2NH4Cl 2 NaCl + H2O + 2B2O3 + 2NH3

B2O3 + 2NH3  2BN + 3H2O

Structure of boron nitride Structure of Graphite

B B B C C C
N N N C C C
N C
B B B B C C C C
N N N C C C

They are soft and used as lubricating material.

2.3.6 Boranes

Structures of the boranes

In diborane there are 12 valency electrons, three from each B atom and six from the
H atoms. Electron diffraction results indicate the structure shown in given figure.

10
 H H
H 1.33 Å 1.19 Å
B B 1.19 Å
H H 1.33 Å
H

The two bridging H atoms are in a plane perpendicular to the rest of the molecule and prevent
rotation between the two B atoms. Specific heat measurements confirm that rotation is hindered.
Four of the H atoms are in a different environment from the other two. This is confirmed that
diborane cannot be methylated beyond Me4B2H2 without breaking the molecule into BMe3.

The terminal BH distances are the same as the bond lengths measured in nonelectrondeficient
compounds. These are assumed to be normal covalent bonds, with two electrons shared between
two atoms. We can describe these bonds as twocentretwoelectron bonds (2c2e), with two
electrons shared between two atoms.

Thus, the electron deficiency must be associated with the bridge groups. The nature of the bonds in
the hydrogen bridges is now well established. Obviously, they are abnormal bonds as the two
bridges involve only one electron from each boron atom and one from each hydrogen atom,
making a total of four electrons. An sp3 hybrid orbital from each boron atom overlaps with the 1s
orbital of the hydrogen. This gives a delocalised molecular orbital covering all three nuclei,
containing one pair of electrons and making up one of the bridges. This is a
threecentretwoelectron bond (3c2e). A second threecentre bond is also formed.

It contains two 3centre 2electron banana bonds (B … H … B). Two electrons from two H atom
and two from two Boron atoms consist of four electrons. An overlap of sp 3 hybrid orbital of B and
1s hydrogen orbital gives the delocalised molecular orbitals of a B … H … B bridge.
H
H
B B
 

B  B

B – H –B bridge

None of the group III elements react directly with hydrogen, but several interesting hydrides are
known. The boron hydrides are sometimes called boranes by analogy with the
alkanes (hydrocarbons). Almost 20 boranes have been reported and 11 are well
characterized. They fall into two series:
1. BnH(n + 4) (called nidoboranes).
2. A less stable series BnH(n + 6) (called arachnoboranes).
Boron hydrides differ from carbon hydrides (i.e. hydrocarbons) that they don’t occur in nature
because of their great affinity for H2O and O2. The compound BH3 which would be analogous to
BF3 doesnot exist because Hatom lacks the electrons that would be needed to participate in BH
bonding and compensate for the incomplete octet of B. BH3 can exist only in complex formation
with donors such as BH3.CO, BH3.N(CH3)3. Molecules of BH3 apparently dimerize spontaneously
when they come in contact with each other to form diborane, B2H6.
Method of preparation
heat
Mg3B2 + 6HCl 3MgCl2 + B2H6

3LiAlH4 + 4BF3  3LiF + 3AlF3 + 2B2H6

11
3LiBH4 + 4BF3  3LiBF4 + 2B2H6

12
2.3.7 Borazole (B3N3H6) (Inorganic Benzene)
heat at
3B2H6.2NH3 200°C
2B3N3H6 + 12H2

Structure of B3N3H6 is

H H H H
+
N B N B
+
HB NH HB + 
NH
N B N B
H H H H

CH3 H
N B
200°C
B2H6 + CH3NH2 HB NCH3
N B
CH3 H

H H H Cl
H – Cl
+
H N B N B
– + H 50°C
B3N3H6 + 3HCl B N ClB NH
(i) Cl
+
N
–
B H
N B
H H H Cl H Cl
Hydrochloride of Borazole B-trichloro borazole

(ii) B3N3H6 + 9H2O  3H3BO3 + 3NH3 + 3H2

ALUMINIUM

(1) Ores of Aluminium : Bauxite (Al2O3 .2H 2O), Cryolite (Na3 AlF6 , Felspar (KAlSi3O8 ),

2.5 COMPOUNDS OF ALUMINIUM

Aluminium oxide or Alumina (Al2O3)

Methods of preparation
 
2Al(OH)3 
 Al2O3 + 3H2O ; Al2(SO4)3 
 Al2O3 + 3SO3

(NH4)2SO4.Al2(SO4)3.24 H2O 
 Al2O3 + 2NH3 + 4SO3+ 25H2O
strong 
2AlF3 + B2O3   Al2O3 + 2BF3

2.5.2 Aluminium Halides

The fluorides of Al, Ga, In and Tl are ionic and have high melting points. The other halides are
largely covalent when anhydrous. AlCl3, AlBr3 and GaCl3 exist as dimers, thus attaining an octet of
electrons. The dimeric formula is retained when the halides dissolve in non-polar solvents such as
benzene.
Cl Cl Cl

Al Al
Cl
Cl Cl

13
 When the halides are dissolved in water, the high enthalpy of hydration is sufficient to break the
covalent dimer into [M.6 H2O]+3 and 3X ions. At low temperatures, AlCl3 exists as a close packed
lattice of Cl with Al+3 occupying octahedral holes. On heating, Al2Cl6 species are formed and the
volume of the solid greatly increases. This illustrates how close the bonding in this compound is to
the ionic/covalent border.

3. THE GROUP14 ELEMENTS (CARBON GROUP)

Carbon is the first member of group 14 or IVA of the periodic table. It consists of five elements
carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). Carbon and silicon are nonmetals,
germanium is metalloid and tin and lead are metals.

Electronic configuration
Elements Electronic configuration ( ns2 np2 )
6C 1s2 ,2s2 2p2 or [He] 2s2 2p2

14 Si 1s2 ,2s2 2p6 ,3s2 3p2 or [Ne] 3s2 3p2

32 Ge 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p2 or [Ar] 3d10 4s2 4 p2

50 Sn 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p6 4d10,5s2 5p2 or [Kr] 4d10 5s2 5p2

82 Pb 1s2,2s2 2p6 ,3s2 3p6 3d10,4s2 4p6 4d10 4 f 14,5s2 5p6 5d10,6s2 6p2 or [Xe] 4 f 14 5d10 6s2 6p2

3.1. Physical properties

(1) Non-metallic nature : The non-metallic nature decreases along the group.
C Si Ge Sn Pb
Non-metal metalloid metal metal or semi metal

(4) Melting point and boiling points

(i) The m.pt and b.pt. of this group members decrease down the group.
Element C Si Ge Sn Pb
m.pt(K) 4373 1693 1218 505 600
b.pt.(K) – 3550 3123 2896 2024
(ii) The m.pt and b.pt of group 14 elements are however, higher than their corresponding group 13
elements. This is due to the formation of four covalent bonds on account of four electrons in their
valence shells which results in strong binding forces in between their atoms in solid as well as in
liquid state.
(5) Atomic radii and atomic volume
(i) Both atomic radii and atomic volume increases gradually on moving down the group due to the
effect of extra shell being added from member to member.
C Si Ge Sn Pb
Atomic radius (pm) 0.77 111 122 141 144
Atomic volume (ml) 3.4 11.4 13.6 16.3 18.27
(ii) The atomic radii of group 14 elements are than their corresponding group 13 elements due to
increase in nuclear charge in the same period.
(iii) Some of the ionic radii involving six co-ordination of these group elements are given below,
C Si Ge Sn Pb
2+
Ionic radius (M ) in pm – – 73 118 119
14
 Ionic radius (M++) in pm – 40 53 69 78

(6) Electronegativity : The electronegativity decreases from C to Si and then becomes constant.
C Si Ge Sn Pb
Electronegativity on pauling scale 2.5 1.8 1.8 1.7 1.6

The electronegativity from silicon onwards is almost is almost constant or shows a comparatively
smaller decreases due to screening effects of d10 electrons in elements from Ge onwards.

(7) Ionisation energy

(i) The ionisation energy decreases regularly down the group; Pb however shows a higher value
than Sn due to poor shielding of inner f-orbitals as a result of which effective nuclear charge
experienced by outer shell electrons becomes more in Pb.

Ionisation energy (kJ mol-1) C Si Ge Sn Pb

IE1 1086 786 761 708 715
IE2 2352 1577 1537 1411 1450
IE3 4620 3284 3300 2942 3081
IE4 6220 4354 4409 3929 4082

(ii) The first ionisation energies of group 14 elements are higher than their corresponding group 13
elements because of smaller size.
(iii) The electropositive character of these elements increases down the group because of decreases
in ionisation energy.

(8) Oxidation state

(i) Presence of four electrons in outermost shell of these elements reveals that the members of
this family can gain four electrons forming M4+ or M4- ions to show ionic nature or exhibit
tetravalent covalent nature by sharing of four electron pairs in order to attain stable
configuration.
(ii) The formation of M4+ or M4- ions require huge amount of energy which is normally not
available during normal course of reactions, therefore, these elements usually do not form
M4+ or M4- ions, but they usually form compounds with covalence of four.
(iii) Ge, Sn and Pb also exhibit +2+ oxidation state due to inert pair effect.
(iv) Sn2+ and Pb2+ show ionic nature.
(v) The tendency to form +2 ionic state increases on moving down the group due to inert pair
effect.
(9) Catenation
(i) The tendency of formation of long open or closed atom chains by the combination of same
atoms in themselves is known as catenation.
(ii) The catenation is maximum in carbon and decreases down the group.
(iii) This is due to high bond energy of catenation.

Bond Bond energy in kJ mol-1

C-C 348
Si-Si 180
Ge-Ge 167
Sn-Sn 155
Pb-Pb No catenation

15
(iv) Only carbon atoms also form double or triple bonds involving p-p multiple bond within
itself.
> C = C<; – C  C –
(v) Carbon also possesses the tendency to form closed chain compounds with O,S and N atoms as
well as forming p-p multiple bonds with other elements particularly nitrogen and oxygen
e.g. C =O; C=N; CN; C=S are the functional groups present in numerous molecules due to
this reason.
(vi) Carbon can form chain containing any number of carbon atoms Si and Ge cannot extend the
chain beyond 6 atoms, while Sn and Pb do not form chains containing more than one or two
atoms.
(vii) The reason for greater tendency of carbon for catenation than other elements in the group may
further be explained by the fact that the C-C bond energy is approximately of the same magnitude as
the energies of the bond between C and other elements. On the other hand, the Si-Si bond is weaker
than the bond between silicon and other elements.

Bond Bond energy (k J/mol) Bond Bond energy (kJ/mol)

C-C 348 Si-Si 180
C-O 315 Si-O 372
C-H 414 Si-H 339
C-Cl 326 Si-Cl 360
C-F 439 Si-F 536

(10) Allotropy
All the elements of group 14 except lead exhibit allotropy.
(iii) Crystalline carbon occurs mainly into two allotropic forms (i) graphite and (ii) diamond (a
third allotropic form called fullerenes e.g. C60 and C70

The phenomenon of the existence of an element in different forms, which have different physical
properties but similar chemical properties, is known as allotropy. Such different forms of an
element are called its allotropes or allotropic forms. Carbon shows allotropy. The various allotropic
forms of carbon can be broadly classified into two classes.
(a) Crystalline form
Diamond and graphite are the two crystalline forms of carbon.
Difference between diamond and graphite
Diamond Graphite
Crystalline, transparent with extra Crystalline, opaque and shiny substance
brilliance. Soft having soapy touch
Hardest form Good conductor of electricity
Bad conductor of electricity Low Density (2.25 g/cm3), lighter than diamond
3
High Density (3.51 g /cm ) heavy Greyish white
Colourless Two dhnensional layer structure having regular hexagonal sheets.
Tetrahedral shaped sp2 hybridization
sp3 hybridisation More stable, less energy
16
 Less stable, more energy CGCD at high temperature and high P
CD  CG ; = – 0.5 k.cal Used as lubricating agent, electrodes, in pencils, crucibles
Used in cutting glass and jewellery; an (due to high m.pt)
abrasive
(b)Amorphous form:
Coal, coke, charcoal (or wood charcoal), animal charcoal (or bone black), lamp black, carbon
black, gas carbon and petroleum coke are the amorphous form of carbon.

3.2. CHEMICAL PROPERTIES

(1) Hydrides : All the elements of group 14 combine with hydrogen directly or indirectly to
form the covalent hydrides, MH 4 (M = C, Si, Ge, Sn or Pb). The number of hydrides and
the ease of preparation decrease on going from carbon to lead.
The hydrides of silicon are called silanes having the general formula Si n H 2n  2 . The
hydrides of germanium are called germanes while those of tin are called the stannanes. Only
lead forms an unstable hydride of the formula, PbH 4 called the plumbane.
Three hydrides of germanium, i.e., GeH 4 ,Ge 2 H 6 and Ge 3 H 8 and only two hydrides of tin
i.e., SnH 4 and Sn 2 H 6 are well known.
(2) Oxides : Carbon forms five oxides CO ,CO 2 ,C 3O 2 (carbon suboxide), C 5O 2 and
C12O 9 ,C 3O 2 is the anhydride of malonic acid and CO 2 is the anhydride of H 2CO 3
(carbonic acid) CO 2 is a non-polar linear molecule due to maximum tendency of C to form
p–p multiple bond with oxygen. Si forms SiO 2 . Pb forms a number of oxides. PbO can
Heat
be obtained by heating Pb(NO 3 )2 , 2Pb(NO3 )2  2PbO  4NO2  O2 . The red
form of PbO is called litharge and the yellow form is massicot. Pb3O 4 (Red lead, or
o
470 C
Sindur) is prepared by heating litharge in air at 470C, 6PbO  O 2   2Pb3O 4 ,
Pb3O 4 is a mixed oxide of PbO 2 .2PbO. Pb2O 3 is called lead sesquioxide. GeO2 ,SnO2 etc.
are also network solids.
Note : SiO 2 ,GeO 2 ,SnO 2 and PbO2 are all solids. CO 2 and SiO 2 is acidic, GeO 2 is
weakly acidic while SnO 2 and PbO 2 are amphoteric in nature. All the elements of group 14
except silicon from monoxides e.g., CO ,GeO ,SnO and PbO. Out of these monoxides only
CO is neutral, while all other monoxides are basic.
(3) Halides : Elements of group 14 react with halogens directly to form tetrahedral and covalent
halides except C where its halide is produced by the action of halogens on hydrocarbons.
PbBr 4 and PbI 4 do not exist because Pb 4 is a strong oxidant and Br  and I  are strong
reductants. Hence Pb 4 ion is difficult to survive in presence of strong reductants Br  and
I  and is immediately reduced to Pb2 .

3.3. ANOMALOUS BEHAVIOUR OF CARBON

Carbon is found to differ in many properties from the rest of the members of group 14. This is
because of the following : (i) Its smallest size (ii) Its high electronegativity (iii) Its property to
catenate (iv) Absence of d-orbitals in it.
Some of the properties in which it differs from other members are,
(1) The melting and boiling points of carbon are very high as compared to the rest to the members
of the family.
(2) Carbon in its diamond form is one of the hardest substance known.
(3) It has maximum tendency to show catenation.
17
 (4) Carbon has high tendency to form P  – P multiple bonds with other elements like nitrogen,
oxygen, sulphur etc. Other members of the family form P – d bonds and that also to a
lesser extent.
(5) CO 2 is a gas while the dioxides of all other members are solids.
(6) Carbon shows a maximum covalency of four while other members of the family may expand
their covalency to six e.g., [SiCl 6 ]2 ,[PbCl 6 ]2 etc.
(7) Carbon is not affected by alkalies whereas other members react on fusion. For example, silicon
form silicates, Si  2NaOH  1/ 2O2  Sodium
Na2SiO3  H 2 .
silicate

3.4. COMPOUNDS OF CARBON

3.4.1 Carbon monoxide

Structure of CO

Electronic structure of carbon monoxide may be represented as follows

 +
:C:::O: or C O
Preparation:
(i) By the reduction of carbon dioxide with carbon.
heat
CO2 + C 2CO
(ii) By the reduction of carbon dioxide with zinc or iron.
heat
CO2 + Zn  ZnO + CO
(iii) By the reduction of oxides of heavy metal with carbon. For example,
heat
ZnO + C  Zn + CO

(iv)By heating oxalic acid with sulphuric acid.

COOH H2SO4
CO + CO 2
H2O
COOH
(v) By heating formic acid with sulphuric acid. In this reaction, sulphuric acid acts as a dehydrating
agent.
H SO , 400K
HCOOH     CO
2 4

H O 2

Reactions

(i) With hydrogen

ZnO  Cu
CO + H2 CH3 OH
420  670 K, 300 atm methyl alcohol

(ii) With chlorine

sunlight
CO + Cl2   COCl2
phosgene (or carbonyl chloride)
3.4.2 Carbon Dioxide (Co2)
Preparation
(i) Carbon dioxide may be prepared by the complete combustion of carbon, hydrocarbons, carbon
monoxide etc.
2CO + O2(g)  2CO2(g) + Heat
18
 CH4 + 2O2(g)  CO2(g) + 2H2O
CaCO3 heat CaO + H2O + CO2(g)

(ii) By the action of acids on carbonates

In laboratory, carbon dioxide gas is prepared by the action of dil. HCl on marble chips (CaCO3)
CaCO3(s) + 2HCl(dil.)  CaCl2(aq) + CO2(g) + H2O
(a) With Mg: CO2 + 2Mg  2MgO + C
(b) With Na: CO2 + 4Na  2Na2O + C

Chemical Properties:
(i) Acidic nature
CO2 dissolves in water to give carbonic acid. Therefore, carbon dioxide is called carbonic
anhydride.
CO2 + H2O H2CO3
carbon dioxide carbonic acid
Carbonic acid is a very weak dibasic acid. It ionises in aqueous solutions as,
H2CO3(aq) H+ + HCO 3 (aq) K1 = 4.2  107
HCO 3 (aq) H+ + CO 32 (aq) K2 = 4.8  1011
Carbonic acid being a dibasic acid forms two sets of salts, the hydrogen carbonates, HCO 3 and
carbonates, CO 32 .

(ii) With lime water

When CO2 is bubbled through limewater, it turns milky due to the formation of CaCO 3. When
more CO2 is bubbled, solution becomes clear due to the formation of Ca(HCO3)2. On boiling the
clear solution, milkiness reappears due to the formation of CaCO3 once again.
 CO  CO 2  
heat

Ca(OH)2  
2
 CaCO3   Ca(HCO3)2  CO 2 CaCO3
H2O H O 2 H 2 O

The reaction forms the basis of lime water test for the detection of CO 32 and HCO 3 ions in any
salt/salt mixture.

3.4.4 Carbonates CO 23   and Bicarbonates HCO 3 

Carbonic acid is dibasic acid and gives rise to two series of salts, carbonates (normal salts)
and bicarbonates (acid salts) due to successive removal of the replaceable hydrogens
from H2CO3.

H2CO3 + NaOH  NaHCO3 + H2O

These can also be prepared using the following methods

With NaOH

2NaOH + CO2  Na2CO3

Sodium carbonate

Na2CO3 + H2O + CO2  2NaHCO3

Sodium bicarbonate
By precipitation:
Heavy metal carbonates are precipitated from their salt solutions with washing soda.
BaCl2 + Na2CO3  BaCO3 + 2NaCl
19
 While carbonates of many metals are known, bicarbonates of only alkali metals exist in the solid
state.
3.4.5 Haldies and Carbon
Carbon combines with all the halogens to form tetrahalides, viz, CF 4, CCl4, CBr4 and Cl4, mixed
tetrahalides like CFCl3, CF2Cl2 and CCl3Br and trihalides of the formula CHX3, viz, CHCl3
(chloroform) and CHI3 (iodoform).

General characteristics
(i) The thermal stability of tetrahalides of carbon follows the order,
(ii) The tetrahalides especially those containing both fluorine and chlorine are chemically inert,
noninflammable gases or liquids.
CF4 > CCl4 > CBr4 > CI4
(iii) Freon (CF2Cl2) is used as a refrigerant.
3.4.6 Carbides and Sulphides
Carbides
Carbides are the binary compounds containing carbon and another less electronegative element or
of similar electronegativity. Compounds of carbon and a less electronegative element are called
carbides. This excludes compounds with N, P, O, S and the halogens from this section.

Preparation of carbides
(a) Aluminium carbide is obtained by heating aluminium with carbon in an electric furnance.
electric furnace
4Al + 3C     Al4C3
(b) Silicon carbide is obtained by heating (sand) with carbon in an electric furnance.
2300 K
SiO2 + 2C   SiC + 2CO(g)
(c) Calcium carbide is obtained by heating lime (CaO) with coke in a electric furnance.
electric furnace
CaO + 3C     CaC2 + CO
2300 K

3.5. PREPARATION OF SILICON AND ITS REACTIONS

(3) Properties : Silicon exists in three isotopes 14 Si 29 (most common), 14 Si
30
with air at high
temperature SiO2 form, Si + O 2  Si O 2 .
With steam, Si reacts when heated to redness to liberate hydrogen,
Si + 2 H 2O   Si O 2 + 2 H 2 .
Redness

With halogens, Si reacts at elevated temperature forming SiX 4 except fluorine which reacts at
room temperature.
Silicon combines with C at 2500K forming Silicon Carbide (SiC) known as carborundum (an
2500K
extremely hard substance), Si + C   SiC.
It reacts with metals like Ca, Mg etc in an electric arc furnace to form Silicides ( Ca2 Si, Mg2 Si
etc.)
Silicon dissolves in hot aqueous alkalies liberating hydrogen,
 Na4 SiO4  2H 2 
Heat
Si + 4NaOH 
It also dissolves in fused Na2CO 3 displacing carbon Na2SiO3  C .

20
 (4) Uses of silicon : It is added to steel as ferrosilicon ( an alloy of Fe and Si) to make it acid
resistant. It is used in the pure form as a starting material for production of silicon polymers
(Silicones).
3.6. COMPOUNDS OF SILICON

3.6.1. Carborundum (Silicon Carbide), SiC

It is obtained when a mixture of sand, carbon, common salt and saw dust is strongly heated in an
electric furnace.
SiO2 + 3C  SiC + 2CO
Salt is added to act as flux and saw dust makes the mass porous. Two carbon rods connected by a
thin carbon core act as electrodes in the furnace. Carborundum is
formed round the central core of carbon. It is crushed, washed with H2SO4, NaOH, H2O and then
dried.

Properties
(i) Pure carborundum is colourless, but commercial samples posses yellow, green or blue colour.
(ii) It is very hard mass. However, its hardness is less than diamond.
(iii) It is chemically inert and resists the attack of almost all the reagents except fused caustic soda.
The fused alkali dissolves it in presence of air.
4NaOH + SiC + 2O2  Na2SiO3 + Na2CO3 + 2H2O
Its structure is similar to diamond.

Uses
It is used as an abrasive instead of emery. It is used to make grinder, knife sharpeners, etc. Two
oxides of silicon SiO and SiO 2 have been reported. SiO is thought to be formed by high
temperature reduction of SiO2 with Si, but its existence at room temperature is in doubt.

SiO2 + Si  2SiO
SiO2 is commonly called silica, and it is widely found as sand and quartz. Group IV elements
typically form four bonds. Carbon can form p- p double bonds and hence CO2 is a discrete
molecule and is a gas. Silicon cannot form double bonds in this way using
pp orbitals. Thus, SiO2 forms an infinite three-dimensional structure and hence SiO2 is a high
melting solid.

3.6.2. Hydrolysis of SiCl4

The hydrolysis of SiCl4 is rapid because Si can use a d-orbital to form a five-coordinate
intermediate, and the reaction occurs by an SN2 mechanism.

H
Cl O
Cl Cl

Si add OH eliminate

S
Cl Cl Cl
Si
Cl HO Cl
Cl Cl
Cl
Cl
A lone pair of electrons from the oxygen is donated to an empty d orbital on Si, forming a five-
coordinate intermediate, which has a trigonal bipyramidal structure.
3s 3p 3d
Si (in excited state)

21
 Si having gained four
electrons in SiCl4
3
sp hybridization
SiCl4 having gained a
lone pair from –OH in
the intermediate 3
sp d hybridization
If the hydrolysis is performed on an asymmetrically substituted and consequently optically active,
silicon compound such as MeEtPhSi*Cl, then Walden inversion will occur, resulting in inversion
of the structure from d to l or vice-versa. In a similar way, the reduction of R 1R2R3Si*Cl with
LiAlH4 to give R1R2R3Si*H also involves inversion of structure.
3.6.4. Silicones
These are organosilicon polymers containing SiOSi linkages. These are formed by the
hydrolysis of alkyl or aryl substituted chlorosilanes and their subsequent polymerisation. The alkyl
or aryl substituted chlorosilanes are prepared by the reaction of Grignard reagent and silicon
tetrachloride.
RMgCl + SiCl4  RSiCl3 + MgCl2

Grignard reagent

2RMgCl + SiCl4  R2SiCl2 + 2MgCl2

3RMgCl + SiCl4  R3SiCl + 3MgCl2
R stands for –CH3, –C2H5 or –C6H5 groups.
Hydrolysis of substituted chlorosilanes yield corresponding silanols, which undergo
polymerisation.
R R
Si
O O
R R
Si Si
R O R
Cyclic silicone

R3SiCl on hydrolysis forms only a dimmer

R3Si OH + HOSiR3  R3SiOSiR3 + H2O

Properties

(i) The lower silicones are oily liquids but higher members containing long chains or ring
structures are waxy and rubber like solids.
(ii) Silicones are stable towards heat.
(iii) Chemical reagents have no action on silicones.
(iv) These are nontoxic.
(v) Viscosity of silicone oils remains the same at different temperatures.
(vi) Silicones are good electrical insulators.
(vii) These are water repellents.

22
3.6.5 Silicates
Silicates are metal derivatives of silicic acid, H4SiO4 or Si(OH)4. Silicates are formed by heating
metal oxide or metal carbonates with sand, e.g.
Fused with sand
Na2CO3 SiO2 Na4SiO4, Na2(SiO3)n, etc.

O–
O

–
O O
Si
–
O Oxygen
– –
O  O O Silicon
Plane projection of
silicate ion

Silicates have basic unit of SiO44–, each silicon atom is bonded with four oxide ions tetrahedrally.

There are following types of silicates.

(i) Orthosilicates:
These silicates contain single discrete tetrahedral unit of SiO 44 –
e.g., Zircon ZrSiO4; Forsterite or Olivine Mg2SiO4
Phenacite Be2SiO4; Willemite Zn2SiO4
(ii) Pyrosilicates:
These silicates contain two units of SiO 44 – joined along a corner containing oxygen atom. These
are also called as island silicate.
–O O– O– –
O

O Si Si
– –
–
O O
O–
–
O – O
–O O–
e.g., Thorteveitite Sc2Si2O7;
Hemimorphite Zn3(Si2O7) Zn(OH)2H2O)

(iii) Cyclic structure:

Cyclic or ring silicates have general formula SiO 32  n or  SiO 3  n2n .

Structure and example of cyclic silicates containing Si 3 O 96  and Si 6 O12 

18 ions are given below.

O–
–
O –

–
–
–
O O O O
– –
O O O O
– –
– – –
O O O O–
– –
O O–
–
O

(iv) Chain silicates

(a) Simple chain silicates or pyroxenes are formed by sharing two oxygen atoms by each
tetrahedral. Anions of such chain silicates have general formula (SiO 3 )n2n

23
 – –
O O

– –

O O O O O O
– – –

O– O– O–
(b) Double chain silicates can be formed when two simple chains are joined together by shared
oxygen atoms. These minerals are called amphiboles. The anions of such silicates have
general formula (Si 4 O11 )n6n

e.g., Synthetic silicates Li2SiO3, Na2SiO3

Spodumene LiAl(SiO3)2
Enstatite MgSiO3;

4. THE GROUP15 ELEMENTS (NITROGEN GROUP)

Nitrogen is the first member of group 15 or VA of the periodic table. It consists of five elements
nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) and bismuth (Bi). The elements of this
group are collectively called pnicogens and their compounds as pniconides. The name is derived
from Greek word “Pniomigs” meaning suffocation. Pniconide contain M 3 species.

Electronic configuration
Elements Electronic configuration ( ns2 np3 )

7N 1s2 ,2s2 2p3 or [He] 2s2 2p3

15 P 1s2 ,2s2 2p6 ,3s2 3p3 or [Ne] 3s2 3p3

33 As 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4 p3 or [Ar] 3d10 4s2 4 p3

51Sb 1s2 ,2s2 2p6 ,3s2 3p6 3d10,4s2 4p6 4d10,5s2 5p3 or [Kr] 4d10 5s2 5p3

83 Bi 1s2,2s2 2p6 ,3s2 3p6 3d10,4s2 4p6 4d10 4 f 14,5s2 5p6 5d10,6s2 6p3 or [Xe] 4 f 14 5d10 6s2 6p3

4.1. PHYSICAL PROPERTIES

(1) Physical state : Nitrogen– (gas), phosphorus – (solid) (vaporises easily), As, Sb, Bi–solids.
Note : Nitrogen is the most abundant gas in the atmosphere. It constitutes about 78% by
volume of the atmosphere. Phosphorus is the most reactive element in this group and its
yellow form is always kept under water.
(2) Atomic radii : Atomic radii increases with atomic number down the group i.e., from N to
Bi due to addition of extra principal shell in each succeding elements.
(3) Ionisation energy : The ionisation values of the elements of this group decreases down the
group due to gradual increases in atomic size.
(4) Electronegativity : Generally the elements of nitrogen family have high value of
electronegativity. This value shows a decreasing trend in moving down the group from
nitrogen to bismuth.
(5) Non-metallic and metallic character : Nitrogen and phosphorus are non-metals, arsenic
and antimony are metalloids (semi-metal) and bismuth a typical metal.
(6) Molecular state : Nitrogen readily forms triple bond (two p  –p bonds) and exists as
discrete diatomic gaseous molecule (N  N) at room temperature. Phosphorus, arsenic and
24
 antimony exist in the form of discrete tetra atomic molecules such as P4 , As4 , Sb4 in which
the atoms are linked to each other by single bonds.
(7) Melting and boiling points : The melting points and boiling points of group 15 elements
do not show a regular trend.
Note : M.pt. first increases from N to As and then decreases from As to Bi. Boiling point first
increases from N to Sb. Boiling point of Bi is less than Sb.
(8) Allotropy : All the members of group 15 except Bi exhibit the phenomenon of allotropy.
(i) Nitrogen exists in two solid and one gaseous allotropic forms.
(ii) Phosphorus exists in several allotropic forms such as white, red, scarlet, violet and black form.
(a) White or yellow phosphorus : White phosphorus is prepared from rock phosphate
Ca3 (PO4 )2 , SiO2 and coke which are electrically heated in a furnace.
 
2Ca3 (PO4 )2  6SiO2  6CaSiO3  P4 O10 ; P4 O10  10C  P4  10CO

When exposed to light, it acquires a yellow colour.

(b) Red phosphorus : It is obtained by heating yellow phosphorus, between 240 –250C in the
presence of an inert gas. Yellow phosphorus can be separated from red phosphorus by reaction
with NaOH (aq) or KOH (aq) when the former reacts and the latter remains unreacted.
(iii) Arsenic exists in three allotropic forms namely grey, yellow and black. Antimony also exists
in three forms, viz., metallic, yellow and explosive.
(9) Oxidation state : The members of the group 15 exhibit a number of positive and negative
oxidation states.
(i) Positive oxidation states : The electronic configuration (ns2np3 ) for the valence shell of these
elements shows that these elements can have +3 and +5 oxidation states. In moving down this
group, the stability of +3 oxidation state increases. It may be pointed out here that nitrogen does
not exhibit an oxidation state of +5, because it fails to expand its octet due to nonavailability of
vacant d-orbitals.
(ii) Negative oxidation states : For example oxidation state of nitrogen is –3. The tendency of the
elements to show –3 oxidation state decreases on moving down the group from N to Bi.
(10) Catenation (self linkage) : Elements of group 15 also show some tendency to exhibit
catenation. This tendency goes on decreasing in moving down the group due to gradual
decrease in their bond (M–M) energies.
Note : Out of the various allotropic forms of phosphorus, black phosphorus is a good conductor
of electricity (similarity with graphite).
Proteins, the building blocks of our body contain 16% of nitrogen in them.
Radioactive phosphorus (P 32) is used in the treatment of leukemia (blood cancer).
The disease caused by the constant touch with white phosphorus is called Phossy Jaw.

4.2. CHEMICAL PROPERTIES

(1) Hydrides : All the members form volatile hydrides of the type AH 3 . All hydrides are
pyramidal in shape. The bond angle decreases on moving down the group due to decrease in
bond pair–bond pair repulsion.
NH 3 PH 3 AsH3 SbH3 BiH3
107o 94o 92o 91o 90o

The decreasing order of basic strength of hydrides is as follows :

NH 3  PH 3  AsH3  SbH3  BiH 3 .
25
The increasing order of boiling points is as follows : PH 3  AsH 3  NH 3  SbH 3 .
NH 3 is thermally most stable and BiH3 is least stable. This is because in NH 3 , N – H covalent
bond is the strongest due to small size of N atom. Hence, the decomposition temperature of NH 3
will be the highest. The increasing order of reducing character is as follows,
NH 3  PH 3  AsH 3  SbH 3  BiH 3 .
Note : Diphosphine (P2 H 4 ) and hydrazine (N 2 H 4 ) are other two important hydrides. Hydrazine a
strong reducing agent, is used in organic synthesis and rocket fuels and is prepared as follows,
2NH 3  NaOCl  N 2 H 4  NaCl  H 2O
Phosphine is poisonous and does not form any complexes.
Phosphine forms vortex rings of P2O5 in the form of white smoke when it comes in contact with
air due to combustion. This is due to impurities of diphosphine (P2 H 4 ) .
Phosphine is used to prepare smoke screens in warfare. Calcium phosphide reacts with water to
form phosphine which burns to give clouds of P2O5 which acts as smoke screens.
Liquor ammonia is a concentrated solution of NH 3 in water.
Ammonia will not burn in air, but burns in pure O 2 with a yellowish flame to produce N 2 and H 2O .
(2) Halides : The members of the family form trihalides (MX 3 ) and pentahalids (MX 5 ) . The
trihalides are sp3 -hybridized with distorted tetrahedral geometry and pyramidal shape while
pentahalides are sp3 d-hybridized and are trigonal bipyramidal in shape. The trihalides are
hydrolysed by water and ease of hydrolysis decreases when we move down the group. Hence,
NCl3 is easily hydrolysed but SbCl3 and BiCl3 are partly and reversibly hydrolysed. NF3 is
not hydrolysed due to lack of vacant d-orbital with nitrogen. PF3 and PF5 are also not
hydrolyzed because the P – F bond is stronger than P – O covalent bond. The hydrolysis
products of the other halides are as follows :
NCl3  3H 2O  NH 3  3HOCl ; PCl 3  3H 2O  H 3 PO3  3HCl

2AsCl3  3H 2O  As2O3  6HCl ; SbCl3  H 2O  SbOCl  2HCl ;

BiCl3  H 2O  BiOCl  2HCl

Their basic character follows this decreasing order as NI 3  NBr3  NCl3  NF3 . Except NF3 ,
the trihalides of nitrogen are unstable and decompose with explosive violence. NF3 is stable
and inert. NCl3 is highly explosive. Trifluorides and trichlorides of phosphorus and antimony
act as Lewis acid. The acid strength decreases down the group. For example, acid strength of
tri-chlorides is in the order ; PCl 3  AsCl3  SbCl3 .
Nitrogen does not form pentahalides due to non-availability of vacant d-orbitals. The
pentachloride of phosphorus is not very stable because axial bonds are longer (and hence
weaker) than equitorial bond. Hence, PCl 5 decomposes to give PCl 3 and Cl 2 ; PCl 5 ⇌
PCl 3  Cl 2 .

The unstability of PCl 5 makes it a very good chlorinating agent. All pentahalides act as lewis
acids since they can accept a lone pair of electron from halide ion.
Note : Solid PCl 5 is an ionic compound consisting of [PCl 4 ] [PCl 6 ] , [PCl 4 ] has a
tetrahedral structure, while [PCl 6 ] has an octahedral structure.
Since, PCl 5 reacts readily with moisture it is kept in well stoppered bottles.

26
 PI 5 does not exist due to large size of I atoms and lesser electronegativity difference between
phosphorus and iodine.
Down the group, the tendency to form pentahalides decreases due to inert pair effect. e.g.,
BiF5 does not exist.

(3) Oxides : These elements form oxides of the type X 2O3 , X 2O4 and X 2O5 .

(i) Oxides of Nitrogen : Nitrogen forms two more oxides i.e., N 2O and NO and both are
neutral. Nitrous oxide ( N 2O ) has a sweet taste and its main use is as anaesthetic. When
inhaled in mild quantities it causes hysterical laughter so it is also called Laughing gas. Nitric
oxide (NO) can be obtained by treating a mixture of sodium nitrite and ferrous sulphate with
dil. H 2SO4 . Other oxides of nitrogen are : NO2 , N 2O3 , N 2O5 .

The acidic strength of oxides : N 2O  NO  N 2O3  N 2O4  N 2O5 .

(ii) Oxides of phosphorus : P4 O6 (Phosphorus trioxide), P4 O10 (Phosphorus pentaoxide).

(iii) Oxides of other elements : The decreasing order of stability of oxides of group 15 follows
as, P2O5  As2O5  Sb2O5  Bi2O5

Except P2O5 , all pentaoxides show oxidising properties. Also P2O5 is acidic in nature. N 2O5
is the strongest oxidising agent. The nature of oxides of group 15 elements is as follows,
N 2O3 and P2O3 (acidic) ; As2O3 and Sb2O3 (amphoteric) ; Bi2O3 (basic)

(4) Oxyacids : Oxyacids of nitrogen are HNO2 , HNO3 , (Nitroxyli

H 4 N 2O 4
c acid)
HNO4 , which are
and (Pernitric
acid)

explosive.
Note : HNO3 is called aqua fortis and prepared from air (Birkel and Eyde process) and NH 3
(Ostwald process). It acts as a strong oxidising agent.

Oxyacids of phosphorus are,

(i) H 3 PO2 (Hypophosphorus acid) : Reducing agent and monobasic.
(ii) H 3 PO3 (Orthophosphorus acid) : Reducing agent and dibasic.
(iii) H 3 PO4 (Orthophosphoric acid) : Weak tribasic acid.
(iv) H 4 P2 P7 (Pyrophosphoric acid) : It is obtained by heating H 3 PO4 to 220C. It is tetrabasic.
(v) HPO 3 (Metaphosphoric acid) : It is formed by the dehydration of H 3 PO4 at 316C. Also
exists as a trimer and is monobasic.
(vi) H 4 P2O6 (Hypophosphoric acid) : Tetrabasic
(vii) H 4 P2O5 (Pyrophosphoric acid) : Dibasic acid

4.3. ANOMALOUS BEHAVIOUR OF NITROGEN

Nitrogen is known to differ form other members of the family because of the following facts,
(i) Its small size (ii) Its high electronegativity (iii) Its high ionisation energy (iv) non-availability
of d-orbital in the valence shell. (v) Its capacity to form p-p multiple bonds.
The main points of difference are,
(1) Nitrogen is a gas (N 2 ) while other members are solids.

27
 (2) Nitrogen is diatomic while other elements like phosphorus and arsenic form tetra-atomic
molecules (P4 , As4 ) .
(3) Nitrogen form five oxides (N 2O, NO, N 2O3 , N 2O4 and N 2O5 ) while other members of the
family form two oxides (tri and pentaoxides).
(4) Hydrides of nitrogen show H-bonding while those of other elements do not.
(5) Nitrogen does not show pentacovalency because of absence of d-orbitals while all other
elements show pentacovalency.
(6) Nitrogen dos not form complexes because of absence of d-orbitals while other elements show
complex formation e.g., [PCl 6 ] ,[AsCl6 ] etc.
(7) The hydride of nitrogen (NH 3 ) is highly basic in nature while the hydrides of other elements are
slightly basic.
(8) Except for NF3 , other halides of nitrogen e.g., NCl 3 , NBr3 and NI 3 are unstable while the
halides of other elements are fairly stable.

4.4.1. Preparation of Nitrogen


(i) NH4NO2  N2 + 2H2O
Since ammonium nitrite is very unstable, it cannot be kept as such. Hence nitrogen is usually
prepared by heating a mixture of ammonium chloride and sodium nitrite.
NH4Cl + NaNO2  NH4NO2 + NaCl


NH4NO2  N2 + 2H2O

(ii) Ammonium dichromate on heating decomposes to give nitrogen gas.


(NH4)2Cr2O7  N2 + 4H2O + Cr2O3

2NH3 + 3CuO  N2(g) + 3Cu + 3H2O
NH2CONH2 + 2HNO2  2N2 + CO2 + 3H2O
NaNO2 + HCl  NaCl + HNO2

28
4.4.2. Atomic and Physical Parameters of Nitrogen

Ionisation enthalpy (kJ mol1) H1 1402

H2 2856

H3 4577

Electronegativity 3.0

Covalent radius/pm 70

Ionic radius/pm (N3) 171

4.4.3. Faxation of Atmospheric Nitrogen in Cyanamide Fertilizer (The

Cyanamide Process)

Nitrogen is also fixed as calcium cyanamide on heating it with calcium carbide at 1000°C in an
electric furnace.
electric furnace
CaC2 + N2    
 CaCN2 + C
calcium carbide calcium cyanamide
The mixture of calcium cyanamide and carbon (trade name Nitrolim) is an important fertilizer.

Calcium cyanamide may also be used as a source of ammonia. The ammonia so produced can be
converted into useful fertilizers. Calcium cyanamide is decomposed by water to give ammonia.
CaCN2 + 3H2O  CaCO3 + 2NH3
2NH3 + H2SO4  (NH4)2SO4
P2O5 + 6NH3 + 3H2O  2(NH4)3PO4
CaCl2 + 8NH3  CaCl2.8NH3
By the hydrolysis of metal nitrides
boil
AlN + NaOH + H2O  NaAlO2 + NH3

4.5. AMMONIA

4.5.1. Structure of Ammonia

Ammonia is a covalent molecule. The ammonia molecule is formed due to the overlap of three sp 3
hybrid orbital of N and 1s orbital of each of the three hydrogen atoms. The fourth sp 3 hybrid orbital
of N is occupied by a lonepair. The HNH angle is 107.3°. The HNH bond angle is slightly
less than the tetrahedral angle of 109°28 due to the lone pair  bond pair repulsions, which tend to
push the NH bonds slightly inwards. In liquid and solid state, ammonia is associated due to
hydrogen bonding.

4.5.2. Reaction of Ammonia

With halogens
Ammonia reacts with halogens and the nature of products depends upon the halogen and the
reaction conditions.
29
 (a) With chlorine

With limited amount of chlorine, ammonium chloride is formed but with excess of chlorine
nitrogen trichloride is formed.

8NH3 + 3Cl2(limited)  6NH4Cl + N2

NH3 + 3Cl2(excess)  NCl3 + 3HCl

(b) With bromine

8NH3 + 3Br2  6NH4Br + N2

(c) With iodine

8NH3.NI3  5N2 + 9I2 + 6NH4I


200 C
2NH3 + CO2    NH2CONH2 + H2O
80 100 atm.

Action with heavy metal ions

With the metal ions of Al, Fe, Cr and Zn, it forms metal hydroxides, which are insoluble and form
precipitates.
FeCl3 + 3NH4OH  3NH4Cl + Fe(OH)3
brown
CrCl3 + 3NH4OH  3NH4Cl + Cr(OH)3
green
AlCl3 + 3NH4OH  3NH4Cl + Al(OH)3
white
ZnCl2 + 2NH4OH  2NH4Cl + Zn(OH)2
white
Formation of complex compounds
It forms complex compounds with the soluble salts of copper, silver etc. With copper sulphate solution, it
gives a deep blue coloured complex compound, tetramminecopper(II) sulphate.
CuSO4 + 4NH4OH  [Cu(NH3)4]SO4 + 4H2O

tetramminecopper(II) sulphate

AgOH + 2NH3  [Ag(NH3)2]OH

diammine silver(I) hydroxide

AgCl + 2NH3  [Ag(NH3)2]Cl

insoluble diammine silver(I) chloride

in water (soluble in water)

4.6. OXIDES OF NITROGEN

Oxides of nitrogen provide a fascinating picture from the point of view of their varied structures
and diverse chemical behaviour. They range from N 2O (oxidation state of nitrogen +1) through

30
 NO, N2O3, NO2, N2O4 to N2O5 in which the oxidation state of nitrogen is +5. Nitric oxide(NO) is
colourless, neutral, paramagnetic in which nitrogen has +2 oxidation state.

Oxide Oxidation State of N Physical appearance Structure

Nitrous oxide ( N 2O ) +1 Colourless gas N  N O
Nitric oxide (NO) +2 Colourless N=O
O O
Dinitrogen trioxide ( N 2O3 ) +3 Blue solid N N
O
O O
Dinitrogen tetraoxide ( N 2O4 ) +4 Colourless liquid N N
O O

Nitrogen dioxide ( NO2 ) +4 Brown gas N

O O

O O O
Dinitrogen pentoxide ( N2O5 ) +5 Colourless gas N N
O O

Preparation

Some common methods of preparation of oxides of Group VB elements are described below.
Oxides of nitrogen can be prepared by the methods given below.

Oxide of Nitrogen Preparation

Nitrous Oxide (N2O)
Nitrous oxide (NO)
By heating ammonium nitrate upto 2400C

NH4NO3  N2O + 2H2O
Collected over hot water.
(a) By the action of cold dil. HNO3 on copper turnings (Laboratory method)
3Cu + 8 dil. HNO3  3Cu(NO3)2 + 4H2O + 2NO
(b) By the action of H2SO4 on a mixture of FeSO4 and KNO3 (4:1)
2KNO3 + 5H2SO4 + 6FeSO4  2KHSO4 + 3Fe2(SO4)3 + 4H2O + 2NO
(c) By catalytic oxidation of ammonia.
Pt
4NH3 + 5O2   4NO + 6H2O
0
850 C

Dinitrogen trioxide(N2O3) (a) By the action of 50% HNO3 on arsenious oxide.

Nitrogen dioxide (NO2)
Dinitrogen pentoxide(N2O5)
2HNO3 + As2O3 + 2H2O  NO + NO2 + 2H3AsO4
 250 K
N2O3
(a) By heating nitrates of heavy metals, e.g., lead nitrate.
673K
2Pb(NO3)2   4NO2 + 2PbO + 2O
(b) By heating copper turnings with conc. HNO3.
Cu + 4 conc. HNO3  Cu(NO3)2 + 2H2O + 2NO2
(a) By dehydrating HNO3 with phosphorus pentoxide
4HNO3 +P4O10  2N2O5 + 4 HPO3

4.7. OXOACIDS OF NITROGEN

Name of oxoacid M. F. Structure Oxidation State of N Basicity pKa Nature

Hyponitrous acid H2N2O2 +1 2(dibasic) Very weak Highly

explosive
Nitrous acid HNO2 HN O +3 1 (monobasic) 3.3 Unstable Weak

acid


31
Nitric acid HNO3 H O N  O +5 1 (monobasic) -3.0 Stable, Strong
 acid

Pernitric acid HNO4 O  N O  O  H +5 1 (monobasic) Unstable and

explosive


4.8. MANUFACTURE OF HNO3

1. Ostwald process
Pt Rh
4NH3 + 5O2 Catalyst
  4NO + 6H2O

2NO + O2  2NO2

3NO2 + H2O  2HNO3 + NO

The nitric acid prepared is of 50% concentration.

2. Birkeland Eyde process

Electric
N2 + O2 arc 2NO
o
2NO + O2   2NO2
1000 C

2NO2 + H2O  HNO3 + HNO2

3HNO2  HNO3 + 2NO + H2O
60%
4.8.1. Chemical properties of Nitric Acid

Thermal stability

4HNO3  2H2O + 4NO2 + O2

HNO3 + H2O H3O+ + NO 3

4.8.2. Oxidising properties

2HNO3 (conc.)  H2O + 2NO2 + [O]

2HNO3 (dilute)  H2O + 2NO + 3[O]

H2S + 2HNO3(conc.)  2H2O + 2NO2 + S

3H2S + 2HNO3(dilute)  4H2O + 2NO + 3S

2HNO3(conc.)  H2O + 2NO2 + [O]

SO2 + [O] + H2O  H2SO4

SO2 + 2HNO3 (conc.)  H2SO4 + 2NO2

2HNO3(dilute) + 3SO2 + 2H2O  3H2SO4 + 2NO

2FeSO4 + H2SO4 + [O]  Fe2(SO4)3 + H2O

6FeSO4 + 2HNO3(dil.) + 3H2SO4(dil.)  3Fe2(SO4)3 + 2NO + 4H2O

32
Hydrobromic acid and hydroiodic acid to bromine and iodine respectively.

2HBr + 2HNO3  2H2O + 2NO2 + Br2

2HI + 2HNO3  2H2O + 2NO2 + I2

Nonmetals like carbon, sulphur, iodine, phosphorus, etc are converted to their oxoacids by
concentrated nitric acid, which in turn, is reduced to nitrogen dioxide.

C + 4HNO3  H2CO3 + H2O + 4NO2

S + 6HNO3  H2SO4 + 6NO2 + 2H2O

Iodine is oxidised to iodic acid (HIO3).

I2 + 10HNO3  2HIO3 + 10NO2 + 4H2O

P + 5HNO3  H3PO4 + 5NO2 + H2O

(a) Metals that are more electropositive than hydrogen

(i) Action on zinc

Zn + 4HNO3(conc.)  Zn(NO3)2 + 2H2O + 2NO2

4Zn + 10HNO3(dil.)  4Zn(NO3)2 + 5H2O + N2O
4Zn + 10HNO3(v. dil.)  4Zn(NO3)2 + NH4NO3 + 3H2O
4Mg + 10HNO3(v. dil.)  4Mg(NO3)2 + NH4NO3 + 3H2O

(ii) Action on tin

Sn + 4HNO3(conc.)  H2SnO3 + 4NO2 + H2O
Metastannic acid
4Sn + 10HNO3(dilute)  4Sn(NO3)2 + NH4NO3 + 3H2O
Stannous nitrate
(iii) Action on lead

Pb + 4HNO3 (conc.)  Pb(NO3)2 + 2NO2 + 2H2O

3Pb + 8HNO3(dilute)  3Pb(NO3)2 + 2NO + 4H2O

(iv) Action on iron

Fe + 6HNO3(conc.)  Fe(NO3)3 + 3NO2 + 3H2O

4Fe + 10HNO3(dil.)  4Fe(NO3)2 + N2O + 5H2O
4Fe + 10HNO3(v. dil.)  4Fe(NO3)2 + NH4NO3 + 3H2O

(b) Metals that are less electropositive than hydrogen

Action on copper

Cu + 4HNO3(conc.)  Cu(NO3)2 + 2NO2 + 2H2O

3Cu + 8HNO3(v. dil.)  3Cu(NO3)2 + NO + 4H2O

33
4.8.3. Formation of aquaregia

A mixture of conc. HCl and conc. HNO3 (3:1 by volume) is called aquaregia. It can dissolve
noble metals like gold and platinum.

HNO3 + 3HCl  2H2O + 2Cl + NOCl

Au + 3Cl  AuCl3 ; AuCl3 + Cl  [AuCl4]

Pt + 4Cl  PtCl4 ; PtCl4 + 2Cl  [PtCl6]2

4.9 PHOSPHORUS
Phosphorus is a very reactive element, so it does not occur free in nature. The ores of phosphorus
which normally occur in nature are given as follows

(1) Occurence : Phosphorous occurs mainly in the form of phosphate minerals in the crust of
earth. Some of these are : (i) Phosphorite Ca3 (PO4 )2 , (ii) Fluorapatite Ca5 (PO4 )3 F , (iii)
Chlorapatite 3 Ca3 (PO4 )2 .CaCl2 , (iv) Hydroxyapatite; Ca5 (PO4 )3 OH . Phosphates are
essential constituents of plants and animals . It is mainly present in bones, which contains
about 58% calcium phosphate.

(2) Isolation : Elemental phosphorus is isolated by heating the phosphorite rock with coke and
sand in an electric furnace at about 1770K, 2Ca3 (PO4 )2  6SiO2  Calicum
6CaSiO3  P4 O10 ;
silicate

P4 O10  10C  P4  10CO

(3) Allotropic forms of phosphorus : Phosphorus exists in three main allotropic forms,
(i) White phosphorus, (ii) Red phosphorus, (iii) Black phosphorus

Some physical properties of three forms of phosphorus

Properties White phosphorus Red phosphorus Black phosphorus

Colour White but turns yellow on Dark red Black
exposure
State Waxy solid Brittle powder Crystalline
Density 1.84g cm–3 2.1 g cm–3 2.69 g cm–3
Ignition temperature 307 K 533 K 673 K
Stability Less stable at ordinary More stable at ordinary Most stable
temperature temperature
Chemical reactivity Very reactive Less reactive Least reactive

P P
P

–P PP P
P P
P P
P (White Phosphorus)
Structure of red phosphorus

4.9.1 Chemical Properties of Phosphorus

(i) Reaction with oxygen:

34
 Yellow phosphorus readily catches fire in air giving dense white fumes of phosphorus pentoxide.
Red phosphorus combines with oxygen only on heating. Both of them form either phosphorus
trioxide or phosphorus pentoxide.

P4 + 3O2 heat P4O6

Red phosphorus Phosphorus trioxide

P4 + 5O2 heat P4O10

Red phosphorus Phosphorus pentoxide

(ii) Reaction with chlorine:

Phosphorus reacts with chlorine gas to form tri-and pentachlorides. Yellow phosphorus reacts
violently at room temperature, whereas red phosphorus reacts on heating only.

P4 + 6Cl2  4PCl3

Phosphorus trichloride

P4 + 10Cl2  4PCl5

Phosphorus pentachloride

(iii) Reaction with alkalies (sodium/potassium hydroxide):

Yellow phosphorus dissolves in caustic soda on boiling under an inert atmosphere liberating
phosphine.

P4 + 3NaOH 3H2O boil PH3(g) + 3NaH2PO2

+
Yellow phosphorus Phosphine Sodium hypophosphite

(iv) Reaction with nitric acid: Phosphorus gets oxidised by nitric acid to phosphoric acid.

P4 + 20HNO3 4H3PO4 + 20NO2 + 4H2O

Phosphoric acid

(v) With metals: Phosphorus reacts with metals forming phosphides. For example

6Mg + P4 2Mg3P2
Magnesium phosphide

4.10. PHOSPHINE
(i) By hydrolysing metallic phosphides

Convenient methods of preparing phosphine are by the hydrolysis of metallic phosphides with
water or dilute mineral acids.

Ca3P2 + 6H2O 2PH3 + 3Ca(OH)2

AlP + 3HCl PH3 + AlCl3

(ii) Phosphine may also be obtained by heating phosphorus acid.

heat
4H3PO3 3H3PO4 + PH3
phosphorus acid

35
 With metallic salts: Formation of phosphides

Phosphine unlike ammonia does not precipitate hydroxides of metals on reacting with salt
solutions. On the other hand, it precipitates metals like silver, copper etc., as phosphides when
phosphine gas is passed through aqueous solutions of salts of these metals.

3CuSO4 + 2PH3 Cu3P2 + 3H2SO4

copper phosphide
(black ppt.)

3AgNO3 + PH3 Ag3P + 3HNO3

silver phosphide
(black ppt.)

Uses of Phosphine
(i) It is used for producing smoke screens. Calcium phosphide is used in smoke screens.
Phosphine obtained catches fire to give the needed smoke.

(ii) In Holme’s signals. A mixture of calcium carbide and calcium phosphide is taken in a container
which is pierced and thrown into the sea. Phosphine liberated catches fire and lights up
acetylene. Burning gases serve as a signal to the approaching ships.

4.11. OXIDES OF PHOSPHOROUS

O
143 pm
P
P O 102° O 160 pm

O 123°
O O
127°
O P P
O O O
P P
O 100° O P
P O
O 166 pm O O
Phosphorus trioxide (P4O6) Phosphorus pentoxide (P4O10)

Structures of some oxides of phosphorus

4.12. OXOACIDS OF PHOSPHORUS

4.12.1.Oxyacids of phosphorus
Name Formula Oxidation state of P Basicity Structure
O
Hypophosphorous acid H 3PO2 +1 Monobasic P
H
H OH
O

Phosphorous acid H 3 PO3 +3 Dibasic P

OH
H OH

O O

Hypophosphoric acid H 4 P2O6 +4 Tetrabasic P P

OH
HO OH OH

36
 O

Orthophosphoric acid H 3 PO4 +5 Tribasic P

OH
HO OH

Metaphosphoric acid (HPO 3 )n +5 Monobasic P

HO O

O O

Pyrophospric acid P P
H 4 P2O7 +5 Tetrabasic
(Diphosphoric acid). OH
HO O
OH OH

37
4.12.2.The Phosphoric acid series
Orthophosphoric acid
The simplest phosphoric acid is H3PO4 (orthophosphoric acid). The acid contains three replaceable
H atoms, and is tribasic. It undergoes stepwise dissociation.
 K
H3PO4 H+ + H 2PO 4 ; a1 = 7.5 × 10–3

+ K a2 –8
H2PO 4 2
H + HPO 4 ; = 6.2 × 10
+
HPO 24 H + PO 34 ; K a3 = 1 × 10–12

Three series of salts can be formed

1. Dihydrogen phosphates, for example sodium dihydrogen phosphate NaH 2PO4 , which is slightly
acidic in water
2. Monohydrogen phosphates, for example disodium hydrogen phosphate Na2HPO4, which is
slightly basic in water.
3. Normal phosphates such as trisodium phosphate Na3PO4, which are appreciably basic in
solution.
NaH2PO4 and Na2HPO4 are made industrially by neutralizing H3PO4 with soda ash (Na2CO3),
but NaOH is required to make Na3PO4. All three salts exist in the anhydrous state and also in a
number of hydrated forms, and they are used extensively.
Phosphoric acid also forms esters with alcohols:

(HO)3P O + 3EtOH (EtO)3P O + 3H2O

alcohol water
acid ester
(triethy phosphate)

Phosphates are detected analytically by mixing a solution of the salt with dilute HNO 3 and
ammonium molybdate solution. A yellow precipitate of a complex ammonium 12-
molybdophosphate forms slowly, confirming the presence of phosphates. Arsenates form a similar
precipate but only on heating the mixture.
The orthophosphates of group I metals (except Li) and NH 4 are soluble in water. Most of the other
metal orthophosphates are soluble in dilute HCl or acetic acids. Titanium, zirconium and thorium
phosphates are insoluble even in acids. Thus in qualitative analysis a solution of zirconyl nitrate is
commonly added to remove any phosphate present in solution.
2+
Phosphates can be estimated quantitatively by adding a solution containing Mg and NH4OH
solution to a solution of the phosphate. Magnesium ammonium phosphate is precipitated
quantitatively, and this is filtered, washed, ignited, and weighed as magnesium pyrophosphate
Mg2P2O7.
2+  3
Mg + NH 4  PO 4  MgNH 4 PO 4
2MgNH4PO4  Mg2P2O7 + 2NH3 + H2O

Impure orthophosphoric acid H3PO4 is prepared in large amounts by treating phosphate rock with
–
H2SO4. The CaSO4 is hydrated to gypsum CaSO4 . 2H2O, which is filtered off, and the F is
38
 converted to Na2[SiF6] and removed. The H3PO4 is concentrated by evaporation. Most of the
H3PO4 made in this way is used to make fertilizer.

Ca3(PO4)2 + 3H2SO4  2H3PO4 + 3CaSO4

[3(Ca3(PO4)2). CaF2] + 10H2SO4 + 16 H2O  6H3PO4 + 10CaSO4 + 2HF

Pure H3PO4 is made by the ‘furnace process’. Molten P is burnt in a furnace with air and steam.
First P4O10 is formed by reaction between P and O, and then this is immediately hydrolysed.

P4 + 5O2  P4O10 P4O10 + 6H2O  4H3PO4

Phosphoric acid is hydrogen bonded in aqueous solution, and because of this the ‘concentrated
acid’ is syrupy and viscous. Concentrated acid is widely used and contains about 85% by weight of
H3PO4 (100% pure (anhydrous) H3PO4 is seldom used, but it can be prepared as colourless
deliquescent crystals by evaporation at low pressure). Most of the acid (solution) made in this way
is used in the laboratory, and in food (Kraft cheese Na2HPO4) and pharmaceutical preparations.

H3PO4 may also be made be the action of concentrated HNO3 on P.

P4 + 20HNO3  4H3PO4 + 20NO2 + 4H2O

Orthophosphoric acid loses water steadily on heating.

gentle heat strong heat
H3PO4 220°C H4P2O7 (HPO3)n
orthophosphoric 320°C
pyrophosphoric metaphosphoric
acid acid acid

4.12.3.Polyphosphates

A very large number of polyphosphoric acids and their salts, the polyphosphates, arise by
polymerising acidic [PO4] units forming isopolyacids. These consists of chains of tetrahedral, each
sharing the O atoms at one or two corners of the [PO4] tetrahedron, giving simple unbranched
chains, in a similar way to the formation of pyroxenes by the silicates.

The hydrolysis of P4O10 proceeds in stages, and an understanding of these stages leads to an
understanding of the wide range of phosphoric acids.

P4O10 + 6H2O  4H3PO4 (overall reaction)

O O O O
O

P P P P
P HO O O OH
HO O O

H4P2O7 OH OH OH
OH OH
H5P3O10
Structure of pyrophosphoric acid tripolyphosphoric acid

Polyphosphates are straight chain compounds. The basicity of the various acids, that is the number
of replaceable H atoms, can be found by drawing the structure and counting the number of OH
groups. Thus, orthophosphoric acid is tribasic, pyrophosphoric acid is tetrabasic, tripolyphosphoric
39
 acid is pentabasic, tetrapolyphosphoric acid is hexabasic, and tetrametaphosphoric acid is
tetrabasic.
O
P O OH
P O O
O O HO–P–O–P–OH
OH O O
OH O H OH O
O=P O P=O H
O O O = P O OH P = O HO–P–O–P–OH
O O
P O O
P
O Tetrametaphosphoric
O OH acid
not actually isolated

O O O O O O O
H OH H OH
4HO–P–OH 2HO–P–O–P–OH HO–P–O–P–O–P–O–P–OH

OH OH OH OH OH OH OH
orthophosphoric pyrophosphoric Tetrapolyphosphoric
acid acid acid
Scheme for the hydrolysis of P4O10

4.13 PENTAHALIDES OF PHOSPHORUS

The trigonal bipyramidal is not a regular structure. Electron diffraction on PF 5 gas shows that some
bond angles are 90 and others are 120, and the axial PF bond lengths are 1.58 Å whilst the
equatorial PF lengths are 1.53 Å. In contrast nmr studies suggest that all five F atoms are
equivalent. This paradox may be explained quite simply. Electron diffraction gives an
instantaneous picture of the molecule, whilst nmr gives the picture averaged over several
milliseconds. The axial and equatorial F atoms are thought to interchange their positions in less
time than that needed to take the nmr. The interchange of axial and equatorial positions is called
‘pseudorotation’. PF5 remains covalent and keeps this structure in the solid state. However, PCl 5 is
close to the ioniccovalent borderline, and it is covalent in the gas and liquid states, but is ionic in
the solid state. PCl5 solid exists as [PCl4]+ and [PCl6] the ions have tetrahedral and octahedral
structures respectively. In the solid, PBr5 exists as [PBr4]+ Br- and PI5 appears to be [PI4]+ and I in
solution.

Q. Hydrolysis of NCl3 gives NH4OH and HOCl, while PCl3 on hydrolysis gives H3PO3 and HCl.
Explain.

Solution:

The hydrolysis of PCl3 may be contrasted with that of NCl3 This difference is due to the change in
+   +
polarity of P Cl bond in PCl3 in contrast to N Cl bond in NCl3.

PF3 is not sensitive to H2O due to strong PF bond. F being more electronegative than oxygen
forms a strong covalent bond with P in comparison with PO bond.

NCl3 + 4H2O  NH4OH + 3HOCl

40
  +
violently
ClNCl + H+OH ClNH + HOCl
Cl Cl
2H2O

NH3 + 2HOCl
H 2O

NH4 OH

+ 
slowly
ClPCl + H+OH ClPOH + HCl
Cl Cl
2H2O
O
HOPOH + 2HCl
H

4.14 INTERNAL BONDING USING dORBITALS

The compounds trimethylamine (CH3)3N and trisilylamine (SiH3)3N have similar formulae, but
have totally different structures. In trimethylamine, the arrangement of electrons is as follows:

Electronic structure of nitrogen atomground state

1s 2s 2p

3
sp
Three unpaired electrons form bonds with CH3
groups tetrahedral arrangement of 3 bond pairs
and 1 lone pair (sp3)

In trisilylamine, three sp2 orbitals are used for  bonding, giving a plane triangular structure. The
lone pair of electrons occupy a porbitals at right angles to the plane triangle. This overlaps with
empty dorbitals on each of the three silicon atoms, and results in bonding, more accurately
described as pd bonding, because it is from a full porbital to an empty dorbital. This
shortens the bond lengths of NSi bond. Since, the nitrogen no longer has a lone pair of electrons,
the molecule has no donor properties. Similar pd bonding is impossible in (CH3)3N because C
does not possess dorbitals and hence this molecule is pyramidal. About 200 compounds are now
thought to contain pd bonds.
4.15. CHEMICAL FERTILIZERS
The chemical substances which are added to the soil to keep up the fertility of soil are called
fertilizers.
Types of fertilizers : Chemical fertilizers are mainly of four types,
(i) Nitrogenous fertilizers : e.g. Ammonium sulphate (NH 4 )2 SO4 , Calcium cyanamide CaCN2 ,
Urea NH 2CONH 2 etc.
(ii) Phosphatic fertilizers : e.g. Ca(H 2 PO4 )2 .H 2O (Triple super phosphate), Phosphatic slag etc.
(iii) Potash fertilizers : e.g. Potassium nitrate (KNO3 ), Potassium sulphate (K 2SO4 ) etc.
(iv) Mixed fertilizers : These are made by mixing two or more fertilizers in suitable proportion.
e.g. NPK (contains nitrogen, phosphorus and potassium).
NPK is formed by mixing ammonium phosphate, super phosphate and some potassium salts.

41