13

Group 12 (IIB) – Zinc,

Cadmium, Mercury

Zinc (Zn), cadmium (Cd) and mercury (Hg) are last d–elements in their periods. Their outer electron
configuration is (n – 1)d10ns2. They form +2 ions only (M+2 ions) which have configuration (n – 1)d1o. As
the elements or the ions they form have full filled (n – 1)d orbitals, they are not true transition elements.
However, they form a group of their own and are placed with transition metals. There is some similarity to
transition metals w.r.t. complex formation especially with NH3, CN–, halide ions and amines.

Electronic configuration
Table 13.1
Elements Symbol Atomic no. Electronic configuration
Zinc Zn 30 [Ar] 3d1o4s2
Cadmium Cd 48 [Kr] 4d1o5s2
Mercury Hg 80 [Xe] 4f145d1o6s2

Mercury is unique. It is the only metal which is liquid at room temperature. It is due to very weak metallic
bond in Hg. High promotion and ionization energies for Hg make difficult for electrons to form strong
metallic bond. These effects may be due to inert pair (6S2) valence shell of Hg.

Promotion and Ionization Energies

Table 13.2
Promotion energies Ionization energy (KJmol–1)
s2 → s1p1
Zn 433 I (ev)    II (ev)
Cd 408 906 (9.39) 1733 (17.89)
Hg 524 876 (8.99) 1631 (16.84)
1007 (10.43) 1810 (18.65)

Atomic and Ionic Radii

Atomic radii have the order, Zn < Cd ~ Hg.
The increase in radius from Zn to Cd is due to addition of higher orbit in Cd.
Zn –– 3d104s2, Cd –– 4d105s2
330  Basic Concepts of Inorganic Chemistry

Radii of Cd and Hg are very similar due to lanthanide contraction. Mercury is after lanthanides [Ce(58)
to Lu(71)]. Therefore, increase in orbit number in Hg (5d106s2) is counter balanced by lanthanide contraction.
Hence, Cd and Hg have similar radii.
Ionic radii increase from Zn2+ to Hg2+. Table 13.3

Melting and Boiling Points Element Atomic Ionic radius

radius (Å) M+2, (Å)
All the metals have low cohesive energies and so are soft Zn 1.25 0.74
compared to other transition metals. It indicates weak
metallic bonds in Zn, Cd and Hg. It may be due to non- Cd 1.41 0.95
participation of (n – 1)d electrons in metallic bonding. Hg 1.44 1.02vw
The overall effect results into low mp and bp of these
elements.

Table 13.4
Elements mp(oC) bp(oC)

Zn 420 907

Cd 321 765

Hg –39 357

Metallic bond in Hg is so weak that it is highly vaporizable. It is the main reason of Hg poisoning. The
vapour contains monoatomic Hg. Mercury should, thus, be kept covered.

Ionization Energy
Table 13.5
Variation of ionization energy is not regular for Zn, Cd
and Hg. The order found is, Zn > Cd < Hg. IE(ev)
Elements rM(Å)
The ionization energy of Zn is greater than I II
Cd because atomic radius of Cd is greater than Zn. Zn 1.25 9.39 17.89
Although the radii of Cd and Hg are very similar, the
ionization energy of Hg is greater than Cd. It is due Cd 1.41 8.99 16.84
to the fact that 4f electrons in Hg (4f 5d 6s ) shields
14 1o 2
Hg 1.44 10.43 18.65
nucleus poorly. Therefore, 6s electrons experience
greater effective nuclear charge. Hence ionization
energy of Hg is greater than that of Cd. (The 6s2 electrons are popularly called “Inert Pair”).
The first ionization energy of Hg is highest among the metals. It is due to the fact that valence electrons
of Hg are inert pair (6s2) electrons.

Oxidation states
These elements have valence shell electron configuration (n – 1)d1ons2. First two elements Zn and Cd
show fixed oxidation state of +2 corresponding to ns2 electrons. But Hg shows variable oxidation states,
+1 and +2.
Zn +2
Cd +2
Hg +1, +2
However, in +1 oxidation state Hg is not Hg+, but is a dimer, Hg +22 .
 Group 12 (IIB) – Zinc, Cadmium, Mercury  331

The Hg22+ ion has metal–metal bond i.e., [Hg – Hg]2+. It becomes possible due to 6s1 electronic structure
of Hg+. There is enough proof for Hg – Hg bond in Hg22+. It includes X ray analysis of dry salts and Raman
spectral analysis of salt solutions etc.

Nature of Bonds
The +2 oxidation state is stable for all the metals. Ionic compounds in this oxidations state possess considerable
covalent nature. It arises due to relatively small size and larger number of core electrons (18e) in M+2 ions. It
is not found in +2 ions of group 2 metal ions, Ca+2, Sr+2 and Ba2+ (larger radii and less core electrons, 8e).

Table 13.6
Nature Radius (Å) Core electrons Ion Radius (Å) Core electrons
Ca+2 1.00 8e Zn+2 0.74 18e

Sr+2 1.18 8e Cd+2 0.95 18e

Ba+2 1.35 8e Hg+2 1.02 18e

Thus ZnCl2, CdCl2 and HgCl2 in anhydrous state are covalent. HgCl2 is so much so covalent that it does
not give chromyl chloride test which is common and most authentic for ionic chlorine i.e., Cl–. Therefore
ZnCl2, in anhydrous state is a Lewis acid but not the CaCl2 because CaCl2 is not covalent. It is ionic and has
lattice structure.
However, in hydrated state, ZnCl2 is ionic and is formulated as [Zn(H2O)4]2+ . 2Cl.

Electrode Potential
Table 13.7
Standard electrode potentials for these elements are very
different. The order is Zn < Cd << Hg. It shows that Zn is Elements Eo(volt)
M+2
+ 2e fi M(s)
most reactive and Hg least reactive. (aq)

High positive Eo of Hg shows its noble nature. The Zn –0.76

large difference between Cd and Hg may be due to high
ionization energy of Hg and higher hydration energy of Cd –0.40
Cd+2. Zinc and Cd are above H in electro chemical series Hg +0.85
but Hg is below H. Therefore, Zn and Cd are reducing
agents but not Hg.

Hydration Energy
Energy released for the process,
Mn+(g) + water Mn+(aq)
is called hydration energy. It is given by

Z*e2
ΔHHyd = [1 – (1/D)]
r

It shows that ΔHHyd ∝ Z* and ∝.1/r, i.e., higher the Z* and lower the radius of the ion, higher the
ΔHHyd.
332  Basic Concepts of Inorganic Chemistry

Zinc, Cd and Hg in +2 have high Z* so their hydration energy is high, greater than hydration energies of
group 2 metals +2 ions (i.e., Ca+2, Sr+2 etc.) another factor responsible for higher hydration energies of Zn+2,
Cd+2 and Hg2+ is greater number of core electron (18e) over Gr 2, M+2 ions (8e). Although Ca+2 and Cd+2 have
almost equal ionic radii (00.94Å) hydration energy of Cd2+ is larger than Ca2+.

Magnetic Properties Table 13.8

The metals and their +2 ions have all their electrons paired Ion Cores Hydration energy
and so are diamagnetic
Cd2+ 18e 430KCalmol–1
M (n – 1)d1ons2, M+2 (n – 1)d1o
Ca+2 8e 395KCalmol–1
The Hg+ ion has electron configuration, 6s1 i.e.,
unpaired electron but it exists as Hg 22 + which has no
unpaired electron. Therefore, mercureous compounds are
also diamagnetic.

Colour of Compounds
Some of the compound of Zn, Cd and Hg are coloured but not due to d – d transitions as d orbitals are full
filled (Zn+2 – 3d1o, Cd+2 – 4d1o, Hg2+ – 5d1o).
The compounds are coloured due to crystal defect and charge transfer.
Zinc oxide is yellow when hot but colourless in cold. It is due to defect structure, electron excess. When
ZnO is heated, some O–2 is converted to O2 (O–2 ½O2 + 2e) and escapes the lattice leaving behind
electrons. These electrons move in the lattice from one point to another, making ZnO yellow. But when ZnO
is cooled, it takes up O2 from the atmosphere converting it to O–2 by the electron present in the lattice, (1/2O2
+ 2e O–2). A normal lattice is regenerated and ZnO becomes colourless.

Zn +2 O -2 Zn +2 O -2 Zn +2 O -2 Zn +2 O -2
Δ
O -2 Zn +2 O -2 Zn +2 O -2 Zn +2 2e Zn +2

–Δ
Zn +2
O -2
Zn +2
O -2
Zn +2 O -2 Zn +2 O -2

Figure 13.1
Cd and Hg compounds are coloured due to charge transfer and defect structure.

Table 13.9
Compound Colour Reason
CdO Brown Charge transfer
CdS Yellow Charge transfer
HgS Black Charge transfer
HgS Red Defect structure
HgO Yellow Charge transfer
Red Charge transfer
Hg2I2 Greenish (but difference in colour due to particle size)
HgI2 Red Charge transfer
Charge transfer
 Group 12 (IIB) – Zinc, Cadmium, Mercury  333

Some useful compounds

  1. ZnO: (Philosopher’s Wool)
Applications
(a) As white pigment
(b) Ointment base
(c) Cosmetic industry
(d) As filler and vulcanization activator in rubber titres
(e) As a photoconductor in the Xerox method of electrostatic printing.
  2. ZnS: It is white and insoluble in water.
Applications
(a) In making fluorescent screen
(b) Impure ZnS is a phosphor (i.e., can convert energy, electron beam, into visible light). Such ZnS
is used in making phosphorescent screens useful for X – rays, radioactivity work, radar and
television.
(c) Used in making white pigment, lithopone (ZnS + BaSO4)
ZnSO4 + BaS ↓ZnS + BaSO4↓
  3. Hg2Cl2: (Mercurous chloride):
Applications
(a) Preparation of calomel electrode.
  4. Hg2SO4: (Mercurous sulphate):
Applications
(a) A depolarizer in Weston standard cell.
  5. K2HgI4 [Pot. tetraiodomercurate (11)]
Alkaline solution of K2HgI4 is known as Nessler’s reagent.
(KOH + K2HgI4 Nessler’s reagent)
Nessler’s reagent is very sensitive reagent for NH3 or ammonium salts. It forms brown colouration or
ppt with NH3 or ammonium salts.
NH4+ + 2[HgI4]2– + 4HO– HgO.Hg(NH2) + 7I– + 3H2O
(Brown)

The brown pp is a basic Hg(11) amido iodide and is formulated as

This reaction is used to detect traces of NH3 in drinking water. Drinking +J
water is contaminated by NH3 through sewage water. 2 1+  ,
+J
  6. Cadmium is used in rechargeable dry cells with Ni, Ni/Cd batteries.
Figure 13.2
Biochemistry of Zn, Cd and Hg
1.  Zinc
I t has many important biological roles. A normal human contain about 2g of Zn which is next to Fe, 4g.
Many enzymes contain Zn, some important ones include—
(a) Carbonic anhydrases: Fast acting, speeds up absorption of CO2 by red blood cells in muscles and
tissues. Also helpful in release of CO2 in the lungs. It also regulates pH of blood by creating a buffer
medium containing HCO3– ion.
CO2 + H2O H+ + HCO3–
(b) Dehydrogenases – sugar metabolism
(c) Alcohol dehydrogenase – metabolism of alcohol.
334  Basic Concepts of Inorganic Chemistry

(d) Carboxy peptidase (MW 34300, IZ): Found in pancreas of mammals, catalyses the hydrolysis of
peptide bond at the carboxyl end.

2. Cadmium
It is a major environmental pollutant.
Effects
(a) Itai–Itai diseases (Japan) and ouch–ouch diseases (English): It is joint pain and bone deformation.
Ultimately leads to multiple bone fractures even by coughing. Weakness of bones may be due to
replacement of Ca by Cd as both have very similar radii in +2 oxidation state.
(b) Tobacco smoke contains Cd. It affects liver and kidney. Replaces Zn in some enzymes and thus
preventing their normal function.
(c) Metallothionein: It is the only biological material known to contain Cd. Its function is
unknown.

3. Mercury
Mercury is unique in its biochemistry. Mercury vapours and many of its soluble compounds
are toxic. But some mercury compound, such as the red crystalline variety of HgS, known as
“Makardhwaj” is regarded as life saving drug in “Ayurveda” the classical Indian method of
treatment.
Toxic effect of Hg (Hg+2) is mainly due to two reasons-
(i)  There is no body chemistry for excreting Hg.
(ii) Hg2+ inhibits enzymes, especially those containing the thiol groups (Hg2+ is a soft Lewis acid and
S–2 or S soft Lewis base. So greater affinity for each other). The most famous case of Hg poisoning is
“Miamata disease” of Japan. Organo Hg compounds are more toxic than inorganic ones. Example,
(CH3)2Hg is highly toxic.

Practice Questions

A. Explain the following: (i) Hg and not Zn and Cd shows variable
(a) Position of Zn, Cd and Hg in the periodic oxidation states.
table. (j) Hg2Cl2 and HgCl2 form black and white
(b) Mercury does not resemble Zn and Cd in precipitates with NH4OH
its chemistry. respectively.
(c) Unipositive mercury is a dimmer, Hg22+. (k) An amalgam, and give a few uses.
(d) Unlike Zn cadmium compounds are (l) HgO is found in different colours (red and
extremely poisonous. yellow).
(e) Zn salts dissolve in water as well as in (m) ZnCl2 and MgCl2 differ in mp.
alcohol. (n) ZnS is insoluble in water but CaS is
(f) Hot ZnO is yellow. soluble.
(g) ZnCl2 solution is slightly acidic. (o) Zn(OH)2 dissolves in NaOH and NH4OH
(h) ZnCO3 is not prepared by adding Na2CO3 both.
in ZnCl2 solution. (p) Hg is liquid.
 Group 12 (IIB) – Zinc, Cadmium, Mercury  335

B. Complete the following reactions: (d) K2[HgI4] + KOH + NH3

(a) Zn + dil. HNO3 (e) Hg2Cl2 + NH4OH
(b) HgI2 + KI(excess) (f) HgCl2 + H3PO3 + H2O
(c) ZnCO3 + Co(NO3)2

Objective-Type Questions

1. Which of the following is phosphorescent? 9. Mercury does not form amalgam with
(a) ZnO (b) ZnS (a) Al (b) Ag
(c) ZnCl2 (d) Zn3P2 (c) Fe (d) Zn
2. Spelter is 10. Which of the following forms H2 when heated
(a) Zn – Hg (b) Pure Zn with caustic soda?
(c) impure Zn (d) Zn – Cu (a) Zn (b) Hg
3. Which of the following contains Ni? (c) Mg (d) Cu
11. Zinc blende ore is concentrated by
(a) Brass (b) Bronze
(c) German silver (d) Gun metal (a) Gravity separation
4. Which of the following reactions produces (b) Magnetic separation
yellow HgO? (c) Froth floatation
(a) HgCl2 + ½ O2 Δ  ∆  HgO + 2KCl (d) Leaching
+ CO2 12. Calamine is an ore of
∆   HgO (a) Ca (b) Cd
(b) Hg2O + ½ O2 Δ  
∆   HgO + 2NO + ½ O (c) Cu (d) Zn
(c) Hg(NO3)2 Δ 
∆   HgO
2 2 13. Which of the following is a carbonate?
(d) Hg + ½ O2 Δ   (a) Cuprite (b) Villemite
5. Which of the following gives black ppt. with (c) Siderite (d) Limonite
NH4OH? 14. One mole zinc phosphide on reaction with
(a) HgCl2 (b) Hg2Cl2 excess water will give
(c) K2[HgI4] (d) Hg(NO3)2 (a) One mole phosphine
6. Nesseler’s reagent is (b) Two mole phosphine
(a) K2HgI4 (b) K2HgI4 + NH4OH (c) Two moles phosphoric acid
(c) K2HgI4 + KOH (d) HgI2 + KOH (d) Three moles phosphine
7. Lucas reagent is 15. A metal forms two chlorides A and B. The
(a) HgCl2 + HCl chloride A gives white ppt. with NH4OH but B
gives black ppt. Also A forms a red ppt. with
(b) ZnCl2 + conc. HCl
KI, which dissolves in excess KI to form a
(c) CdCl2 + HCl colourless solution. A and B respectively are
(d) HgCl2 + conc. HCl (a) HgCl2 and Hg2Cl2
8. Corrosive sublimate is (b) Hg2Cl2 and HgCl2
(a) HgCl2 (b) Hg2Cl2 + Hg (c) ZnCl2 and Hg2Cl2
(c) Hg2Cl2 (d) HgCl2 + Hg (d) HgCl2 and ZnCl2

Answers

1. (b) 2. (c) 3. (c) 4. (c) 5. (b) 6. (c) 7. (b) 8. (a) 9. (c) 10. (a)
11. (c) 12. (d) 13. (c) 14. (b) 15. (a).
14
Group – 13 (IIIA)
B, Al, Ga, In, Tl

Boron, Al, Ga, In and Tl are p – block elements and have three valence electrons (ns2np1).
Group in p – block = valence electrons + 10.
So, these elements belong to group – 13.

Electron configuration and core electrons

Table 14.1
Electron At. No. Electron configuration Core electrons
B 5 [He] 2s22p1 2
Al 13 [Ne] 3s23p1 8
Ga 31 [Ar] 3d1o4s24p1 18
In 49 [Kr] 4d 5s 5p
1o 2 1
18
Tl 81 [Xe] 4f145d1o6s26p1 18

The difference in the number of core electrons and presence
of 4f electrons in Tl has profound effect on the chemistry of these
elements. Valence orbitals include p-orbitals. With the filling
of p – orbitals, non-metallic property develops. Boron is thus a
non-metal (slightly metallic). However, non-metallic nature
decreases with increase in atomic number and Al, Ga, In and Tl
are metals. Boron is a semiconductor but others display metallic
conduction. All the elements are solid.
B has rhomohedrae structure, B12.
Gallium and In have unusual structures. Gallium has
exceptionally low melting point (~30°C) but its boiling point is
high (~2070°C). It is the longest liquid range (30–2070OC) of $O FFS
any known substance. Therefore, Ga is used for high temperature
7O KFS
thermometry in a quartz envelope.
Aluminium and Ga are amphotric and dissolves in NaOH Figure 14.1
solution on boiling.
 Group – 13 (IIIA) B, Al, Ga, In, Tl  337

Al + NaOH + H2OH Na AlO2 + H2

Boron reacts when fused with NaOH.
fused
2B + 6NaOH fused 2Na3BO3 + 3H2

General Properties

Table 14. 2
Property B Al Ga In Tl
Atomic radius (Å) 0.82 1.18 1.26 1.44 1.48
Ionic radius, M+3(Å) 0.2 0.5 0.62 0.81 0.95
Metallic radius (Å) – 1.43 1.41 1.66 1.71
Ionisation I 8.3 5.95 6.0 5.8 6.1
Enthalpy (ev) II 25.2 18.82 20.0 18.8 20.3
III 38.0 28.44 30.6 28.0 29.7
Electronegativity 2.0 1.5 1.6 1.7 1.8
mp (°C) 2180 660 29.8 157 303
bp (°C) – 2327 ~2250 2070 1553
E°, M3+/M (V) –0.73 –1.66 –0.56 –0.34 +0.72

Note:
(i) Radius of Tl+ is 1.44Å and Eo Tl+/Tl is –0.34V.
(ii) Variation of atomic radius is not regular, (i.e., do not increase down the group), and rAl ~ rGa and rIn ~ rTl+.
The equivalence is due to d – orbital contraction for Al – Ga and lanthanide contraction for In – Tl.
(iii) The first IE of Al and Ga are almost equal due to similarity in radii.
(iv) The IE of In < Tl. It is due to higher effective nuclear charge (Z*) for Tl. It results as 4f electrons are least
shielding.
(v) E° for Al (Al+3 – Al) is high inspite of its very high III ionisation energy. The very high hydration energy
of Al3+ causes this reaction to proced,
Al+3 + water fi Al+3(aq) ∆HHyd ~ 4665KJmol−1
The main reason for high hydration energy is very high charge to radius ratio for Al3+ (~6)

Oxidation states and nature of bond

The group –13 elements show variable oxidation states of +3 and +1. For lighter members +3 state is more
stable than +1. Thus for Tl, +1 state is more stable than +3. It is due to inert pair effect. The 6s2 pair does not
prefer to form bonds and is called inert pair. The basic reason for such an effect is bond energy. The M–Cl
bond energy in MCl3 compounds are as follows:

Table 14. 3
MCl3 M – Cl, energy (KJmol–1)

Ga 242
In 206
Tl 153
338  Basic Concepts of Inorganic Chemistry

The ionization energies of B is very high. It is, therefore, covalent in its compounds, always tricovalent
(2s22p1 electrons).
In +3 oxidation state, Al has very high charge to radius ratio (~6.0). So, it is also covalent in its anhydrous
compounds. However, in aq. solution tricovalent Al (e.g., AlCl3) becomes ionic due to high hydration energy
of Al+3 (4665KJmol–1) [Al(OH2)6]3+.3Cl–. The soluble compounds are quite acidic due to hydrolysis (high
charge to radius ratio of Al+3).
) &O
[Al(OH2)6] + H2O
+3
  H3O + [Al(H2O)5OH]
+ +2

% $O
Tl is ionic in +1 oxidation state, TlCl ionic. The Tl ion resembles
+

) ) &O &O
K+ and Rb+. It is because radii of the ions are comparable (K+ ~ 1.38Å,
Tl ~ 1.5Å, Rb ~ 1.52Å). Therefore, TlOH is a strong base like group (Six electrons around B or Al)
– 1 hydroxides. Tricovalent compounds, MX3, are electron deficient Figure 14.2
as octet around the central atom is not complete.
Such compounds remove their electron deficiency by:
(i) Back – bonding
In BX3, B is sp2 and has a vacant p – orbital perpendicular at the triangular plane. X – atom has filled
p – orbital. They overlap resulting into π–bonding.

)
)
% 5HVRQDQFH
%
) )
) )
Figure 14.3

(ii) Coordination with Lewis bases

B has vacant orbital which accepts electron pair form F–.
)

% )Ā%)  Ā
) )
  $O2+ +2Ā $O2+  Ā

Figrue 14.4

Al(OH)3 + HO– Al(OH)4–

(iii) Polymerization
AlCl3 removes electron deficiency by dimerization.
2AlCl Al2Cl6
Dimer is made easily because Cl has lp and Al has vacant orbital. &O &O  &O
AlCl3 is not stabilized by back bonding. It is due to the following $O $O
&O &O
facts:  &O
(i) p – orbital of Al is large, so p – p overlap is not effective. Figrue 14.5
(ii) 8 electron core in Al causes larger repulsion (8e – 8e) destabilizing
back bonding effective.
 Group – 13 (IIIA) B, Al, Ga, In, Tl  339

 ;
; ;
BX3 can not stabilize by dimerization. %
%
B is small in size. The dimer has a small ringn ; ; ;
have so, it is not stable.
Figrue 14.6

Hydrides
Boron forms a series of volatile molecular hydrides called Boranes, B2H6, B4H10, B5H9, B6H10 etc. Boranes
were first prepared by Alfred Stock in the year 1912 to 1936.
Mg3B2 + 6HCl B2H6 + 3MgCl2
(trace)
2Mg3B2 + 12HCl B4H10 + 6MgCl2 + H2
(major)
Diborane, B2H6, is simplest. Two series of boranes are found:
(i) Bn Hn + 4 B2H6, B5H9 ect (nideo – boranes)
(ii) Bn Hn + 6 B4H10, B5H11 ect. (arachno – boranes) Table 14. 4
The Bn Hn + 4 series compounds are more stable. Boranes Formula Name
are named as
The last number in the name indicates number B2H6 Diborane – 6
of hydrogen atoms. B4H10 Tetraborane – 10
B5H9 Pentaborane – 9

Diborane (B2H6)
It is a gas (bp – 92.6oC) spontaneously flammable in air. It can be prepared in many ways:

diglyme
(i) 4BF3 + 3NaBH4 3NaBF4 + 2B2H6

ether
(ii) 8BF3 + 6LiH B2H6 + 6LiBF4
diglyme
(iii) 2NaBH4 + I2 B2H6 + 2NaI + H2

ether
(iv) 4BCl3 + 3LiAlH4 2B2H6 + 3AlCl3 + 3LiCl
This reaction is quantitative
(diglyme – diethylene glycol dimethyl ether H3C OCH2 – CH2 – O – CH2 – CH2OCH3)

Properties
(i) It spontaneously burns in air.
B2H6 + 3O2 B2O3 + 3H2O
(ii) It is instantly hydrolyzed by water or alkali.
B2H6 + 6H2O 2H3BO3 + 6H2

B2H6 + 2NaOH + 2H2O 2NaBO2 + 6H2

340  Basic Concepts of Inorganic Chemistry

(iii) It is electron deficient and forms addition compound with Lewis bases.

2008C
B2H6 + CO H3B : CO
high P
(iv) Some more reactions are summarized.
2

%++  
2

&+  ±2+
 (W  2
&+  ±2+
+&O 1+ ǻ
+  %  +  &O  %  1  +  +  
&O  %  +   1+ H[FHVV
%&O  +&O 
%1[
 ǻ
0H 62 1D2+

%  +  0H  

Figrue 14.7

(v) Hydroboration: The reaction of B2H6 in ether with unsaturated hydrocarbons, called hydroboration. It
gives mainly anti-Markownik off, cis-hydrogenation or hydration.

+ 2 5±&+  ±&+  
5 +
& & 5±&+  ±&+    %
+ + + 2 5±&+  ±&+  ±2+
GLJO\PH
&2 ± R &

+ 2 
>5±&+  ±&+  ±  &%2@   5±&+  ±&+    &±2+


Figrue 14.8

Structure of B2H6
Diborane (B2H6) is stoichiometrically identical to C2H6. But they have different structures.
 Group – 13 (IIIA) B, Al, Ga, In, Tl  341

Table 14. 5
Molecule Valence electrons Structures
 + +
C2H6 4x2 + 1x6 = 14 

+ & & +
 + +
Electron deficient
B2H6 3x2 + 1x6 = 12 structure as above not
possible

Ethane has 14 valence electrons and there are seven bonds in C2H6. Therefore a 2c – 2e bonding scheme
is possible. But B2H6 has only 12 valence electron. Therefore 2c – 2e bonding scheme is not possible in B2H6
as it is basically electron deficient.
Methods of structure determination reveal that B2H6 has a H – bridge + + +
% %
structure like
+ + +
This structure has two types of B – H bonds
Figrue 14.9
(i)  Terminal B – H bonds. These are 2c – 2e bonds.
H
(ii) Bridge B B bonds (a 3c – 2e bond). This bridge bond is explained by the concept of multicentre
bonding.
In a 3c – 2e multicetre bonding, 2 electrons are used to join three centres (3 atoms).
In B2H6 structure, B is sp3.
V
%(VWDWH

VS  K\EULGV
Figrue 14.10

Two out of these four hybrids at each B overlap with the 1s orbital of the H–atom to give four terminal
B – H bonds.

+ +
% %


Figrue 14.11
All these B – H bonds are in the same plane.
The bridge B – H – B bonds are formed when sp3 hybrid at B having electron, sp3 hybrid vacant at other
B – atom and 1s orbital of H – atom overlap.

+
+ + + +
% % % %
+ + + + +

Figrue 14.12
342  Basic Concepts of Inorganic Chemistry

These are perpendicular to the terminal bonds. This is three centre – 2 electron multicentre bonding
(3c – 2e bonding). This bond is called t –bond or banana bond or bent bond.
Terminal and bridge H atoms are not equivalent. It is proved by IR, Raman spectra and chemical reaction
also.
Diborane forms tetramethyl derivative, B2H2Me4, only showing chemical equivalence of four H –
atoms.
Aluminium hydride is polymeric, (AlH3)x. It has also H – bridge structure,

+ +
$ $ $
+ +
Figrue 14.13

The H – bridge, Al – H – Al has 3c – 2e bonding.

Borazole (B2N3H6)
When B2H6 and NH3 in the ratio 1 : 2 heated at high temperature borazole is formed.
High
B2H6 + NH3 B2N3H6
temp
(1 : 2)
Borazine resembles benzene in structure. The π bond in borazine is, however, formed by back bonding,
involving filled p – orbital at N and vacant orbital at B.

+ +

+ % + + % +

1 1 1  1 

% % % % 
+ 1 + + 1 +

+ +
Figrue 14.14

Thus borazine has aromatic character (4n + 2)π electrons. It is called inorganic benzene.
Borazine unlike benzene is more reactive towards addition reactions.
B3N3H6 + 3HCl   B3N3H9Cl3

1D%+  % 1 + 
3K±&O
1+  &O%&O  %
   1  +  &O  

&+ 0J%U

%  1  +  &+   

Figrue 14.15
 Group – 13 (IIIA) B, Al, Ga, In, Tl  343

Substituted borazine can be prepared as

Disubstituted borazine B3N3H4X2 can have four isomers (there are only three for C6H4X2).

; ;

% %
;
+1 1 +1 1+

+% %+ +% %

1 1 ;
+ +
>,@>,,@

 ;
+
% %
;
+1 1 +1 1+

+% %+ +% %+
1 1

; ;
>,,,@>,9@

Figrue 14.16

Boron nitride (BN)x

When B2H6 is heated at high temperature with excess NH3, boron nitride is formed.

% % %

1 1 1 1

% % % %

 1 1

% % %
1 1

Figrue 14.17

The B – N, π bond is formed by overlap of filled p–orbital at N and vacant p – orbital at B.

344  Basic Concepts of Inorganic Chemistry

Oxygen compounds (oxide and hydroxides)

Boron is inert towards O2 at ordinary temperature. But it burns with green flame when heated strongly in O2.
∆
2B + 3/2O2 B2O3
High
temp.
But B2O3 is usually made by dehydrating boric acid.
∆ red heat
H3BO3 HBO2 B2O3
(~1008C)
Boric oxide (B2O3) is acidic in nature. Onbeing heated with transition metal oxides B2O3 forms
metaborates which have colours.
Cr2O3 + 3B2O3 2Cr(BO2)3, [Green]
CuO + B2O3 Cu(BO2)3, [Blue]
This is the basis of borax bead test in salt analysis.
Boric oxides (B2O3) also react with very highly acidic oxides like P4O10 forming boron phosphate.

2B2O3 + P4O10 ∆ 4BPO4

In this reaction B2O3 is basic.
Aluminium reacts rapidly with O2 but only at the surface to form Al2O3. The thin film of Al2O3 on the
surface prevents further reaction.
At high temperature Al burns in O2 with brilliant white light forming Al2O3. The reaction is highly
exothermic.
2Al + 3/2O2 Al2O3 + Q
The ΔHf of this reaction is very high, –1670 KJmol–1, higher for any other metal oxide.
There are two forms of anhydrous Al2O3(alumina):
(i) α – Al2O3 (corundum) and
(ii) γ– Al2O3
Hydrous oxide

}
Al2O3 . x H2O
~10008C
or α – Al2O3
γ – Al2O3
~4508C
Al2O3 . x H2O γ – Al2O3
The α – Al2O3 is very hard (9 on Moh’s scale), and resistant to hydration and attack by acids.
Gem stones ruby, blue sapphire are mixed metal oxides:
Ruby α – Al2O3 + (Cr+3)
Blue sapphire α – Al2O3 + (Fe2+, Fe3+ and Ti+4)
Fibrous Al2O3 and ZrO2 form a fiber known as “Saffil”.
Alumina (Al2O3) is extremely stable (ΔHf = –1670 KJmol–1). Therefore, Al–powder is used to reduce
metal oxides to metal, especially transition metal oxides,
Cr2O3 + 2Al 2Cr + Al2O3 + Q
3Mn3O4 + 8Al 9Mn + 4Al2O3 + Q
 Group – 13 (IIIA) B, Al, Ga, In, Tl  345

The reactions are highly exothermic. So much so heat is evolved that the reduced metal is obtained in
the molten state. This process is known as Alumino Thermic Reduction or Thermite Reduction or Goldsmidt
Alumino Thermic Reduction.

Boric Acid
B2O3 is acidic and dissolves in water to form Boric Acid.
B2O3 + 3H2O 2B(OH)3
It is a weak acid (pKa = 9.0), moderately soluble in water. In water it acts as a Lewis acid, accepting HO–
from water and thereby releasing a proton,(H+).
B(OH)3 + H2O B(OH)4– + H+
Thus, B(OH)3 behaves a monoprotic acid. The acid strength of boric acid is increased in the presence of
a polyol like glycerol, mannitol etc., (but not ethylene glycol). The acidity is increased due to formation of a
complex (chelate), and so boric acid can be titrated with NaOH.

& 2+ +2  2+ & 2 2+

 % %
+  2
& 2+ +2 2+ & 2 2+

& 2+

& 2+

& 2  2 &
%
& 2 2 &

Figrue 14.18

The complex has spiran like structure. Hence, often called Borospiranic acid.

+
Structure of Boric Acid + 2 2
+ % +
2 2
The aluminium hydroxide is amphoteric. It can be precipitated
2
when an aluminum salt solution is treated with NH4OH. + + %
%

2 2 2 2 +
water + + +
AlCl3 sol. Al+3(aq) + 3Cl–(aq) +
2 2 2 2
+ + +
%

Al+3(aq) + 3nh4oh ↓Al(OH)3 + 3NH4+ (aq) 2

%

(Gelatinous white) 2 % +
2
2 2 +
The ppt. is actually [Al(H2O)3(OH)3]
+
Al(OH)3 is amphoteric because Al – OH and O – H bonds can
react with equal ease.
Figrue 14.19
Therefore, Al(OH)3 dissolves in conc. NaOH or dil. HCl both.
346  Basic Concepts of Inorganic Chemistry

HO¯
(HO)2 AlO¯ + H 2 O

(HO) 2 Al – O – H

Al +3( a q) + H 2 O
H3 O+

Figrue 14.20

Halides
All elements form halides of the type MX3.
∆
2M + 3X2 2MX3
Cu +2
The compound TlI3 is not Tl(III) iodide but is Tl(I) triiodide, +I¯
Fe 3+ X
Tl+I3–. Many other metals in their higher oxidation state also do not
form stable iodides. Example, Pb +4

The iodides actually formed are CuI, FeI2 and PbI2.

Boron trihalides, BX3, are known for all the halogens. Their Figrue 14.21
gerneral properties are as follows:

Table 14. 6
Property BF3 BCl3 BBr3 BI3
Physical state Gas Volatile liq. Volatile liq. Unstable white solid

ΔHf (250°C) gas, KJmol–1 –1123 –408 –208 –

mp (°C) –127 –107 –46 50

bp (°C) –99.9 12.5 91.3 210

Bond distance (Å) (B – X) 1.30 1.75 1.87 2.10

Bond energy (KJmol–1) (B – X) 646 444 368 267

The boron trihalides, BX3, are hydrolyzed by water, but BF3 is hydrolyzed partially.
BF3 + 3H2O H3BO3 + 3HF

3BF3 + 3HF 3BF4– + 3H+

3H+ + 3H2O 3H3O+

4BF3 + 6H2O H3BO3 + 3BF– + 3H3O+

BF4– + H2O [BF3OH]– + HF

Other halides are hydrolyzed completely to boric acid.
BCl3 + 3H2O H3BO3 + 3HCl
 Group – 13 (IIIA) B, Al, Ga, In, Tl  347

The fluoride of Al (and Ga, In, Tl also) is ionic (XF large) having high mp.
The other halides of Al i.e., AlX3 (X = Cl, Br, I) are covalent when anhydrous.
They exist as dimer. &O
&O &O
The dimeric formula is retained when it dissolves in benzene (non-polar
$O $O
solvent). But when it is dissolved in water, the covalent dimer is broken to &O &O &O
ionic species.
Figrue 14.22
water –
Al2Cl6 2[Al(H2O)6] + 6Cl (aq)
3+

It is due to very high hydration enthalpy of Al+3 (~4665KJmol–1)

Lewis Acid Strength of BX3

;
Boron trihalides are electron deficient (only six electrons around B) and function
as Lewis acids. If electronegativity and steric factor are considered, the Lewis acid
strength should be, BF3 > BCl3 > BBr3 > BI3. % ;
However, the actual strength found is, BF3 < BCl3 < BBr3 < BI3
It is explained, in terms of B–halogen π–bonding. In BX3, boron is sp2 ;
hybridized and BX3 is triangular planar. The pz orbital at B is vacant.
But Pz orbitals at each halogen is filled (i.e., has 2 electrons). These orbitals Figrue 14.23
overlap side-wise forming π bond.

; ;

% ; % ;

; ;

Figrue 14.24

Such a π–bond is delocalized as all the halogens are capable of forming π-bonds. The π–bond
effectiveness is maximum in BF3 as B and F are comparable in size. With increase in size of the halogen
π–bond effectiveness decreases. Thus electron deficiency at B is maximum in BI3 and minimum in BF3.
Hence the Lewis acid strength is
BF3 < BCl3 < BBr3 < BI3
Alums
Alums are hydrated double salts which contain large M+, small M+3 and SO4–2 ions. Their general formula is,
M+ M+3 (SO4)2.12H2O, where,
M+ = Na+, K+, NH4+ etc.
M+3 = Al+3, Fe+3, Cr+3, Ti+3, V+3, Co+3 etc.
The Li+ ion does not form alum as it is too small to produce a stable crystal structure. The alum crystals
are large octahedra which contain [M(H2O)6]+, [M(H2O)6]+3 and two SO4–2 ions. They are found very pure.
KAl(SO4)2.12H2O Potash alum
KCr(SO4)2.12H2O Chrome alum
NH4Al(SO4)2.12H2O Ammonium alum
KFe(SO4)2.12H2O Ferric alum
348  Basic Concepts of Inorganic Chemistry

Alums are prepared by crystallization of equimolar solutions of the two sulphates.

K2SO4 + Al2(SO4)3 K2SO4.Al2(SO4)3.24H2O
or
KAl(SO4)2.12H2O
Potash alum, KAl(SO4)2.12H2O (fitkiri) is used as a mordant in dyeing. It is also used as antiseptic.

Isolation of B
Ores
1. Borax Na2B4O7.10H2O
2. Kernite Na2B4O7.H2O
3. Coleminite Ca2B6O11.5H2O

Most important ore is borax and B is isolated from borax.

Steps
1. Borax to Boric acid crystal
2. Boric acid to B2O3
3. Red. Of B2O3 to B.

Reactions
(a)  Powdered borax + conc. HCl is heated to produce boric acid.
∆
Na2B4O7 + 5H2O + 2HCl 2NaCl + 4H3BO3
    Hot solution on cooling gives crystals of H3BO3.
∆
(b)  2H3BO3 B2O3 + 3H2O↑ Crystal
(c)  B2O3 B (amorphous)
∆
B2O3 + 3Mg 2B + 3MgO
Boron produced contains impurities of Mg3B2, B2O3 and MgO.
The impurities are removed by washing with aquous NaOH, HCl and finally with HF; which produces
B of ~95% purity.
B2O3 + 6NaOH 2Na3BO3 + 3H2O
Mg3B2 + 6HCl 3MgCl2 + B2H6
B2O3 + 6HF 2BF3 + 3H2O

Crystalline B
It may be obtained by the following methods.
Ta – filament
(i)  2BF3 2B + 3F2↑
∆
(ii)  Van Arkel method
W or Ta – filament
2BI3 B + 3I2↑
Red heat
 Group – 13 (IIIA) B, Al, Ga, In, Tl  349

Practice Questions

A. Explain the following: (q) Al2O3 when heated with Co(NO3)2 forms
(a) Atomic radii of Al and Ga are almost equal. blue mass.
(b) B2 is paramagnetic. (r) Al(OH)3 is an amphoteric hydroxide.
(c) First IE of Al is lower than Mg. (s) Anhydrous AlCl3 is not obtained when
(d) The B – F bond is more polar than B – Br Alcl3.6H2O is heated.
bond but BF3 is a weaker Lewis acid than (t) Progressive addition of NaOH solution to a
BBr3. solution of AlCl3 till higher pH (pH ~ 10)
(e) Boric acid is strong in the presence of (u) LiBH4 is soluble in water whereas LiAlH4
glycerol (or other polyols). explode in water.
(f) Cupric oxide forms blue mass when heated B. (i) How will you convert B2H6 into
with borax. (a) (BN)X
(g) Al is a good reducing agent for transition (b) B3N3H6
metal oxides. (c) B2H2Me4
(h) Boron does not exist as B+3 in its (d) B2H5Cl
compounds. (e) B(OCH3)2
(i) Al is stable in air and water although it is (f) B(OH)3
very electropositive. (ii) How will you convert...
(j) Tl is more stable in +1 oxidation state. (a) B2O3 into crystalline Boron
(k) How does H3BO3 ionize in water? (b) BCl3 into B2H6
(l) The substance TlI3 contains what ions and (c) Al2O3 into potash alum
why? (d) AlCl3 into LiAlH4
(m) AlF3 does not resemble BF3 and is a weak (iii) Draw the structure of the following:
Lewis acid. (a) B2H6
(n) Boric acid in methanol when heated gives (b) B3N3H6
vapours, which will colour a flame green. (c) Na2B4O7.10H2O
(o) Draw the structure of B2H6 and explain (d) Al(O.t–Bu)3
bonding. (e) (BN)X
(p) Anhydrous AlCl3 is covalent but hydrated (f) Isomers of B3N3H4Cl2
salt is ionic.

Objective-Type Questions

  1. Which of the following is expected not to exist?   4. The correct order of atomic radii of Gr 13
(a) B5H11 (b) B5H9 elements is
(c) B5H10 (d) B6H10 (a) B < Al < Ga < In
(b) B < Al ~ Ga < In
  2. The correct Lewis acid strength order is
(c) B < Al < Ga ~ In
(a) BBr3 > BCl3 > BF3
(d) B < Ga < Al ~ In
(b) BF3 > BCl3 > BBr3   5. Which of the following represents an alum where
(c) BCl3 > BBr3 > BF3 M1 and M2 are mono and tripositive metal ions?
(d) BBr3 > BF3 > BCl3 (a) (M1) (M2) (SO4)2.12H2O
  3. Which of the following processes does not (b) (M1)3 (M2) (SO4)3.12H2O
involve a catalyst?
(c) (M1)2 (M2)2 (SO4)4.12H2O
(a) Ostwald process (b) Contact process
(c) Thermite process (d) Lane’s process (d) (M1)4 (M2)2 (SO4)5.12H2O
350  Basic Concepts of Inorganic Chemistry

  6. Crystalline Boron can be prepared by (c) Poor screening power of d – orbitals in

(a) Dow process Ga.
(b) Down’s process (d) None of these
(c) Van Arkel method 15. Consider the following statements for B2H6 and
(d) Degusa process mark the correct one.
  7. The correct stability order of BX3 (X = F, Cl, I. All B – H bonds in it are equivalent
Br, I) molecules is II. Four B – H bonds are equivalent.
(a) BF3 > BCl3 > BBr3 > BI3 III. It is electron deficient.
(b) BF3 > BBr3 > BCl3 > BI3 IV. It has multicentre bonding.
(c) BI3 > BBr3 > BCl3 > BF3 (a) I, II and III, (b) II, III and IV
(d) BCl3 > BI3 > BBr3 > BF3 (c) I, III and IV (d) I, II and IV
  8. Which is correct for B2 molecule? 16. When excess NaOH solution is added in potash
(a) KKσ22Sσ*22Sσ22pz alum the product is
(b) KKσ22Sσ*22Sπ1px = π12py (a) A bluish precipitates
(c) KKσ22Sσ*22Sπ22pz (b) A white precipitate
(d) KKσ22Sσ*22Sπ12py = π12py (c) A greenish precipitate
  9. When Al2O3 is heated with Co(NO3)2, Which of (d) Clear solution
the following coloured mass is obtained? 17. Borax, Na2B4O7.10H2O contains
(a) Blue (b) Green (a) Two four and two three coordinated B.
(c) Yellow (d) Orange (b) One four and three three coordinated B.
10. Alum is a (c) Three four and one three coordinated B.
(a) Double salt (b) Complex salt (d) All three coordinated B.
(c) Acidic salt (d) Basic salt 18. Colemanite is an ore of B, which is formulated
11. When K2S is added to an aq. solution of AlCl3, as
which of the following can precipitate? (a) CaB2O7.5H2O (b) CaB4O7.5H2O
(a) Al2S3 (b) Al(OH)3 (c) Ca2B6O11.5H2O (d) Ca3B6O11.5H2O
(c) [Al(H2O)3.(OH)3] (d) None of these 19. One mole magnesium boride when treated with
12. How many isomeric disubstituted borazine, dil. HCl, produces
B3N3H4X2 are possible? (a) One mole B2H6 (b) Two mole B2H6
(a) 6 (b) 4 (c) Three mole B2H6 (d) 1.5 mole B2H6
(c) 5 (d) 3 20. When a paste of borate, solid CaF2 and conc.
13. When aluminum hydroxide dissolves in NaOH H2SO4 is heated in a flame, the colour produced
solution, the product is is
(a) [Al(H2O)2(OH)4]– (a) Red (b) Green
(b) [Al(H2O)3 (OH)3] (c) Blue (d) Violet
21. B2O3 can dissolve in water to form
(c) [Al(H2O)4 (OH)2]+
(a) One acid (b) Two acids
(d) [Al(OH) (H2O)5]2+
(c) Three acids (d) Four acids
14. The radii of Al and Ga are almost equal because 22. Which of the following is not a proton acid in
(a) Greater screening power of d – orbitals in general way?
Ga. (a) PO(OH)3 (b) B(OH)3
(b) Greater screening power of s – orbitals in (c) SO2(OH)2 (d) SO(OH)2
Ga.

Answers

1. (c) 2. (a) 3. (c) 4. (b) 5. (a) 6. (c) 7. (a) 8. (b) 9. (a) 10. (a)
11. (c) 12. (b) 13. (a) 14. (c) 15. (b) 16. (d) 17. (a) 18. (c) 19. (a) 20. (b)
21. (c) 22. (b)
 15
Group – 14 (IVA)
C, Si, Ge, Sn, Pb

Element of this group are p–block element. Carbon and Si are non-metals (Si slightly metallic), Ge is
metalloid, Sn and Pb are metals.

Carbon
Carbon has three isotopes, they are:

Table 15.1
Isotope No. of neutron Abundance Nature
12C 6 98.9%
Stable isotopes
13C 7 1.1%
14C 8 Trace Radioactive
t1/2 = 5770yrs

The radioisotope 14C (t1/2 = 5770 years) can be produced by thermal neutron irradiation of Al – nitride.

 1+ + 
 1 Q  Q


&
   +&S+ S


In the atmosphere, 14C is produced by the action of the neutrons in cosmic rays on nitrogen (like above
reaction). Its formation and absorption of 14CO2 by living systems (plants and organisms) is used in radiocarbon
dating to determine age of archaeological species. Libby developed this method for which he got Nobel Prize
for Chemistry (1960).
Table 15.2

Catenation Bond Bond Energy

(KJmol–1)
The property of self-linking is known as catenation. It depends mainly C–C 356
on bond energy. The C – C bond energy is very high. Therefore, C has Si – Si 210 – 250
maximum catenation property. The bond energy decreases down the Ge – Ge 190 – 210
group and so also the catenation property, i.e., Sn – Sn 105 – 145
C >> Si > Ge ≈ Sn >> Pb
Sulphur also shows catenation because S – S bond energy is relatively high. Boron, Si, P shows
heterocatenation as B – O, Si – O and P – O bond energies are high. (Table 15.3)
352  Basic Concepts of Inorganic Chemistry

Allotropy and Structure  Table 15.3

All the elements are solid. Only Carbon and Sn show allotropy. Bond Bond Energy
Carbon has three crystalline allotropes: (KJmol–1)
(a) Graphite S–S 226
(b) Diamond B–O 560 – 790
(c) Fullerence Si – O 368
P–O ~ 340
Tin is found as α-Sn, and β-Sn.

Table 15.4
Element Allotrope Structure
Graphite Layer structure
C Diamond Cubic structure
Fullerence Carbon cluster
Si – Diamond structure
Ge – Diamond structure
α – Sn Diamond structure
Sn β – Sn Cubic structure
γ – Sn Simple cubic structure
Pb – ccp

Graphite
It is soft dull looking greasy substance and is
good conductor of electricity. Graphite has two– &
dimensional layerd structure. & &
The layers are made up of sp2 hybridized C
atoms. Each C is joined with three other C atoms
through σ–bonds forming hexagonal rings. Each & & &
C is left with its fourth valence electron in a p – & & & &
orbital. They overlap and form π bonds. These π
bonds are delocalized. Therefore, all C – C bond
distances in graphite are equal (1.415Å). Sheet & & & &
to sheet distance in graphite is 3.35Å. It is known & & &

as C – dimension. Layers are joined by weak van
der Waals force.
The weak force between layers allows one & & &
layer to slide over the other. It imparts softness & &
to graphite. It is, therefore, used in pencils
for writing. Due to delocalized π electrons
graphite is a conductor (though along the sheet Figure 15.1
not perpendicular to it). Hence, it is used as
electrode.

Intercalation compounds of graphite

The layered structure of graphite allows molecules and ions to penetrate between the layers. Such aggregates
are known as intercalation or lamellar compounds. These are of two types:
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  353

(i) Those in which graphite becomes non-conducting. Example, graphite oxide and graphite fluoride,
and
(ii) Those in which conductivity of graphite is retained or even enhanced. For example, C8M (M = K,
Rb, Cs). They have high electrical conductivity because metal is present between the layers
as M+.

Diamond
It is a colourless, transparent, an hardest substance known and is an insulator. &
Cut diamond is sparkling solid (due to refraction). Diamond has cubic unit
cell. Each C is sp3 hybridized and is joined with four other C atoms through
σ – bonds.
&
As C – C bond energy (356KJmol–1) is very high and diamond has a &
&
giant structure, it is very hard. This structure is responsible for its insulator
property.
&
Density of diamond (3.51g/cc) is greater than graphite (2.22g/cc). This
shows that to change graphite into diamond, pressure must be applied. There
is an equilibrium. Figure 15.2
15000 atom
Graphite    diamond
300k

Graphite can be transformed into diamond at a reasonable rate at high pressure and ~ 3000 K in the
presence of a transition metal (Fe, Cr, Pt) catalyst.

Fullerenes
Fullerenes are carbon clusters having cage like structures. They were discovered by R. F. Curl, H. W. Croto
and R.E. Smalley. They were awarded the 1996 Nobel Prize for the discovery of fullerenes.
Electric spark –∆ C6H6
Graphite rod Vap Soot
Ar atmosphere
Crystal
Wine red sol.
Mustard colour crystal C60, C70 (trace)
Fullerenes C60 and C70 can be separated by chromatographic method over alumina. Many other fullerenes
also exist such as C32, C50, C76, C84 etc. Carbon clusters upto 600 atoms have been observed.
The C60 cluster is called Buckminster fullerence in the honour of American architect Robert Buckminster
Fuller.
Its (C60) structural features are as follows:

• Spherical structure (like a soccer ball)

• It has twelve (12) five-memberd rings and twenty (20) six-membered rings.
• Five-membered rings are fused with six-membered rings only.
• Six-membered rings are fused with five–membered and six-membered rings both.
• Carbon atoms in C60 are sp2 hybridized making three 3σ bonds.
• Rest one electron with each C-atom in a 2p orbital forms π-bonds.
• The π-bonds are delocalized to impart aromatic nature to C60.
• Average C — C distance is around 1.44Å.
354  Basic Concepts of Inorganic Chemistry

Structure of C60 
Silicon exists only in diamond structure. A graphite like structure for
Si is not possible because it has no propensity to form (p – p)π bond.
Tin exists in three forms, α – Sn , β – Sn and γ – Sn.

a– Sn     β – Sn  γ – Sn
(Grey) (White) (Brittle)
(Non-metallic (Metallic distorted (Rhombic)
diamond structure) close packed)
Figure 15.3
Semiconductor property of Si and Ge
Silicon and Ge are important semiconductor materials. Pure Si and Ge are non-conductor of electricity.
However, when they are dopped with group-13 or group-15 elements, they become semiconductor.
(i) Ge dopped with In
Ge – 4s24p2
In – 5s25p1
When Ge is dopped with In, there is one electron less at In site. There develops a positive hole in
the lattice which makes Ge conducting. Such a semiconductor is called p – type (positive – type)
semiconductor.
(ii) Ge dopped with As
Ge – 4s24p2
As – 4s24p3
When As is dopped in Ge, there is one electron excess at As site. Due to this excess electron Ge conducts
electricity. Such a semiconductor is called n – type (negative type).

*H *H *H *H

*H *H ,Q *H

,Q *H *H *H *H

*H *H *H *H *H *H *H *H

*H *H *H *H

*H *H *H *H

*H *H *H *H
*H *H *H *H
$V $V *H
*H *H

*H *H *H *H

*H *H *H *H

Figure 15.4
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  355

Physical properties of group – 14 elements

Table 15.5
Property C Si Ge Sn Pb
Atomic no. 6 14 32 50 82
Electronic structure –2s22p2 –3s23p2 3d104s24p2 4d105s25p2 4f145d106s26p2
Atomic radius (Å)
0.77 1.17 1.22 1.40 1.44
[covalent radius]
Ionic radius (Å) 0.15 0.41 0.53 0.71 0.84
Metallic radius (Å) – – 1.37 1.62 1.75
Ionization energy
11.3 8.2 7.8 7.3 7.4
(ev) [I]
[II] 24.4 16.3 15.9 14.6 15.0
Electronegativity 2.5 1.9 1.8 1.7 1.7
mp (°C) >3550 1410 937 232 327
bp (°C) 4827 2355 2830 2260 1744

Note:
(i) The radii of Si and Ge are very similar due to d – block contraction. Also Sn and Pb have almost similar
radii due to lanthanide contraction.
(ii) Ionization energy vary as C > Si ~ Ge > Sn < Pb. Silicon and Ge have comparable IE due to similarity
in their radii.
The radius of Sn is smaller than Pb but Pb has higher IE than Sn. It is due to higher Z* for Pb as f –
orbital is least shielding.

Oxidation states and Bonding

Group – 14 elements show variable oxidation states of +2 and +4. The stability of +2 state is very stable for
Pb. It is due to inert pair effect.

C +4 +2
Si
Ge
Sn
Pb

Stability decreases Stability increases

Carbon and Si have high ionization energy. Therefore, they are covalent in their compounds.
Tin and Pb form ionic compounds having appreciable covalent nature. It is because Sn and Pb are not
very large and have 18e core.
Carbon and Si differ widely in their bonding pattern. It is because of the following reasons:
356  Basic Concepts of Inorganic Chemistry

Table 15.6
Property C Si
Valence orbitals and
2s22p2 3s23p2 (3d0)
electrons
Number of bonds or
4 only More than 4 (5 or 6)
coordination number
No (p – p) π bonding but
Very effective
π – bonding (p – d) π bonding. Using
(p – p) π bonding
vacant 3d orbitals
C – C bond energy 356KJmol–1 226KJmol–1
Catenation property Very high Low, however,
heterocatenation is
pronounced due to strong
Si – O bond (368KJmol–1).

The features of certain Si compounds having Si – O and Si – N bonds are explained by (d – p)π bonding. For
example,
(CH3)3N Δr Pyramidal
(SiH3)3N Δr Planar
(SiH3)2O L Si – O – Si ≈ 1440 
Trisilylamine, (SiH3)3N, is trigonal planar due to (d – p) π bonding
involving filled N 2pz orbital and vacant Si 3dxy orbitals, 6L±16L 1
The large angles at O of disilyl ethers (R3Si)2O, is due both to
electronic and steric factors.

Figure 15.5
Carbides
Binary compounds of carbon are called carbides, SiC, CaC2, Al4C3 etc. These are of three types.

Ionic carbides
There are Three types of ionic carbides
(a)  Methanides
(b)  Acetylides
(c)  Propynide
Ionic carbides are decomposed by water (or dil. Acid) at room temperature. The liberated anions are also
immediately hydrolysed. It affords a method of classification.

(a) Methanides : (C–4 unit)

Those carbides which are hydrolysed to give CH4 are called methanide. They are supposed to contain C–4
unit.
Be2C + 4H2O   2Be(OH)2 + CH4
Al4C3 + 12H2O   4Al(OH)3 + 3CH4
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  357

(b) Acetylides : (C2–2 unit)

Those which are hydrolysed to C2H2 are called acetylides. They are common and formed by Group – 1,
Group – 2, Mg, Ca, Sr, Ba, Zn, Cd, Cu, Ag, Al and La metals.

Gr – 1
M2C2
Cu, Ag

Gr – 2
MC2
Zn, Cd

Al, La M2(C2)3

CaC2 + 2H2O   Ca(OH)2 + C2H2

Al2(C2)3 + 6H2O   2Al(OH)3 + 3C2H2

(c) Propynide : (C4–

3
unit)
Such carbides hydrolyse to propyne
Mg2C3 + H2O   2Mg(OH)2 + CH3 – C ≡ CH

Covalent carbides
Elements which compares with C in size and electronegativity form such carbides, Be, B, Si etc. Boron and
Si carbides are more important.

SiO2 + 2C ∆ Si + 2CO
High temp
Si + C SiC

Silicon carbide (SiC) is called carborundum. It is very inert and extremely hard.
High temp
B2O3 + C B4C
B4C is also very hard, infusible and inert. It is used to make bulletproof clothing.
These covalent carbides ( or α – Al2O3) are comparable in hardness to diamond (Moh’s scale)

Hardness   Diamond > B4C > SiC > α – Al2O3

Interstitial carbides
Transition metals form such carbides, in which C atoms occupy octahedral voids. Such materials are very
hard, electrically conducting and have very high mp. For example, TiC, ZrC. MoC, WC etc.

Oxides
Elements of this group form oxides of the type MO and MO2. Carbon forms suboxides also, e.g., C3O2.
358  Basic Concepts of Inorganic Chemistry

Table 15.7
Oxides C Si Ge Sn Pb

CO SnO PbO
MO X GeO
(neutral) ampoteric
MO2 CO2 SiO2 GeO2 SnO2 PbO2
  acidic  ampoteric

Carbon monoxide (CO)

CO is formed when carbon burns in limited O2 (or air).
2C + O ∆ 2CO
2

In laboratory, CO is prepared by heating formic acid, HCOOH (or oxalic acid) with conc. H2SO4.
Conc. H2SO4
HCOOH CO + (H2O. H2SO4)
∆
It is dehydration of HCOOH.
It forms many important gaseous mixtures for the industrial use.
(i) Water gas or synthesis gas CO + H2
(ii) Producer gas CO + N2
(iii) Coal gas CO + H2 + CH4 + CO2
• CO is a neutral oxide
• Carbon monoxide has a triple bonded C atom, one σ and two π bonds (best explained by MO model).
• It has highest bond energy (1070 KJmol–1) among diatomic molecules.
• CO is a weak Lewis base but forms stable aggregate with B2H6.
B2H6 + 2CO === 2OC   BH3
However, with BF3, it interacts only weakly.
BF3 + CO == F3B   CO
In this adduct, BF3 is found to be planar and B – C distance is very large 2.89Å. Such an adduct is often
called van der Waals molecule.
• CO, however, is a strong ligand towards transition metals and form variety of complexs known as carbonyls,
Ni(CO)4, Fe(CO)5 etc. They are stable due to synergic bonding (of organometallic compounds).
• CO is very toxic and rapidly forms a bright red complex with haemoglobin of blood. Thus
preventing haemoglobin to carry oxygen to cells, causing oxygen deficiency to unconsciousness and
then death.

Carbon dioxide (CO2)

It is produced when C burns in excess of O2 (or air).
C+O ∆ CO
2 2

Thermal decomposition of di-and trivalent (M+2 and M+3) metal carbonates gives CO2
CaCO ∆ CaO + CO
3 2
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  359

All metal carbonates give CO2 with dil. acid.

Na2CO3 + 2HCl    2NaCl + H2O + CO2
Mg CO3 + 2HCl    MgCl2 + H2O + CO2
• CO2 is on acidic oxide.
• It dissolves in water to form weakly acidic solution (carbonic acid).
H2O + CO2     [H2CO3]
Free acid is not stable enough to be isolated.
• Carbonic acid is a gem diol and is, therefore, unstable.
2+
2 &
2+

However, salts are known

0+&2  
2+ $FLGLFVDOW
2 & 0 *URU1+  
2+ 0  &2  
1RUPDOVDOW
Solid acidic salts, MHCO3, are known only of Gr–metals (not Li) and NH +4 ion.
• The CO3–2 ion is conjugate base of a weak acid. Therefore, hydrolyze in water to give basic solution.

CO3–2 + H2O    HCO3– + HO–

• CO2 is biologically important.
(i)  It maintains pH of blood, due to the equilibrium.
CO2 + H2O    HCO3– + H+
(ii)  It is the main component of photosynthesis.
Chlorophyll
6CO2 + 6H2O Sun light C6H12O6 + 6O2
(Glucose)

(iii)  The reverse process of the above takes place in the process of respiration.
C6H12O6 + 6O2     6CO2 + 6H2O + Energy
• CO2 is used in the synthesis of urea.

ǻ 1+  
&2  1+   +  1&2  1+  2 &+  2
$PPRQLXP 1+  
FDUEDPDWH 8UHD

• CO2 is also used in soft drinks.

• CO2 is gas at NTP and has the structure O == C == O. The (p – p)π bonding is very effective. Therefore,
even in solid state discrete CO2 molecules exist. The intermolecular forces are weak van der Waals’
force.
• Solid CO2 is called ‘ dry ice’ or ‘cardice’.
360  Basic Concepts of Inorganic Chemistry

  Silicon dioxide, SiO2, unlike CO2 is a solid. The (p – p)π bonding is not effective in SiO2 like CO2.
It is due to larger size of Si and more core electrons (8e) in Si. Therefore, to stabilize, SiO2 contains a
continuous lattice of Si and oxygen atoms joined by covalent bonds. Each Si is sp3 and is joined with
4 O – atoms and each O – atoms with two Si – atoms. A macromolecule is formed; hence, SiO2 is
a solid.

Suboxide (C3O2)
2 2
It is a foul smelling gas. It can be produced by dehydrating
malonic acid with P2O5 in vacuum at ~150°C. 2 6L 2 6L 2
&22+ 3 2 
&+  &  2  +  23  2   2 2
&22+
2 6L 2 6L 2
The molecule is linear, O == C == C == C == O, carbon
atoms are sp – hybridized. 2 2

Compounds with C – N bonds Figure 15.6

Cyanogens (CN)2
It is flammable gas, vary toxic and is water soluble. It can be prepared by the reactions
(i) Catalytic oxidation of HCN by NO2.
CaO – glass
2HCN + NO2 (CN)2 + NO + H2O

(ii) aq. phase oxidation of CN– by Cu2+

2Cu2+ + 4CN–     2CuCN + (CN)2

[Acidified S2O8–2 also oxidize CN– to (CN)2

(iii) Dry (CN)2 can be made by th reaction
Hg(CN)2 + HgCl2     Hg2Cl2 + (CN)2
• Cyanogen is similar in many ways to halogens, and is known as pseudohalogen. Like halogens it
disproportionate in basic solution.
(CN)2 + 2HO–     CN– + OCN– + H2O
• A mixture of O2 and (CN)2 (1 : 1) burns, producing one of the hottest flames (5050K) known from a
chemical reaction.
• The (CN)2 molecule is linear N ≡ C – C ≡ N (C atoms are sp – hybridized).

Hydrogen cyanide (HCN)

It is a covalent poisonous colourless gas. Liquid HCN (b.p.25.6°C) is highly associated molecule through
H – bonding (like H2O). Its dielectric constant is very high (107 at 25°C). It is a very weak acid in aq.
solution (pka = 9.1) but pure liquid is a strong acid.
B + HCN     BH+ + CN–
It can be prepared as:
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  361

(i) Small scale

NaCN + HCl     ↑ HCN + NaCl

(ii) Manufacture 
(a) Degussa process
1200oC
CH4 + NH3 HCN + 3H2
Pt.
(b) Andruso process
Pt/Rh catalyst
CH4 + 3O2 + NH3 2HCN + 6H2O
> 800oC

Hydrogen cyanide is thought to be a small +
1+  
molecule in the earth’s primeval atmosphere to 1
produce biologically important chemicals. It :DWHUWUDFH 1
is because under pressure with traces of water +&1
1+
and NH3, HCN pentamerizes to adenine, one
+LJK3DQG7 1
of the constituents of DNA. 1
DGHQLQH
Uses
(a) As a laboratory reagent. Figure 15.7
(b) To produce adiponitile NC – CH2 – CN
for Nylon
(c) To make NaCN and many cyanocomplexes.

Cyanides (CN–)
NaCN is very important, among the cyanides. It can be prepared as:
(a) NaOH + HCN     NaCN + H2O

(b) CaCN2 + C + Na2CO3 fuse CaCO3 + 2NaCN

~600oC
(c) NaNH2 + C NaCN + H2

General observation for the cyanides

• Cyanides of electropositive metals are water soluble. Example NaCN, KCN etc.
• Cyanides of Ag+, Hg+ and Pb+2 are very insoluble.
• Cyanide forms many stable complexes with transition metals, [Fe(CN)6]4–, [Mn(CN)6]4–, [Ni(CN)4]2–
etc.
• With respect to bonding it is similar to CO (synergic bonding).
• Cyanide is a π – acid ligand.
• The cyanide complex K4[Fe(CN)6] is analytically important, to dectect Fe3+ and Cu2+.
• Cyano complexes of Ag and Au are important in their extraction.
• Cyanide is similar to I– in reducing action
Cu2+ + 2I–     CuI + ½I2
Cu2+ + 2CN–     CuCN + ½ (CN)2
But CN is different from I– with respect to complexation.
–
362  Basic Concepts of Inorganic Chemistry

CuI + I–    X
CuCN + 3CN   –
  [Cu(CN)4]3–
• Cyanides are called pseudo halide.
• KCN is extremely toxic. Its toxicity is due to complexation with metals in enzymes and haemoglobin in
the body. Thus preventing normal body chemistry and quickly causing death.
• :
Cyanide is isoelectronic to N2 and has the structure [:N ≡ C ]−
• Cyanides are ambidentate i.e., it can bond through C (cyanide) or N (isocyanide).

Halides
Compounds containing C – F bond
The chlorofluorocarbons (Freons) are prepared by replacement of chlorine in a chloroalkane.
CHCl3 + 2HF     CHClF2 + 2HCl
2CCl4 + 3HF     CCl2F2 + CCl3F + 3HCl
The CFC are
• Odourless
• Inert
• Non-toxic
• Non-corrosive
They are used as:
• Refrigerant
• Propellant gas in aerosol spray
The CFCs are harmful as green house gas and can deplete O3 concentration.
CF2Cl2 Cl•
•
Cl
O3 O + ClO
The use of CFCs is banned in many countries (UK, USA)

Tetrafluoroethene (F2C = CF2)

It is made as follows:

2CHClF2 ~700 C F2C = CF2 + 2HCl

o

The C2F4 polymerizes to polytetrafluoroethene (PTFE).

P/NH4+/∆ __( F C – CF __
F2C = CF2 ) x
Persulphate 2 2
(PTFE)

It is
• Hard solid plastic
• Chemically inert
• Heat resistant (softening above 300°C)
• Electrical insulator
• Lowest coefficient of friction of any known substance which decreases with temperature.
• Polymer is used for coating frying pans (non-stick) and in non-lubricated bearings.
• It is also used as patch material in heart surgery.
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  363

Halides MX2 and MX4

Group – 14 elements form tetrahalides of the type MX4 (X = F, Cl, Br, I) except PbI4.
PbI4 does not exist due to strong oxidizing power of Pb+4 and reducing nature of I– ion. The Pb+4 is strong
oxidizing agent due to greater stability of Pb+2 (inert pair effect).
Thus, MX4, [M = C, Si, Ge, Sn, X = F, Cl, Br, I]
Germanium, Sn and Pb also for MX2. The stability of MX2 is maximum for Pb+2.
SnF2 is sparingly soluble in water and is used in fluoride containing tooth pastes.
The MX4 halides are all colourless except GeI4 and SnI4 which are bright orange solids. Colour in these
halides is due to charge transfer.
Sn +4 I¯ Ge +4 I¯
Silicon tetrahalides differ in physical state.
e e
SiF4 SiCl4 SiBr4 SiI4
Figure 15.8
Gas liq. liq solid

Fumes in air
All tetrachlorides except CCl4 are hydrolyzed by water.
Carbon tetrachloride is not hydrolyzed because:
(a) carbon in CCl4 is coordinatively saturated.
(b) C – Cl bond is less polar.
XC = 2.5, XCl = 3.0, Δχ = 0.5
Silicon tetra chloride (SiCl4) is extensively hydrolyzed. It is because:
(a) Si – Cl bond is more polar
XSi = 1.8, XCl = 3.0, Δχ = 1.2
(b) Si in SiCl4 can increase its coordination number by using 3d orbitals
The hydrolysis of SiCl4 can be represented as

&O &O&O

6L + 6L
2 &O &O
&O &O + ±+&O
2
&O
+ +

+ 2
6L2+&O  +&O
6L2+ 
   Figure 15.9
The tetra halides of Si, Ge, Sn and Pb can increase their coordination numbers by using d orbitals and
can form haloanions.
SiF4 + 2F–   SiF62–
SnCl4 + 2Cl   SnCl6–
The hexacoordinated halo anions are octahedral having sp3d2 hybridized central atom (Si)
364  Basic Concepts of Inorganic Chemistry

Hydrides
All elements of this group form covalent hydride.
Carbon forms a large number of chain and ring compounds due to high catenation property. They are:
Alkanes Cn H2n + 2
Alkenes CnH2n
Alkynes CnH2n – n
Cyclo alkanes and cycolalkynes
Aromatic hydrocarbons (C6H6)
Silicon (others also) form saturated hydrides only which are called silanes, SinH2n+2(Si ~8).
SiCl4 + LiAlH4     SiH4 + AlCl3 + LiCl
Silanes are much more reactive than alkanes due to partial positive charge at Si,
Cδ– – Hδ+ Siδ+ – Hδ–
Ge GenH2n+2 Germane (Ge ≈ 5)
Sn SnnH2n+2 Stannane (Sn ≈ 2)
Pb PbH4 Plumbane

Silicones
They are organosilicon polymers having empirical formula approximately R2SiO. Polymers are very stable
due to strong Si – O and Si – C bonds. Silicones can be prepared as oils, resins, plastics etc. They are:
• Inert
• Water repellent
• Heat resistant
• Electrical insulator
All these properties make silicones very useful.
Hydrolysis of alkyl chlorosilanes produces products having Si – OH bonds. They do not dehydrate like
gem diols (of C).
R Cl R OH R
Si + H 2O Si Si == O
Cl (—2HCl) R OH R
R

On the other hand, as soon as Si – OH bonds are formed, condensation sets in, and polymers (silicones)
are formed. By regulating the condition of the reations silicones of desired
(i) Chain lengths,
(ii) Ring sizes, and
(iii) Cross links can be produced.
+  & &O +  & 2+
6L +  2 6L +&O
+  & &O +  & 2+

&+  &+   &+   &+  

+ 2
6L  6L 6L 6L
+2 2+ +2 2+ 2 2 2
&+   &+   &+   &+  
 +  & &O +  & 2+
6L +  2 6L +&O
+  & &O +  & 2+
Group – 14 (IVA) C, Si, Ge, Sn, Pb  365

&+  &+   &+   &+  

+ 2
6L  6L 6L 6L
+2 2+ +2 2+ 2 2 2
&+   &+   &+   &+  
6LOLFRQH

Ring Polymer
&+   &+  

6L +  2 6L +&O

&O &O +2 +2
&O 2+

&+   &+  
&+   &+  
6L  6L
2 6L 2 6L 2
+2 2+ +2 2+
2+ 2+
  2 2
2+ 2+
+2 2+ +2 2+
2 6L 2 6L 2
6L 6L
&+   &+  
&+    &+  
6LOLFRQH

Carefully controlled hydrolysis produces rings of desired size,—three, four etc—Si atoms
2
&+   &+   &+   &+  
6L 6L 6L 2 6L
&+   &+   &+   &+  
2 2 2 2
&+   &+  
6L 6L 2 6L
&+   &+  
+  & &+  
7ULVF\FORGHPHWK\OVLOR[DQH 7HWUDNLV±F\FORGLPHWK\OVLOR[DQH

Uses
• As a protective coating.
• As lubricants.
• Oils as insulators in high voltage transformers.
• In silicone rubbers.
366  Basic Concepts of Inorganic Chemistry

Silicates
Silicates are solids having Si – O bonds. Most of the rocks and even soil contain silicates. Alkali metal
silicates are water soluble. They are made on a large scale as
~1500°C
Na2CO3 + SiO2 Na4SiO4,(Na2SiO3)n + CO2↑

They are used in detergents. The concentrated aq. solution of Na4SiO4 is solid like and as known as water
glass. Variety of silicates are found but in all the basic unit is the SiO4 tetrahedron.

2Ā

RU
6L

2Ā 2Ā
2Ā
Figure 15.10
Each O – atom carries one unit negative charge. In polymeric silicates SiO4 units share O – atom(s). It
provides a way of classification.

Orthosilicates (Mononuclear silicates)

These are silicates having discrete SiO44– ions. Metal ions are surrounded by O–atoms.

Table 15.8
Silicate Mn+ coordination no.
Phenacite Be2SiO4 4

Willemite Zn2SiO4 4

M2SiO4 (M+2, Mg+2, Mn+2, Fe2+) 6

Zircon ZrSiO4 8

Pyrosilicates (Si2O7–6)
When two SiO4 units share only one O – atom pyrosilicates, Si2O7–6, are formed. These are also discrete
units.
2Ā 2 2Ā
6L 6L
2Ā 2Ā
2Ā 2Ā

The Si – O – Si angle varies from 131 – 180°.

Thortevitite Sc2(Si2O7)
Hemimorphite Zn4(OH)2Si2O7
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  367

Chain silicates
(a) Pyroxenes
(b) Amphiboles
Pyroxenes are single strand infinite chains of composition (SiO 32 - )n. They are produced by sharing two O –
atoms of SiO4 units.

Ā
2 Ā
2 Ā
2

2 2 2 2
6L 6L 6L

2 2 2
Ā Ā Ā

  6SRGXPHQH Figure
 15.11
/L$O6L2    
  'LRSVLGH  &D0J6L2    
Spodumene

 LiAl(SiO3)2
:ROODVWRQLWH &D  6L2   
Diopside CaMg(SiO3)2
Wollastonite Ca3(SiO3)2

Amphiboles
They are double-strand cross-linked chains of composition (Si4O116– )n. In amphiboles some SiO4 share two
and others three O – atoms. Amphiboles always contain (HO) groups joined to the metal ions. Asbestos are
amphiboles.

Ā Ā
Ā Ā
Ā
Ā

Ā
Ā Ā

Ā Ā
Ā Ā
Figure 15.12
Tremolite, Ca2Mg5 (Si4O11)2(OH)2 is an amphibole.

Cyclic silicates
When two O – atoms of SiO4 tetrahedron are shared, a cyclic silicate is formed. They have general formula
SinO3n2n–.
Rings with three and six tetrahedra are common: Si3O96– and Si6O 12
18 . For example,
-
368  Basic Concepts of Inorganic Chemistry

Wollastonite Ca3(Si3O9)
Beryl Be3Al2(Si6O18)

Ā
Ā
Ā
Ā

Ā Ā
Ā Ā
Ā 6L  2  Ā Ā Ā
Ā   Ā
6L  2
Figure 15.13

Sheet silicate
When three O – atoms of SiO4 tetrahedra are shared infinite two-dimensional sheet is formed. Their general
formula is Si2O52–. Sheets are held together by weak forces. Sheets are bound together by metal ions in
between them.
Clays and Mica are sheet silicates.
Kaolinite Al2(OH)4(Si2O5)
Talk Mg3(OH)2(Si2O5)2

Three dimensional silicates

When all the four O – atoms of SiO4 units are shared, a three dimensional lattice is formed. Quartz (SiO2) is
an example of this class. The structure is a tetrahedral net work.

2 2
6L
2 6L 2 6L 2

RU 2 2
6L
6L 6L
2 6L 2 6L 2

2 2
6L

Figure 15.14

Isolation of Si
Occurrence: Silicon is found as,
(a) Silica – SiO2
(b) Silicates – These are of various types.
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  369

Silicon is mainly obtained from silica, SiO2.

(i) Si is isolated by heating SiO2 with high purity coke (or CaC2).
SiO2 + 2C D
fi Si + 2CO↑
(ii) Pure Si is made by reducing SiCl4 with Na or Mg.
SiO2 + 2C D
fi Si + 2CO↑
Si + 2Cl2 D
fi SiCl4
SiCl4 + 4Na D
fi Si + 4NaCl
Or, SiCl4 + Mg D
fi Si + 2MgCl2
(iii) Ultra pure Si for transistors or computer chips is prepared by zone–refining.

Practice Questions

A. Explain the following: B. Fill in the blanks

(a) Graphite is electrical conductor but (a) The hydrolysis of R3SiCl yields
diamond in an insulator. ____________________________.
(b) Si has diamond structure only but not an (b) The allotrope of carbon C60 is called
allotrope like graphite. _________________________.
(c) CCl4 is not hydrolysed but SiCl4 is rapidly (c) Photosynthesis is a reaction which is
hydrolyzed in water. followed with _________ ΔG.
(d) Silicon does not form R2Si = O like ketones (d) Tin(11) oxide [i.e., SnO] on dissolution in
(R2C = O). NaOH produces ___________.
(e) Catenation property. (Why does Si has (e) With an excess of SnCl2, HgCl2 gives
much less tendency to catenation than C). ___________________ precipitate due to
(f) HCN is a weak acid in water but in the pure the formation of ___________________.
state is a strong acid. (f) Chrome yellow is ___________________
(g) CO2 is gas but SiO2 is a solid. ___________________.
(h) SiF4 is incompletely hydrolyzed in water. (g) Pb3O4 is called ______________________
(i) R3Si – OH (silanol) is stronger acid than __________________.
R3C – OH. (h) The structure of SiC is like ___________.
(j) The single bond energies are as C > Si but (i) SiF4 is _________________________
N < P, O < S and F < Cl. hydrolyzed in water.
(k) CF4 is not a Lewis acid but SiF4 is a Lewis (j) SnI4 is __________stable and coloured due
acid. to__________________________.
(l) The first ionization energy of C is greater
than that of B but reverse is true for second C. What happen when
ionization energy. (a) Pb3O4 is treated with conc. HCl.
(m) Trisilylamine [(SiH3)3N] is a weaker base (b) Aluminium carbide is treated with water.
than (CH3)3N. (c) Dil HNO3 is slowly reacted with Sn.
(n) Diamond is hard but graphite is soft. (d) NaOH solution is added to SnCl2 solution.
(o) Carbon monoxide is not a good Lewis base (e) Carbon dioxide is passed in a suspension
for Fe3+. of lime stone (CaCO3) in water.
370  Basic Concepts of Inorganic Chemistry

(f) CO2 is passed through a concentrated aq. (i) AlCl3 solution is treated with NaHCO3.
solution of NaCl (brine) saturated with (j) Calcium carbide is strongly heated with
NH3. N2.
(g) Pb3O4 is treated with HNO3.
(h) CO2 is passed over heated potassium
superoxide (KO2).

Objective–Type Questions

  1. Synthesis gas is a mixture of   8. CO is absorbed by

(a) CO + N2 (b) CO + H2 (a) Pyrogallol (b) CHCl3
(c) CH4 + CO (d) CO2 + N2 (c) NH4OH + CuCl (d) CCl4
  2. Which of the following is true for CO?   9. Which of the following halide of C is used as
(a) Acid refrigerant?
(b) Base (a) CF4 (b) CCl4
(c) Doner (c) CH2F2 (d) CCl2F2
(d) Door and acceptor both. 10. Malonic acid is dehydrated over conc. H2SO4,
  3. The number and type of bonds between two the product is
carbon atoms in CaC2 are (a) CO (b) CO2
(a) One σ bond (c) C3O2 (d) CO3–2
(b) One σ and one π bond 11. Butter of Sn is
(c) One σ and two π bonds (a) SnCl2.2H2O (b) SnCl2.4H2O
(d) One σ and one and a half π bond. (c) SnCl4.5H2O (d) SnCl4.4H2O
  4. Which of the following is least stable and has 12. The basic unit in chain and cyclic silicates is
doubtful existence? (a) Si2O76– (b) (SiO3)n2n–
2n–
(a) PbI4 (b) SnI4 (c) (Si2O5)n (d) SiO44–
(c) GeI4 (d) CI4 13. Which of the following statements is correct for
  5. The material used in solar cells contain Gr – 14 elements?
(a) Ti (b) Sn (a) Atomic radius decreases
(c) Si (d) Cs (b) The hydroxides are getting less basic
  6. Which of the following is correct for glass? (c) The stability of +2 oxidation state
increases.
(a) Crystalline solid
(d) The first ionization energy increases.
(b) Covalent solid
14. Lead pencil contains
(c) Amorphous solid
(a) PbS (b) CuS
(d) Super cooled liquid
(c) Pb (d) Graphite
  7. The correct order of decreasing C – O bond
15. CO2 in water is an equilibrium system, CO2 +
length of CO, CO2 and CO3­–2
H2O H+ + HCO3– . Mark the correct
(a) CO2 > CO > CO3–2 statements.
(b) CO3–2 > CO2 > CO (i) It maintains pH of blood.
(c) CO2 > CO3–2 > CO (ii) CO2 lowers pH causing haemoglobin to
(d) CO > CO2 > CO3–2 release more O2.
 Group – 14 (IVA) C, Si, Ge, Sn, Pb  371

(iii) Carbonic acid is strong. 17. Which of the following elements forms only
(iv) Carbonic acid HCO3– system is not a one hydride?
buffer. (a) Si (b) Ge
(a) I, II (b) II, III (c) Sn (d) Pb
(c) III, IV (d) I, IV 18. Carbon is not used as a reducing agent in the
16. The common basic structural unit of asbestos, extraction of transition metals because
mica and quartz is (a) C is a weaker reducing agent
(a) SiO2 (b) C is converted into CO2 at high
(b) (SiO3)n2n– temperature
(c) SiO44– (c) C forms stable carbide.
(d) (Si2O5)nn– (d) None of these

Answers

1. (b) 2. (d) 3. (c) 4. (a) 5. (d) 6. (d) 7. (b) 8. (c) 9. (d) 10. (c)
11. (c) 12. (b) 13. (c) 14. (d) 15. (a) 16. (c) 17. (d) 18. (c)
16
Group – 15 (VA)
N, P, As, Sb, Bi

Elements of this group are called Pnicogens. (Greek, pnigmos-suffocation, many compounds of the group
elements have suffocating oduour, so this name). There is a transition from non-metal to metal.
Nitrogen and Bi do not show allotropy whereas P, As and Sb have allotropes.

Table 16.1
Property N P As Sb Bi

Physical Diatomic
Solid Solid Solid Solid
state gas, N2
Allotropic forms
Structure N≡N BCC

Allotropes – White (P4) As4 Sb4

Red (P4)x
Black P Black As and Sb

Note:
(i) Nitrogen is diatomic gas, N2 at NTP. It is due to very effective (p – p)π bonding in N2.
N 2s22p3 i.e., three unpaired electrons in p – orbitals. There are one σ and two π bonds in N2. Nitrogen
is sp–hybridized.

1 1 1{1

Figure 16.1
The σ bond is formed by linear overlap of sp – hybrids, and π bonds by side wise overlap of px – px and
py – py p – atomic orbitals. The lps are in sp type hybrids. The molecule is non–polar.
(ii) P is large in size. The (p – p)π bonding is not effective in P. Therefore, P is not stabilized as P2. In normal
conditions, phosphorous is P4 (white P). The P4 unit is tetrahedral. Each P is sp3 hybridized and is joined
with three other P atoms. The fourth sp3 orbital is occupied by a l.p. The structure is
 Group – 15 (VA) N, P, As, Sb, Bi  373

3
  G 3±3 c
3 3 ‘333  R 

3
Figure 16.2
The PPP angle in P4 is 60o. Therefore, there is large angle strain in P4, which makes it highly reactive (white
P inflames in air, so it is kept in water).

Allotropes of P
Phosphorous has three main allotropes:
(a) White phosphorous (P4)
(b) Red phosphorous (P4)X
(c)  Black phosphorous (layer structure)
• The white phosphorous, P4 is Td (explained above). It is highly reactive, inflames in air. So it is kept
under water.
• Red phosphorous is polymeric solid which has P4 units joined together.
3 3

3 3 3 3
3 3
Figure 16.3
• It is stable, less reactive (than P4) due to polymeric structure.
•  It is insoluble in organic solvents (CS2, CCl4 etc.).
250oC
•  P4 (CO + I ) Red P i.e., (P4)X
2 2

Black P
It has layer structure having hexagonal rings. The P – P – P angle ~ 100o i.e., it is almost a strainless structure.
The P – P distance is 2.20Å. It is most stable form and is inert.
(Hg/black P(little))
P4 High P/∆ Black – P

Table 16.2

General properties of group elements

Property N P As Sb Bi
Atomic no. 7 15 33 51 83
Electronic structure [He] [Ne] [Ar] [Kr] [Xe]
2s22p3 3s23p3 3d1o4s24p3 4d1o5s25p3 4f145d1o6s26p3
Atomic radius (Å) 0.70 1.10 1.21 1.41 1.52
Ionic radius (Å) 1.71 2.12 2.22 (As–3) 0.92 (Sb+3) 1.08 (Bi+3)
(N–3) (P–3)
(Continued)
374  Basic Concepts of Inorganic Chemistry

Property N P As Sb Bi
Electronegativity 3.07 2.06 2.0 1.82 1.67
m.p. (°C) 210 44.1 (P4) 841 (36 atm) 630 271
b.p. (°C) 195.8 280 615 1375 1560
(sublimes)
Ionization I 14.5 10.5 9.8 8.6 7.3
energy (ev)) II 29.6 19.7 – – –

Note:
(i) Nitrogen is generally trivalent and can expand its valence (or coordination number) only to a maximum
of four i.e., tetravalent.
:NH , :NF
3 3
Trivalent PH3, PCl3 Trivalent
NH
+
Tetravalent
4
PH4
+
Tetravalent
(ii) Phosphorous is tri and tetra valent as well as penta and hexavalent. PCl5 Pentavalent
The penta and hexavalency is achieved by P using its vacant
–
3d orbitals. PCl6 Hexavalent

V S G

3 *URXQGVWDWH

([FLWHGVWDWH

6S  GK\EULGRUELWDOV
3HQWDYDOHQW

Figure 16.4
P is hexavalent when a pentavalent P (PCl5) accepts a Lewis base
PCl5 + Cl– → PCl6– (P is sp3d2).
(iii) N cannot form NCl5 as N – has no d orbitals in its valence shell.

Oxidation state and nature of bond

Nitrogen shows oxidation states from –3 to +5 and forms stable compounds in all the oxidation states.
Table 16.3
Oxidation states Example
–3 NH3, NH4+
–2 NH2 – NH2 (hydrazine)
–1 H2N – OH (hydroxylamine)
0 N2
+1 N2O
+2 NO
+3 N2O3, HNO2
+4 NO2
+5 N2O5, HNO3
 Group – 15 (VA) N, P, As, Sb, Bi  375

Phosphorous shows following oxidation states only:  Table 16.4

(i) Nitrogen and P in their –3 oxidation states have noble Oxidation states Example
gas configuration. However, this change requires –3 PH3
large amount of energies (P–3, 1450KJmol–1). –2 P2H4
Therefore, ionic nitrides and phosphides are formed 0 P4
by a few metals, +1 H3PO2
Li3N → (Li+)3N–3 +3 P4O6, H3PO3
+5 P4O10, H3PO4
Mg3N2 → (Mg2+)3.(N–3)
Na3P → (Na+)3P–3
Zn3P2 → (ZN+2)3(P–3)2
(ii) Nitrogen and P have high ionisation energies. Therefore, nature of bonds in N and P compounds are
mostly covalent. Nitrogen achieve stable configuration in the following way:
(a)  By forming three single covalent bonds.

1 2FWHW 

(b)  Double and triple bonds.
N ≡ N, C ≡ N, C = N–, –N = N–
(c)  Tricovalent N (using lp) is a Lewis base,
:
H3N → H+ = [NH4]+
(iii) There are some stable compounds of N in which its valence shell is not complete. Example, NO, NO2.
These species have unpaired electrons and are paramagnetic.
(iv) P does not form many of the compounds like N. It is because P can not enter into (p – p)π bonding which
is very effective in the case of N.

Table 16.5
N P (species do not exist)
N2O P2O
N2O3 P2O3
N2O5 P2O5
–
NO2 PO2–
NO3– PO3–
N3– P3–
CN– PN–

(v)  The tri and penta oxides of P are actually dimeric P4O6 and P4O10.

Hydrides
All elements of this group form MH3 type hydrides. They are colourless, foul smelling, poisonous gases.
General characteristics of the hydrides vary as:
376  Basic Concepts of Inorganic Chemistry

(i)  Properties which decrease down the group

Table 16.6
Property NH3 PH3 AsH3 SbH3 BiH3

Decreases
Heat of formation (ΔHf)

M – H bond energy (KJmol–1) 391 322 247 255

Decreases
Thermal stability

Decreases
Donor property

Decreases
HMH bond angle

Water solubility NH3 water soluble (due to H – bonding)

others are insoluble

(ii)  Properties which increase down the group

Table 16.7
Property NH3 PH3 AsH3 SbH3 BiH3

Increases
Reducing power

Increases
Mp (oC)

Toxicity Increases

Note:
(i) Phosphine is a poor donor than NH3. It can be seen from their proton affinities,
NH3(g) + H+(g) = NH4+(g) ΔHo = 866KJmol–1
PH3(g) + H+(g) = PH4+(g) ΔHo = 770KJmol–1
That is, NH3 is a stronger base than PH3 
(ii) Structure of hydrides: NH3 is tetrahedral in structure and N in NH3 is sp3 hybridized. It is because N is
small in size and to reduce bp – bp resulsion it uses hybrid orbitals. Three sp3 orbitals form N – H bonds
and fourth sp3 orbital accommodates lp.

1 S+1+ |  
+
+

+
Figure 16.5
 Group – 15 (VA) N, P, As, Sb, Bi  377

Shape of NH3 is Δr pyramidal.

1 +
H – atoms are at the corners of an equilateral triangle and N – atom is
above that triangle.
The hydrides PH3, AsH3 and SbH3 have bond angles very near to 90o. +
+
Hydride PH3 AsH3 SbH3
Figure 16.6
LHMH ~ 93.5° ~ 92° ~ 91°

These angle suggest that pure p–orbitals (np3) are used for M – H 3 +
bonds by P, As and Sb. It is due to large size of P, As and Sb. The central
atoms are not sp3 hybridized. Therefore, lp in these MH3 molecules are +
present in s-type atomic orbital. This explains their poor donor ability. +
Therefore, PH3 is a much weaker base than NH3. The molecules are Δr Figure 16.7
pyramidal.

Important hydrides of N and P

Table 16.8
N P
Ammonia – NH3 Phosphine – PH3
Hydrazine NH2 – NH2 Diphosphine P2H4
Hydroxylamine H2N – OH (not stable)

Ammonia NH3
It can be prepared in many ways:
(i) Any ammonium salt on heating with alkali forms NH3.
NH Cl + NaOH ∆ NH + NaCl + H O
4 3 2

2NH4OOCCH3 + Ca(OH)2 → NH3 + Ca(CH3COO)2 + 2H2O

(ii) Ionic nitrides are hydrolyzed by water to produce NH3.
Mg3N2 + 3H2O 2NH3 + 3MgO
(iii) NH +4 – salts, which contain non-oxidizing anions, on heating gives NH3.

NH4Cl(s) ∆ NH3 + HCl

Non-oxidizing anions are Cl–, SO4–2, CO3–2, CH3COO–, PO 34- etc.

However, NH4+ salts which contain oxidizing anions forms N2 or N2O on heating.

NH4NO3(l) N2O + 2H2O

NH4NO2 N2 + 2H2O

(NH4)Cr2O7 N2 + Cr2O3 + 4H2O

(iv) NH3 is manufactured by
378  Basic Concepts of Inorganic Chemistry

(a)  Haber’s Process

High P
~ 450oC
N2(g) + 3H2(g) 2NH3(g)+Q
Fe (Fe2O3) Catalyst
Mo (Promotor)
(b)  Cyanamid Process
Electric furnace
CaC2 + N2 CaCN2 + C
(~11000C)
Nitrolim
Δ
CaCN2 + 3H2O ↓CaCO3 + 2NH3

Phosphine PH3
(i) When a mixture of white P (P4) and NaOH solution are heated, PH3 is formed.
P + 2NaOH + 3H O ∆ 3NaH PO + PH
4 2 2 2 3

In this reaction some P2H4 is also formed as side product. It is inflammable in air.
(ii) Ionic phosphides react with water to form PH3
Ca3P2 + 6H2O    3Ca(OH)2 + 2PH3
NH3 is highly soluble in water but PH3 is insoluble in water. Ammonia dissolves in water due to
H – bonding
+ 2 +
+
2 + 1 + 2 +
+
2 +
+ + +
Figure 16. 8
PH3 cannot form H – bond, so it is insoluble in water.

Oxides of N and P
Nitrogen forms stable oxides form +1 to +5 oxidation states whereas common P oxides are found in +3 and
+5 oxidation states only.
Nitrogen and P oxides

Table 16.9
Oxide Oxidation state of N/P Physical state Colour Magnetic property
N2O +1 Gas Colourless
Diamagnetic
NO +2 Gas Colourless
Paramagnetic
N2O3 +3 Solid Blue
Diamagnetic
NO2 +4 Gas Brown
Paramagnetic
N2O4 +4 Gas Colourless
Diamagnetic Diamagnetic
N2O5 +5 Gas Colourless
P4O6 +3 Solid Colourless Diamagnetic Diamagnetic
P4O10 +5 Solid Colourless
 Group – 15 (VA) N, P, As, Sb, Bi  379

The oxides of N can be prepared as:

Dinitrogen oxide (or nitrous oxide) N2O

It is obtained when a melt of NH4NO3 is heated (250 – 260oC)
NH NO ∆ N O + 2H O
4 3(l) 2 2

Nitric oxide (NO) is impurity in this preparation. It is removed by passing the gaseous mixture through FeSO4
solution; which absorbs NO.

Structure
It is iso electronic to CO2 and has linear structure. But unlike CO2 it has dipolemoment (0.16D). It shows
resonance
 
1 1 21 {12

   G 1±1  cG 1±2  c

Nitric oxide (NO)

•  Copper reacts with dil. HNO3 (8M) to form NO. It is reduction of NO3–.
8HNO3 + 3Cu     3Cu(NO3)2 + 4H2O + 2NO
•  Dry NO can be prepared by the reaction,
3KNO2(l) + KNO3(l) + Cr2O3(s)     2K2CrO4 + 4NO
•  Commercially, NO is obtained by catalytic oxidation of NH3 (Ostwald process for HNO3)
Pt catalyst
4NH3 + 5O2 ∆ 4NO + 6H2O
It is odd electron molecule (11 electrons) and is paramagnetic. Bonding in NO is best understood by
molecular orbital model. The MO configuration is
NO: σ12(σ1*)2(σ2)2(π)4(π*)1
Bond order = (8 – 3)/2 = 2.5
The N – O distance is 1.14Å which is intermediate between double and triple bond distances. The π*
electron is lost easily to give nitrosonium ion, NO+, which forms many salts.
– –
N2O3 + 3H2SO4     2NO + 3HSO4 + H3O . From solution NO HSO4 is isolable.
+ + +

Table 16.10
NO NO+
Electron configuration σ12(σ1*)2(σ2)2(π)4(π*)1 σ12(σ1*)2(σ2)2(π)4
Bond order 2.5 3.0
N – O distance (Å) 1.14 1.05
Magnetic property Paramagnetic μ = √3BM Diamagnetic
Stability NO+ > NO
380  Basic Concepts of Inorganic Chemistry

Nitric oxide is a good ligand and form variety of complexes with transition metal which are known as
nitrosyls, Na2[Fe(CN)5NO].

Dinitrogen trioxide N2O3

It can be obtained by mixing NO and NO2 in equimolar quantities at low temperature.
NO + NO2 {EQ 6}
In gaseous state it has the structure

2 2
1 1
2

Figure.16.9
The N – N distance is very large, 1.864Å.

Nitrogen dioxide NO2 (N2O4)

(i) Cu + conc. HNO ∆ NO2
3

Cu + 4HNO3 ∆ Cu(NO3)2 + 2H2O + 2NO2

(ii) Nitric oxide is oxidized easily to produce NO2
NO + ½ O ∆ NO
2 2

(iii) Di or trivalent metal nitrate decomposes on heating to NO2.

Pb(NO ) ∆ PbO + 2NO + ½ O
3 2 2 2

NO2 is an odd electron (17 electrons) molecule and is paramagnetic. It has the structure

1
S212a  
2 2 G 1±2 c

Figure 16.10
The unpaired electron ensures ready dimerization to a diamagnetic colourelss species N2O4 (dinitrogen
tetraoxide).
2NO2 N2O4
N2O4 is planar.

2 2
1 1
2 2
    G 1±1  c
    G 1±2 c

Figure 16.11
 Group – 15 (VA) N, P, As, Sb, Bi  381

Nitrogen pentaoxide N2O5

It is obtained by dehydration of HNO3 by P2O5.
2HNO + P O ∆ 2HPO + N O
3 2 5 3 2 5

N2O5 is solid and in this state it is NO . NO 3- i.e., nitronium nitrate. In gaseous state it has the
2+

structure,

2 2
1 2 1
2 2
Figure 16. 12
In anhydrous H2SO4 (or HNO3 or H3PO4) it produces NO2+.
N2O5 + 3H2SO4 ≡ 2NO2+ + 3HSO4– + H3O+
Therefore, this mixture is often used for anhydrous nitration of benzene
12  
&&O 1 2 + 62 

Figure 16. 13
P – oxides P4O6 and P4O10
Stream of air
(P4)X P4O6
6000C

Excess air or O2
P4 P4O10
Δ
These oxides are solids.
They differ from N oxides in stoichiometry and structure. It is due to inability of P to form (p – p)π bonds.
P4O6 and P4O10 both have cage structure. The structures are based upon P4 tetrahedra.

P4O6
In this oxide P – atoms form a regular tetrahedron and O – atoms are present at six edges of the tetrahedron
and bridge P – atoms.
3
2 2
2

3
2 3

2 3 2

Figure 16. 14
All O – atoms are equivalent and P – O distance is 1.64Å.
382  Basic Concepts of Inorganic Chemistry

P4O10
In this oxide P4 tetrahedron has six edge–bridging O – atoms and four terminal O – atoms. The terminal P – O
bonds have (d – p)π bonding. Therefore, there are two types of P – O distances in P4O10 large bridging P – O
and small terminal P – O distances.
2

3
2 2
2
2
2 3 2 3 2 3
3
2 2
2 G±S ʌERQGLQJLQ3 2  

Figure 16. 15
dP–O (bridging) = 1.604Å
dP–O (terminal) = 1.429Å
Oxy acids of N
+3 nitrous acid HNO2
+5 nitric acid HNO3

Nitrous acid (HNO2)

It is a weak acid (pKa = 3.3, Ka = 4.5 x 10–4) and the pure liquid acid is unknown.
Cold metal nitrite solution when treated with dil. acid (HCl) HNO2 is fomed.
0 – 58C
HCl + NaNO2 HNO2 + NaCl
Salt free acid can be prepared by the reaction.
Ba(NO2)2 + H2SO4   2HNO2 + BaSO4↓
In gaseous state it decomposes as
Δ
2HNO2 NO + NO2 + H2O
In aq. solution it decomposes on heating as
Δ
3HNO2 H3O+ + NO3– + 2NO

HNO2 as oxidizing and reducing agent

Nitrogen in HNO2 is in +3 oxidation state which is intermediate for nitrogen. This oxidation state can decrease
as well as increase. Therefore, HNO2 is oxidizing and reducing agents both.
NO2– + e + 2H+     NO + H2O Oxidizing agent
It oxidizes
Fe2+     Fe
3+
 Group – 15 (VA) N, P, As, Sb, Bi  383

I–     I2
Sn+2     Sn
+4

C2O4–2     CO2
Fe2+     Fe +e
3+

NO2– + e + 2H+     NO + H2O

Fe2+ + NO2– + 2H+     Fe + NO + H2O
3+

HNO2 as reducing agent

NO2– + H2O   –
  NO3 + 2e + 2H
+
Reducing agent
It reduces
MnO4– to Mn+2
Cl2 to Cl–
Nitrites are very toxic. But is used for preservation of ham and other meat products. It is because NO2–
decomposes into NO, forms red colour with haemoglobin and so improves the colour of meat.
But during cooking NO2– (or NO) react with protein to form carcinogenic nitrosoamines (R2N → NO).
Also, nitrite inhibit the growth of clostridium botulinum which may cause food poisoning. Thus, nitrite is a
toxic substance.

Structure of NO2– ion

It is trigonal planar in structure but angular in shape. Nitrogen atom in NO -2 is sp2 hybridized.

∠ONO ≈ 1158C
N
dN–O = 1.1Å

O O

Figure 16. 16
Nitric acid (HNO3)
Pure HNO3 is a colourless covalent compound. It has no action on metal and carbonates. But in aq.
solution it is a strong monoprotic acid (ionizes 100%). It is oxidizing agent and oxidizing power
increases with concentration. Solution or conc. acid looks yellowish. It is because of its decomposition to
produce NO2.
4HNO3     4NO2 + O2 + 2H2O
(Brown)

The acid can be prepared by heating a metal nitrate with conc. H2SO4.
Δ –Δ
2NaNO3 + H2SO4 Na2SO4 + 2HNO3(vap) HNO3(l)
384  Basic Concepts of Inorganic Chemistry

Methods of Manufacture
(i)  Birkeland – Eyde process
Electric
Electric 2 O O2 H2HO/O
2O/O
2 2
N2N+2 +O2O2 spark
spark 2NO(OXD
2NO 2NO
) )2NO2 2
(OXD
HNO
HNO3 3

This method is obsolete.

(ii)  Ostwald process

This method uses NH3 for HNO3.
PtPt catalyst
catalyst
4NH
4NH 3+
3+ 5O5O2 2 5 atoms
4NO+ +6H
4NO 6H
2O2O
5 atoms
0 0
800
800 CC

NO is oxidized by O2 to NO2 and NO2 is dissolved in water counter current to give HNO3.
2NO + O2   2NO2

3NO2 + H2O   2HNO3 + NO

NO is recycled in oxidation chamber. This process produces ~ 60% HNO3 by wt. Further distillation
gives only upto ~ 68% acid (a constant boiling mixture is formed).
Very concentrated acid is produced as
(i) Dehydrating HNO3 with conc. H2SO4.
(ii) Mixing the acid with a 72% Mg(NO3)2 solution followed with distillation.

Reactions
This is an oxidizing agent and reacts with metals, non–metals, and other chemical substances.
(i) HNO3 + Non-metals
•  dil. HNO3 has no action on any non-metal.
•  Even conc. HNO3 has no action on N2, O2, F2, Cl2 and Br2.
•  Conc. HNO3 reacts with B, C, P, S and iodine. The reaction is

Conc. HNO3 + B → H3BO3 C gives CO2

C → CO2 because carbonic
P → H3PO4 acid (H2CO3) is
S → H2SO4 not stable.
NO2 I → HIO3

The reactions can be written as:

[2HNO3     N2O5 + H2O] x 3 (I)

[N2O5     2NO2 + O] x 2 (II)

[C + 2O     CO2] (III)

C + 4HNO3     2NO2 + 2H2O + CO2
 Group – 15 (VA) N, P, As, Sb, Bi  385

First two steps (I and II) are common to all reactions.

[2HNO3     N2O5 + H2O] x 3 (I)
[N2O5     2NO2 + O] x 2 (II)
[S + 3O     SO3] (III)
[SO3 + H2O     H2SO4]

S + 6HNO3     H2SO4 +6NO2 + 2H2O
(ii)
HNO3 + Metal
Reaction product depends on conc. of HNO3, temperature and nature of the metal.
•  Gold does not react even with conc. HNO3.
•  Relatively noble metals Cu, Ag etc form NO with dil. and NO2 with conc. HNO3 (metal forms
nitrate)
•  Reactive metals Fe, Zn, Sn, Mn, Mg etc., react as:

HNO3 Very dilute N2O

Dil. NO
Conc. NO2 + M – nitreate
Vap N2
< 1M acid NH4+

•  Very dil HNO3 forms H2 with Mg and Mn

Mn + 2HNO3     H2 + Mn(NO3)2
(iii) Devarda’s alloy (Cu/Al/Zn) with NaOH reduces NO 3- to NH3. This reaction is quantitative and may be
used for the estimation of nitrate.
Alloy + NaOH     [H]
HNO3 + [8H]     NH3 + 3H2O

Aquaregia
A mixture of conc. HCl and HNO3 in the ratio 3 : 1 is called aquaregia. This is a powerful oxidizing agent and
dissolves metals like Au and Pt. The two acids on mixing react as
3HCl + HNO3     NOCl + 2Cl + H2O
The presence of NOCl and Cl makes aquaregia a powerful oxidizing agent.
Au + 3Cl     AuCl3
AuCl3 + Cl–   –
  AuCl4 (or HAuCl4, chloroauric acid)
Pt + 4Cl     PtCl4
PtCl4 + 2Cl–   2–
  PtCl6 ( or H2PtCl6, Chloroplatinic acid)
It is the high conc. of Cl– which further stabilizes the product (AuCl3 or PtCl4).
386  Basic Concepts of Inorganic Chemistry

Oxy acids of P
The common oxy acids of P are:

Table 16.11
Oxidation Name Formula Proticity Structure
state of P
Hypophosphorous acid
+1 H3PO2 1 Td.
(phosphinic acid)
+3 Phosphorous acid H3PO3 2 Td.
+5 Metaphosphoric acid (HPO3)n 1 Td. Polymeric and contain PO4 Td. units
Td.
+5 Orthophosphoric acid H3PO4 3
Highly hydrogen bonded
+5 Pyrophosphoric acid H4P2O7 4 Td. (two tetrahedra joined through
O – atom)

Note:
(i) In H3PO2 two H – atoms are directly linked with P i.e., PH2(O)OH. So it is monoprotic (OH ionizes)
(ii) In H3PO3 there is only one P – H linking PH(O)(OH)2 i.e., diprotic.
(iii) Metaphosphates have polymeric structure chain like as well as cyclic, (PO3)nn–.

Hypophosphorous acid H3PO2 [H2PO(OH)]

It can be prepared by heating white P with Ba(OH)2 and then treating the reaction mixture with dil. H2SO4 to
ppt. out BaSO4.
2P4 + 3Ba(OH)2 + 6H2O     PH3 + 3Ba(H2PO2)2
3Ba(H2PO2) + 3H2SO4     6H3PO2 + 3BaSO4↓
The solution crystallizes to H3PO2.
It is a reducing agent due to P – H bonds.
4AgNO3 + H3PO2 + 2H2O     4Ag + H3PO4 + 4HNO3

Structure

3
H3PO2 is Td, 2+
P is sp3 hybridized. +
+
Figure 16.17
Phosphorous acid H3PO3 [HPO(OH)2]
It is a diprotic acid i.e., has two OH groups and third hydrogen is directly linked to P i.e a P – H bond.
It can be prepared as:
(i) By dissolving P4O6 in water (P4O6 is anhydride of H3PO3).
P4O6 + 6H2O     4H3PO3
 Group – 15 (VA) N, P, As, Sb, Bi  387

(ii) By the hydrolysis of PCl3 with water

PCl3 + 3H2O     H3PO3 + 3HCl
The sols on crystallization give white crystals of H3PO3.
•  H3PO3 disproportionate on heating.
4H3PO3     3H3PO4 + PH3
•  It is reducing agent due to P – H bond.
H2O + 2AgNO3 + H3PO3     2Ag + 2HNO3 + H3PO4
2HgCl2 + H3PO3 + H2O     Hg2Cl2 + 2HCl + H3PO4

Structure
3
H3PO3 is Td, P is sp3 hybridized. 2+
+
Phosphoric acids 2+
Orthophosphoric acid H3PO4 Figure 16.18
Metaphosphoric acid (HPO3)n
Pyrophosphoric acid H4P2O7
These all can be obtained by controlled hydration of P4O10 (P – pentaoxide).

Small amount A little Water

P4O10 water (HPO 3 )n more water H4P2O7 (excess) H3PO4
Meta acid Pyro acid Ortho acid

The reverse process takes place when H3PO4 is heated

~2200C ~3200C high

H3PO4 H4P2O7 (HPO3)n P4O10
temp.

The pure H3PO4 is manufactured by furnance process.

The molten P is burnt in a furnance with air and steam which produces H3PO4
P4 + 5O2     P4O10
P4O10 + 6H2O     4H3PO4

•   It is solid but is highly hygroscopic and changes into solution by absorbing water.
•  It is a tribasic acid.
H3PO4 ≡ H+ + H2PO4– K1
– –2
H2PO4 ≡ H + H2PO4
+
K2
– –3
HPO4 ≡ H+ + H2PO4 K3

K3 < K2 < K1 (K = ionization constants)

•  H3PO4 forms three types of salts.
NaH2PO4 (acid salt) Primary (or 1o) phosphate
388  Basic Concepts of Inorganic Chemistry

NaH2PO4 (acid salt) secondary (or 2o) phosphate

Na3PO4 (normal salt) Tertiary (or 3o) phosphate
These salts behave differently on heating.
+  32  
1D2+
5HSODFHPHQWRI+  E\1D  

1D+  32   1D  +32   1D  32  
        
ǻ+  2 ǻ+  2 ǻ

1D32   1D  3  2   ;
0HWDSKRVSKDWH 3\URSKRVSKDWH

Figure 16.19
Dehydration of 1o and 2o phosphates takes place because of the presence of H atoms in the salts. The 3o salts
do not dehydrate, as it has no H.
•  In aq. solution H3PO4 is extensively H – bonded.

2 + 2 +
+
2 3 2 + 2 +
+
2 +
2 + +
Figure 16. 20
The H – bonding makes concentrated H3PO4 syrupy and viscous.
Metaphosphoric acid is polymeric. Linear and cyclic polymeric structures are found.

/LQHDUFKDLQ
2 2 2

 2 2
 2 3 3 3 2
32  Ā

 2 2 2
± ± ±

Figure 16.21
The most common cyclic ones are cyclotrimetaphosphates (P3O9–3) and cyclotetrametaphosphates
(P4O124–)
 Group – 15 (VA) N, P, As, Sb, Bi  389

±
± 2
2 2 2 2 2
2
3 3 2
3 3 ±
2 2 2
2 ±
2 2

3 3 3
2
± 2 2
2 2
2 2 ±
±
&\FORWULPHWDSKRVSKDWH &\FORWHWUDPHWDSKRVSKDWH
3  2   Ā 3  2   Ā
Figure 16. 22
There are two types of P – O bonds,

(i) The ring and terminal bonds.

(ii) The terminal O – atoms are equivalent due to resonance.

Acid strength of H3PO2 , H3PO3, and H3PO4

H3PO2 H3PO2, H3PO4
H2PO(OH) HPO(OH)2 PO(OH)3
All have only one free O – atom, so seems similar in acid strength
H3PO2 ~ H3PO3 ~ H3PO4
But there is difference in acid strength.

Table 16. 12
H3PO2 H3PO3 H3PO4

Conjugate base H2PO2– HPO3–2 PO4–3

Negative charge per O – atom –1/2 = 0.5 –2/3 = 0.66 –3/4 = 0.75

When negative charge per O – atom is high, the anion has larger attraction for H+. The acid ionizes less
and is weak and vice versa. Thus, decreasing order of acid strength is,
H3PO2 > H3PO3 > H3PO4
pKa 1.2 1.8 2.15

Halides
Two series of halides are formed by the elements of this group. The MX3 and MX5 halides. Nitrogen forms
only NX3 type halides. It is due to the fact that N does not have suitable d – orbital in its valence shell. The
other elements P, As and Sb form MX3 and MX5 halides both. MX5 halides are formed due to the presence of
d – orbitals in the valence shell. Bismuth forms only BiX3 halides. (The +3 state is stable for Bi due to inert
pair effect).
390  Basic Concepts of Inorganic Chemistry

Tihalides MX3
Properties of MX3

Table 16. 13
Property N P As Sb Bi
Increases
Stability

Increases
Ionic nature of bond

Increases
mp

Increases
bp

Decreases
Hydrolysis tendency

N Trihalides

Table 16. 14
Property NF3 NCl3 NBr3 NI3
Physical state Gas Liquid Unstable

Structure Td Td -- --

Stability Very stable Explosive -- --

Reactivity Unaffected by water Readily hydrolyzed -- --

P Trihalides
Table 16. 15
Property PF3 PCl3 PBr3 PI3
Physical state Gas Liquid Liquid Solid
Pyramidal
Structure

Decreases
Stability

Increases
Bond angle

Reactivity towards water All hydrolyzed by water rapidly

The trichorides hydrolyze by water.

NCl3, PCl3     Completely
AsCl3     Like NCl3 and PCl3
 Group – 15 (VA) N, P, As, Sb, Bi  391

SbCl3     Partially
BiCl3     Partially
NCl3 + 3H2O     NH3 + 3HOCl
PCl3 + 3H2O     H3PO3 + 3HCl
AsCl3 + 3H2O     H3AsO3 + 3HCl
The SbCl3 and BiCl3 are hydrolyzed to oxy salts.
MCl3 + H2O     MOCl + 2HCl (M = Sb, Bi)
The NCl3 is hydrolyzed to a base (NH3) whereas PCl3 is hydrolysed to an acid (H3PO3). It is due to the
fact that NCl3 is an electron pair donor but PCl3 is an acceptor as P has vacant 3d orbitals.

&O &O
&O &O &O
1 1 &O
+  2
&O  1++2&O 1+  +2&O
$PPRQLDEDVH
2 + 2
+ + +

 Figure 16. 23

&O &O &O &O &O

3 3 &O &O
3 2++&O
&O
2 +
2 ZDWH U
+ + +
32+  +&O

7DXWRPH ULVDWLRQ

+322+  
3KRVSKRURXVDFLG
Figure 16. 24
Pentahalides of P
The pentahalides of P are PX5. In this group of compounds P has more than eight electrons around it. It is
valence expansion of P by the use of vacant d orbitals present in phosphorus.
392  Basic Concepts of Inorganic Chemistry

Table 16. 16
PF5 PCl5 PBr5 PI5
Physical state Gas Liquid Solid Solid
Structure (gas) tbp Tbp Not well known and
Present as PBr +4 Br− appears to be PI+4I–
Stability Decreases

Reactivity (towards H2O) Increases


The PF5 is tbp in gas, liquid and solid states. However, PCl5 gas or )
liquid is tbp but it crystallizes to form [PCl4]+ [PCl6]–. In this change, PCl5 )
is a Cl– ion donar as well as Cl– acceptor.
2PCl5   – 3
  PCl4 PCl6
+
)
The ions PCl4+ and PCl6– are Td and octahedral respectively. )
PCl5 is widely used to prepare chloroderivatives of RCOOH and R – OH.
)
4R – COOH + PCl5     4R – COCl + H3PO4 + HCl Figure 16. 25
4R – OH + PCl5     R – Cl + H3PO4 + HCl
It also replaces –OH from H2SO4.
PCl5 + H2SO4     ClSO2OH + POCl3 + HCl
Chlorosulphonic
acid
PCl5 + ClSO2OH → ClSO2Cl + POCl3 + HCl
Sulphuryl
Chloride
PCl3 and PCl5 both react with P4O10 to produce phosphoryl chloride.
6PCl3 + 6Cl2 + P4O10     10POCl3
6PCl5 + P4O10     10POCl3
PCl5 is hydrolyzed by water to H3PO4.
PCl5 + 4H2O     H3SO4 + 5HCl

Isolation of N and P
Nitrogen occurs in nature mainly as N2, (~78% by volume of the earth’s atmosphere). It is also found as
nitrates. NH4+ compounds and organic compounds.

N2 in laboratory
A mixture of NH4Cl and NaNO2 is heated to prepare N2 in laboratory.
Δ
NaNO2 + NH4Cl NH4NO2 + NaCl
Δ
NH4NO2 + NH4Cl Δ N2 + NaCl + 2H2O
 Group – 15 (VA) N, P, As, Sb, Bi  393

Ammonium nitrite is an explosive so it is not heated alone.

Pure N2
It can be prepared by heating NaN3 or (NH4)2Cr2O7
Δ
2NaN3 2Na + 3N2
Δ
(NH4)2Cr2O7 N2 + Cr2O3(s) + 4H2O

Manufacture of N2
It is prepared in large scale by liquefaction and fractional distillation of liquid air. It is because N2 and O2
differ in their bps (N2 bp – 196oC, O2, – 183oC)

CO2 High P/ –Δ Liquid air Fractional

N2↑
free air (N2 + O2) distillation

Isolation of P
Phosphorus occurs mainly as Ca3(PO4)2 in
(a) Phosphorite Ca3(PO4)2
(b) Fluorapatite 3Ca3(PO4)2CaF2
(c) Chlorapatite 3Ca3(PO4)2.CaCl2
P is obtained by the reduction of phosphate rock [Ca3(PO4)2] with SiO2 and coke in an electric furnance.

2Ca3(PO4)2 + 6SiO 6CaSiO3 + P4O10

(Slag)
P4O10 + 10C P(vap) + 10CO
–Δ

P4 (white)
White phosphorus is inflammable in air. So, it is kept under water.

Fertilizers
The substance, which increases the fertility of soil, is known as fertilizer. Chemical fertilizers are substances
which provide essential nutrients to plants. Among various essential elements N, P and K are most vital.
Therefore, nitrogenous, phosphatic and potash fertilizers are most common. Those fertilizers which provide
all the three are called NPK or mixed or complete fertilizers.

Essential qualities of a good fertilizer

(i) The fertilizer should be water soluble so that assimilated by the plants easily.
(ii) It should provide essential nutrients over a long period.
(iii) It should not be heat producing with soil; otherwise the plants will be damaged.
(iv) It must be basic, as slightly alkaline soil is essential for the proper growth of plants (any soil above pH
– 10 and below pH – 3 becomes sterile).
(v) It should keep the soil loose.
(vi) It should be dry and finely powdered for uniform distribution.
394  Basic Concepts of Inorganic Chemistry

Nitrogenous fertilizers
1. Ammonium Sulphate (NH4)2SO4
Aquous suspension of gypsum is saturated with NH3 gas and then CO2 gas is passed. It produces
(NH4)2SO4.
2NH3 + H2O + CO2   (NH4)2CO3
CaSO4 + (NH4)2CO3   (NH4)2SO4 + CaSO3↓
Solid CaCO3 is filtered out. The solution on evaporation under vacuum and cooling gives crystals of
(NH4)2SO4.
Fertilizer action
Basic compound Nitrifying
(NH4)2SO4 in soil NH3 Bacteria Nitrate (used by plants)

2.  Calcium cyanamide (CaCN2)
It is prepared by heating a mixture of CaC2 and N2 gas at high temperature (~1100°C).
Δ
CaC 2 + N 2 CaCN 2 + C

Nitrolum
 When added to soil it decomposes to CaCO3 and NH3. Ammonia is then converted into nitrate, which
is used by plants. It is a slow acting substance.

3.  Calcium ammonium nitrate (CAN, Ca(NO3)2, NH4NO3)

Manufacture of this fertilizer uses N2 from air and H2 from water. NH3 is produced by Haber’s process
and HNO3 from NH3 by Ostwald process.
)UDFWLRQDO
$LU HYDSRUDWLRQ 1 
+DEHU¶V 2VWZDOG
1+   +12  
(OHFWURO\VLV SURFHVV SURFHVV
:DWHU + 
Figure 16. 26
Nitric acid is finally neutralized by powdered lime stone (CaCO3) and NH3 to get the fertilizer CAN.
2HNO3 + CaCO3     Ca(NO3)2 + CO2 + H2O
HNO3 + NH3     NH4NO3
CAN     NH4NO3.Ca(NO3)2
The pellets of CAN are coated with calcium silicate (soapstone) to protect them from moisture.
1+ 
4.  Urea 2 &
1+  
 
It is manufactured by heating a mixture of CO2 and NH3 at high pressure (~200 atm).
Δ
2NH3 + CO2 H2N – COONH4
Ammonium carbamate
 Group – 15 (VA) N, P, As, Sb, Bi  395

Δ
H2N – COONH4 (~25 atm) H2N.CO.NH2 + H2O
Urea
It is most commonly used fertilizer and is preferred over (NH4)2SO4 and CAN. The latter ones make soil
acidic (NH4+ + H2O     NH3 + H3O ) which is bad.
+

Phospatic fertilizers
1. Calcium superphosphate or Super phosphate of lime
[Ca(H2PO4)2H2O.2CaSO4.2H2O]
(a)  From phosphonte
It is prepared by treating phosphonte or bone ash with calculated quantity of H2SO4 (~70%).
Ca3(PO4)2+ 2H2SO4 + 5H2O     Ca(H2PO4)2. H2O + 2CaSO4.2H2O
It has undesirable CaSO4 (insoluble).
(b)  From fluorapatite[3Ca3(PO4)2.CaF2]
Fluorapatite on reaction with calculated amount of H2SO4 gives calcium superphospate

3Ca(PO4)2.CaF2 + 7H2SO4     3Ca(H2PO4)2 + 7CaSO4 + 2HF

2.  Triple superphosphate 3Ca(H2PO4)2

(a) From phoshorite
It is manufactured by the action of orthophosphoric acid on phosphorite rock.
Ca3(PO4)2 + 4H3PO4     3Ca(H2PO4)2
(b) From fluorapatite [3Ca3(PO4)2.CaF2]
3Ca3(PO4)2.CaF2 + 14H3PO4     10Ca(H2PO4)2 + 2HF

3.  Calcium superphosphate nitrate or nitrophosphate Ca(H2PO4)2+2Ca(NO3)2

It is manufactured by the action of HNO3 on phosphorite rock
Ca3(PO4)2 + 4HNO3     Ca(H2PO4)2 + 2Ca(NO3)2
It is better as N and P both are present.

4.  Phosphatic slag or Thomas slag

It is the byproduct of steel industry. When iron ore is blasted with limestone, calcium phosphate and Ca
silicate are produced as slag. This is cooled and finally powdered and used as fertilizer.
P4 + 5O2     P4O10
6CaO + P4O10     2Ca3(PO4)2
CaO + SiO2     CaSiO3
Potash fertilizers
Potassium is essential for growth of plants. It also helps uptake of other nutrients. Potassium chloride, KNO3
and K2SO4 are used as fertilizers.
396  Basic Concepts of Inorganic Chemistry

Practice Questions

A. Account for the following: (v) Why is pure phosphoric acid syrupy?
(a) Nitrogen is gaseous N2 whereas phosphorus (vi) The N – N bond energy (~160 KJmol–1) in
is P4, solid. NH2 – NH2 is much less than C – C bond
(b) Phosphorus exists in allotropic forms but energy (350KJmol–1) in CH3 – CH3.
not nitrogen. B. Write equations for effect of heat on:
(c) Nitrogen forms only NCl3 but P forms PCl3 (a) NH4NO3 (b) NaNO3
and PCl5 both.
(c) Cu(NO3)2.XH2O (d) NH4NO2
(d) NH3 is stronger base than PH3.
(e) NaN3 (f) NaH2PO4
(e) Bond angle in NH3 (~107o) is much larger
than in PH3 (~93o). (g) (NH4)2Cr2O7 (h) (NH4)2CO3
(f) NH3 is soluble in water but PH3 is (i) (NH4)2C2O4
insoluble. C. Write balanced equations when water reacts
(g) The hydrolysis of NCl3 gives a base (NH3) with the following:
whereas PCl3 gives an acid (H3PO3). (a) NCl3 (b) PCl3
(h) The b.pt. of NH3 is greater than PH3 (c) CaCN2 (d) AlN
although molecular wt. of PH3 is high.
(e) Li3N (f) NO2
(i) Red P is less reactive than white P.
(g) P4O10 with little water
(j) Iron reacts very slowly with conc. HNO3.
D. Complete the following writing balanced
(k) Coloured paramagnetic NO2 dimerizes
equations.
readily to colourless diamagnetic N2O4.
(l) H3PO2 is monoprotic acid. (a) KNO2(l) + KNO3(l) + Cr2O3(s)    
(m) The P – O bond length in POCl3 is short _______ +________.
(1.45Å) compared to the sum of the single (b) NH4NO3(s)     _____+ _____.
bond covalent radii of P and O (1.83Å).
(c) NH4NO3(l)     _____ + _______.
(n) There are two types of P – O bond distances
in P4O10. (d) I. N
 H3 + NaOCl     _______ +
__________.
(o) NF3 is not a Lewis base for BF3 but F3N –
O is stable compound. II. NH3 + H2N – Cl + NaOH  
(p) The oxyacids of N and P in their +5   ________+ _________.
oxidation state differ in formula (N → (e) HNO3 + P4O10     __­___ +
HNO3, P → H3PO4). _____.
(q) On gentle heating HNO3 give NO2 but (f) N2O5 + HClO4  
H3PO4 gives a condensation product   _________+
_________.
pyrophosphoric acid, H4P2O7.
(g) I. [Fe(H2O)6]2+ +NO3¯+H+   
(r) NaH2PO4 on heating gives sodium meta-
phosphate but Na3PO4 resist temperature. [Fe(H2O)6]+3+____ + _____ +H2O.
(s) Nitric oxide, though an odd electron II. [Fe(H2O)6]2+ + _________ 
molecule, is diamagnetic in liquid state.  
__________ + H2O.
(t) The experimentally determined N – F bond
length in NF3 is greater than the sum of the (h) NO + SO2 + H2O     ____+ ___.
single bond covalent radii of N and F. (i) P4 + conc. HNO3     ________ +
(u) Mg3N2 hydrolyzed to NH3 but HCl is not _______ + _________.
obtained from MgCl2 on reaction with (j) CaC2 + N2     ________ +
water at room temperature. ________.
 Group – 15 (VA) N, P, As, Sb, Bi  397

(k) Sn + conc. HNO3     ________ A + CH3COOH   C + SO2 + HCl

+ _________ + _______.
2C + (CH3)2Cd     2D + CdCl2
(l) NH3 + Cl2     _____+ _______. (c) In the following reactions identify A, B, C
and D and write structure of D.
(m) P4O10 + PCl5     __________.
NH3 + NaOCl    A+B
E. (a) In the following equation, identify D and NH3 + A + B     C + NaCl + D
sketch structures of A, B, C and D.
(d) Identify A, B and D in the following
A + 2B + H2O   reactions and write structure of A.
  C + 2D
Ca3(PO4)2 + SiO2 Δ   A+B
[A = HNO2, B = H2SO3, C = NH2 – OH]
A + C    D + CO
(b) Identify A, B, C and D in the reactions (Carbon)
PCl5 + SO2     A+B

Objective-Type Questions

1. Which of the following is formed when conc. (b) Each P forms three bonds in both.
HNO3 is mixed with P4O10? (c) Each P forms four bonds in both.
(a) N2O (b) NO2 (d) Both have similar solubility.
(c) N2O3 (d) N2O5 7. For the reaction, MH3 + H+ fi MH4+ (M =
2. Very dilute HNO3 forms NH4NO3 with N, P, A, Sb), which of the following has highest
(a) Cu (b) Ag proton affinity?
(c) Zn (d) Hg (a) NH3 (b) PH3
3. Brown ring compound is (c) AsH3 (d) SbH3
(a) [Fe(H2O)4NO]SO4 8. Ammonia on reaction with hypochlorite anion
(b) [Fe(H2O)5NO]SO4 form
(c) [Fe(H2O)6NO]SO4 (a) NO (b) N2H4
(d) [Fe(H2O)5]NO2 (c) HNO2 (d) N2O
4. Which of the following gives metaphosphate 9. Which of the following is the strongest base?
on heating? (a) SbH3 (b) AsH3
(a) NaH2PO2 (b) Na3PO4 (c) PH3 (d) NH3
(c) Na2HPO4 (d) NaH2PO4 10. Conc. HNO3 reacts with iodine to give
5. Mark the correct answer using codes. White (a) HOIO3 (b) HOIO2
phosphours has (c) HOIO (d) HOI
(I) Six P – P σ bonds 11. Ammonia gas can be dried over
(II) Four lone pairs (a) CaO
(III) Four P – P σ bonds (b) Anhydrous CaCl2
(IV) P P P angle of 60° (c) P4O10
(a) I, II, III (b) I, II, IV (d) conc. H2SO4
(c) II, III, IV (d) I, III, IV 12. Which one of the oxides of nitrogen is a
6. Which of the following is correct for white and coloured gas?
red phosphorus both? (a) N2O (b) NO
(a) PPP angles are equal. (c) NO2 (d) N2O4
398  Basic Concepts of Inorganic Chemistry

13. One mole of calcium phosphide (or Zinc phosphide) 19. By the action of hot conc. H2SO4, phosphorus
on reaction with excess of water gives changes to
(a) One mole of phoshine (a) Phosphorus acid
(b) Two moles of phosphine (b) Metaphosphoric acid
(c) Two moles of phosphorus acid (c) Orthophosphoric acid
(d) Two moles of phosphoric acid (d) Pyrophosphoric acid
14. The CN– ion and N2 are isoelectronic. But in 20. Nitrogen is not liberated by the thermal
contrast to CN–, N2 is chemically inert because decomposition of
of (a) NaN3 (b) NH4NO3
(a) Low bond energy (c) NH4NO2 (d) (NH4)2Cr2O7
(b) Unsymmetrical electron distribution 21. The number of P – O – P bonds in cyclic
(c) Absence of bond polarity trimetaphosphate ion is
(d) Presence of more electrons in bonding (a) One (b) Two
orbitals. (c) Three (d) Four
15. Ammonium dichromate is used in some 22. Ammonium compound which on heating does
fireworks. The green coloured powder blown not give ammonia is
is (a) (NH4)C2O4 (b) (NH4)2SO4
(a) CrO(O2)2 (b) CrO3 (c) NH4NO2 (d) (NH4)2CO3
(c) Cr2O3 (d) CrO(O2) 23. Which of the following mixture is used to
16. Which of the following can separate nitric oxide produce signal in oceans?
from nitrous oxide? (a) CaCl2 + Ca3P2 (b) CaO + Ca3P2
(a) Ammoniacal silver nitrate (c) CaC2 + Ca3P2 (d) Zn3P2 + Ca3P2
(b) Sodium nitroprusside 24. Gr – 15 elements form hydride of the type
(c) Ferrous sulphate solution MH3 (M = N, P, As, Sb). The bond angle HMH
(d) Lucas reagent. decreases in the order
17. Phosphine reacts with CuSO4 solution to form (a) N > P > As > Sb
(a) Copper phosphate (b) Sb > As > P > N
(b) Copper phosphate (c) N = P > As > Sb
(c) Copper phosphide (d) N > P = As > Sb
(d) Copper hypophosphite 25. The hybridization of P in metaphosphate ion
18. White phosphorus is kept in (PO3–) is
(a) Alcohol (b) Ether (a) sp2 (b) sp3
(c) Kerosene (d) Water (c) sp d
3
(d) None of these

Answers

1. (d) 2. (c) 3. (b) 4. (d) 5. (b) 6. (b) 7. (a) 8. (b) 9. (d) 10. (b)
11. (a) 12. (c) 13. (b) 14. (c) 15. (c) 16. (c) 17. (c) 18. (d) 19. (a) 20. (b)
21. (c) 22. (c) 23. (c) 24. (a) 25. (b).
 17
Group – 16 (VIA)
O, S, Se, Te, Po

Introduction
Elements of this group are O, S, Se, Te, and Polonium.
Oxygen, S, Se and Te are non-metallic. They are called chalcogens (ore forming, as many of the metal
ores are either oxide or sulphide).
Polonium is metallic and radioactive. It was discovered by M. Curie. Its name Polonium was derived
from the homeland, Poland, of M. Curie. It is found in U and Th ores as a radioactive decay product. It can
be made by bombarding 209Bi with neutrons in a nuclear reactor.

%L  Qĺ %LJ

  

3R E
Polonium–210 is α–active and has a half–life of 138.4 days (i.e., t½ 138.4 days).

Physical state of the elements

Oxygen at s.t.p. is gas and exists as dioxygen i.e., O2. It is stable due to very effective pπ – pπ bonding
(E0 = 0 = 496KJmol–1). Bonding in O2 is best explained by MO model. It has MO electron configuration.
      
2 ..ıVıVıS]ʌS[ ʌS\ʌS[ ʌS\
The bond order is 2 i.e., one σ and one π bond.
According to valence bond model O2 has two three-electron bonds.
2 2
A three electron bond is equivalent to half-bond.
Both the above bonding models show that O2 has two unpaired electrons. It is, therefore, paramagnetic
(μ =√8 BM).
Like oxygen, S is not S2 at stp. It is because S can not form effective (p – p)π bond. The (p – p)π
bonding in S is not effective due to large size and 8–e core in S. ordinary S is solid and exists as S8. The S8
has puckered ring structure (crown structure).
6 6
6 6 6 6
6
6
Figure 17.1
In the solid S8, rings are packed over one another.
400  Basic Concepts of Inorganic Chemistry

Allotropy of O and S
Oxygen
It has two allotropes:
(i) Dioxygen O2
(ii) Trioxygen O3 (ozone)
The structure and bonding in O2 is explained above. 2
Ozone (O3) has bent structure.
2 2
The O – O distance in O3 is 1.28Å. It is intermediate between single (1.41Å) and
double bonds (1.21Å). Thus O3 has resonance structure, Figure 17.2

2 2
2 2 2 2

Figure 17.3
However, O3 is polar due to coordinate bond and bent structure. The central O–atom is sp2 hybridized.

Sulphur
Sulphur forms open and cyclic species Sn, n = 2 to 20 because of its ability for catenation. Solid allotropes
are:
(i) Ordinary or α-sulphur or orthorhombic–S.
(ii) β - sulphur or monoclinic
(iii) Cyclo–Sn n = 6 to12
(iv) Plastic – S

α-Sulphur or orthorhombic – S (a, b, c and α, β, g = 9)

• Common form of S at 25°C.
• It is bright yellow, mp = 112.8°C.
• Insoluble in water.
• Soluble in CS2.
• S8 and has crown ring structure.

β -Sulphur or monoclinic (a, b, c; α, g = 90°, β)

• α -S changes at 95.5°C to β -sulphur.
• It is dull yellow, mp = 119°C.
• Insoluble in water.
• Soluble in CS2.
• S8 and has crown ring structure.

Cyclo –S
It contains Sn ring, n = 6 to 12, 18 and 20 also. The rings are similar in
• S – S distance (2.05Å)
• SSS angles ~106°
• S – S bond energy ~265KJmol–1.
They are soluble in CS2, benzene etc.
 Group – 16 (VIA) O, S, Se, Te, Po  401

Plastic – S or catena – S
• It is obtained when molten S is poured in ice cold water.
• It contains long zig – zag chain of S – atoms.
• It is insoluble in CS2.
• It transforms slowly to Sα.

Effect of heat on S
Sulphur undergoes variety of changes on heating. They are:

(i) S8 ∆ melt to a yellow transparent mobile liquid.

> 160°C
(ii) Melt brown, viscosity increases and reaches its maximum at ~200°C, when it is tar like.
(iii) Temperatures > 200°C viscosity decreases, mobility increases till the bp (444.6°C) when it is dark red
liquid.
(iv) At temperature above bp – red vapour, turning yellow as the temperature is raised. This is believed to
contain S8, S6 etc.
(v) At ~1000°C, Sulphur is S2 which is paramagnetic and has a structure similar to O2.
Viscosity of liquid S and temperature
Viscosity of liquid S increases gradually and is maximum at around 200°C. It is believed due to the formation
of long chain polymeric structure of S – atoms. As temperature increases, S8 rings break and radical ends are
generated. Then those radicals join together to produce long chain structure. The chain length is maximum
at 200°C (around 8x105 atoms). Therefore, the viscosity is highest. When temperature is raised beyond
200°C, the chains break leading to smaller chains. Therefore, viscosity decreases and behaviour parallels to
a liquid.

Oxidation state and nature of bond

Table 17.1
Oxidation states O S
–2 Na2O, CaO
Na2S, CaS, H2S etc
H2O
Na2O2, BaO2 H2S2
–1 (peroxide)
H2O2 Na2S2
–1/2 MO2
–
(superoxide) (M = K, Rb, Cs)
0 O2, O3 S8
+1 O2F2 –
+2 OF2 –
+4 – SF4, SO2
+6 – SO3, SF6, H2SO4 etc.

Note:
(i) Oxygen has positive oxidation state only with F because F is only more electronegative than O, (XF =
4.0, XO = 3.5).
–1
(ii) The oxidation state for O is found only in the superoxides KO2, RbO2 and CsO2.
2
402  Basic Concepts of Inorganic Chemistry

(iii) Sulphides, except alkali metals and Ca, Sr, Ba have covalent nature because S–2 ion is easily
polarizable.
Oxygen has high electronegativity. Therefore, it is ionic only in highly electropositive metals, Gr – 1 and Ca,
Sr and Ba. i.e., M2O or MO.
It is, however, mostly covalent, which it achieves in the following way:
(a) By forming two single bonds, – O –, (i.e., H2O, R – O – H, R – O – R).
(b) By forming double bonds, = O, (C = O, N = O, P = O, S = O etc).
(c) By forming three single bonds, H3O+ or 4 single bonds, which is rare, e.g., in Be4O(CH3COO)6, the basic
Be – acetate.
In addition to the above mode of bonding, O has strong ability to form H – bond. It very much
distinguishes oxygen from S which has little tendency for H – bonding.
Oxygen differs in its chemistry from Sulphur. The reasons are given below:

Table 17.2
O S
(a) Valence orbitals are s and p only (a) Valence orbitals are 3s, 3p and 3d,
2s22p4. the configuration is 3s23p4(3d°).
(b) It can form a maximum of 4 bonds (b) It can form more than four bonds
only but mainly is di and trivalent. by the use of 3d orbitals.

(c) Highly electronegative, so (c) No such compounds are known

stabilizes higher oxidation state of because S is less electronegative.
metals, Mn2O7, CrO3, OsO4 etc.
(d) Forms strong pπ – pπ bonds. (d) No pπ – pπ bond instead forms
strong dπ – pπ bonds.
(e) No tendency towards catenation. (e) Much higher catenation ability.
(ES–S = 226KJmol–1).

Note
Catenated compounds of S are the following:
(i) Polysulphides, S n-2 , where n = 2, 3, 4 etc. They are coloured due to charge transfer, e.g., yellow
ammonium sulphide generally denoted as (NH4)2S2.
(ii) Sulphanes of the type X – Sn – X, where X = H, Cl, CN etc., compounds corresponding to n = 100 are
reported.
(iii) Polysulphonic (or sulphane disulphonic) acids. They have the general formula.

HO3S – Sn – SO3H, where n up to 22.

  The well-established polythionate anions are for n = 1 to 4. However, there is evidence for anions
upto n = 22.
S2O6–2 Dithionate ion
2–
S3O6 Trithionate ion
 Group – 16 (VIA) O, S, Se, Te, Po  403

General properties of the elements

Table 17.3
Property O S Se Te Po
Atomic no. 8 16 34 52 84
Electronic
[He]2s22p4 [Ne]3s23p4 [Ar]3d104s24p4 [Kr]4d105s25p4 [Xe]4f145d106s26p4
structure
Atomic radius
0.74 1.03 1.17 1.37 –
(Å)
–
Radius X 2 (Å) 1.4 1.7 1.84 2.07 –
Electronegativity 3.5 2.5 2.48 2.01 1.76
mp (°C) 119 221 450 254
bp ( C)
°
444.6 684.8 990 962

Hydrides
All the elements of group–16 form hydrides of the type MH2 i.e., H2O, H2S, H2Se, H2Te and H2Po (it is
prepared only in trace amounts).
Water is liquid at room temperature due to extensive association of H2O molecules through intermolecular
H – bonding (Cf Hydrogen). Other hydrides (H2S to H2Te) are foul smelling toxic gases. These hydrides are
weak acid in aquous solution but H2O is amphoteric. Hydrogen sulphide (hydrosulphuric acid), H2Se and
H2Te can be prepared as:
FeS + H2SO4 FeSO4 + H2S↑
FeSe + 2HCl FeCl2 + H2Se
Al2Te3 + 6H2O 3H2Te + 2Al(OH)3

General properties of hydrides

Table 17.4
Property H2O H2S H2Se H2Te
ΔHf Decreases
Thermal stability Decreases
Bond angle Decreases
Reducing power Increases
Acid strength Increases
Toxicity Increases
B.p. H2O highest due to extensive H – bonding. For H2S, H2Se
and H2Te molecular mass is controlling factor.
Order H2Te > H2Se > H2S
Overall order H2O >H2Te > H2Se > H2S
404  Basic Concepts of Inorganic Chemistry

Acid strength of MH2

Table 17.5
Acid H2O H2S H2Se H2Te
Conjugate base Te -2
O -2 S -2 Te -2
–
Size of (M 2) rO - 2 < rS - 2 < rSe -2
< rSe-2
Charge density on conjugate O -2 > S -2 > Te-2 > Te -2
base (charge/radius)

The greater the charge density on the conjugate base greater is its attraction for proton. It suppresses
ionisation making the acid weak. Oxygen also forms H2O2, the hydrogen peroxide (details in compound
section). It is prepared in the laboratory by the action of dil. acid on a metal – peroxide.
Na2O2 + 2HCl 2NaCl + H2O2
3BaO2.8H2O + 2H3PO4 3H2O2 + Ba3(PO4)2 + 24H2O

Industrial preparation of H2O2

(i) By the electrolysis of conc. H2SO4 or (NH4)2HSO4.
(ii) By auto oxidatioin of 2 ethylanthraquinol.

Electrolysis of conc. H2SO4

H2SO4 H+ + HSO4–
Cathode reaction 2H+ + 2e H2
–
Anode reaction 2HSO4 H2S2O8 + 2e
(peroxy disulphuric acid)
Anode solution is hydrolyzed by water to give H2O2. Fractional distillation of hydrolyzed anode solution
produces H2O2 upto 90–98%.
H2S2O8 + H2O H2SO5 + H2SO4
(Caro’s acid)

H2SO5 + H2O H2O2 + H2SO4

Auto oxidation of 2 – ethylanthraquinol

2+ $LU2 
2
& + 
+  2 

2+ 2
+ 3Gǻ
Figure 17.4
 Group – 16 (VIA) O, S, Se, Te, Po  405

H2O2 is a bluish viscous liquid, i.e., denser than H2O. It is due to the fact that H2O2 is more associated
through H – bonding than water. However, pure H2O2 is colourless liquid (bp 150.2°C, mp – 0.43°C).
H2O2 decomposes even at room temperature to give oxygen,
H2O2 H2O + [O]
It is, therefore, a bleaching agent.
Colour + [O] Colourless
As bleaching is oxidative, it is permanent.
Aquous (an 30%) solution of H2O2 is used as or oxidant. It is a reducing agent also. The oxidation number
of oxygen in H2O2 is –1, which is intermediate for oxygen. Therefore, it is oxidant and reductant both.

H2O2 as oxidant
H2O2 + 2H+ + 2e 2H2O [E° = 1.77 V]
In this reaction H2O2 is reduced (O–1­ to O–2). So it is oxidant. As pot (E°) is high, it is a strong oxidant.
It is oxidizing agent in basic medium also,
HO2– + H2O + 2e 3HO– [E° = 0.87]
The reaction in basic medium is fast.
It oxidizes Fe2+ → Fe3+, I– → I2, NO2– → NO3–, AsO33– → AsO4–3, S–2 → SO4–2 etc.
4– 3–
[Fe(CN)6] [Fe(CN)6]
H2O2 is used to clean blackened old paintings (due to oxidation of PbS to PbSO4).

H2O2 as reductant

H2O2 2H+ + 2e + O2  (E° = -0.68V)

It is not a strong reducing agent. It reduces
MnO4– → Mn+2, ClO– → Cl–, Ag+ → Ag etc.

Strength of H2O2
The strength of H2O2 is denoted as volume strength, e.g., 10V, 20V etc. H2O2.
The volume strength denotes the volume of O2 produced at s.t.p. For example, a 10V H2O2 means a
solution of which 1ml produces 10 ml O2 at s.t.p.
The other units are:
(i) g/l strength of H2O2 = (68/22.4)Xv
(ii) Normality of H2O2 = V/5.6
(iii) Mol/l or Molarity = V/11.2

Acid strength of H2O2 and H2O

Acid strength of H2O2 is greater than H2O.
H2O2 H+ + HO2– K(25°C) = 1.5 × 10–12

H2O H+ + HO– K(25°C) = 1.0 × 10–14

It is because oxidation number of oxygen in H2O is –2 and in H2O2 is –1.
406  Basic Concepts of Inorganic Chemistry

Structure of H2O2

+
c
a 
a  c
+

Figure 17.5
This structure is like an open book.

Halides
As fluorine is more electronegative than oxygen the binary compound of O and F is called oxygen fluoride
not fluorine oxide. Sulphur forms variety of halides in +1, +2, +4 and +6 oxidation states.

Common halides of O and S

Table 17.6
Oxidation states O S

+1 O2F2 S2X2 (X = F, Cl, Br, I)

+2 OF2 SX2 (X = F, Cl, Br)
+4 – SX4 (X = F, Cl)
+6 – SF6

In addition to the above, S also forms some very important oxohalides. They are SOX2, (X = F, Cl, Br) i.e.,
SOF2, SOCl2, SOBr2.
The sulphur tetrafluoride (SF4) can be prepared by the reaction.
70 – 90 C
o

3SCl2 + 4NaF    SF4 + S2Cl2 + 4NaCl

It is highly reactive and is hydrolyzed by water
SF4 + 2H2O SO2 + 4HF
The SF6 is produced by direct fluorination of sulphur. Traces of SF4 and S2F10 are also formed.
S8 + 22F2 5SF6 + (trace SF4 + S2F10)
Sulphur hexafluoride is chemically very inert. It is used as an insulating medium for high voltage
electrical equipment. However, the break down product of SF6, SF5CF3 (trifluoromethyl sulphur penta
fluoride) has green house effect. It is very stable and expected to remain in the atmosphere for about 1000
years (CH4 lasts for 10 years and CO2 for 100 years).

SOCl2
Thiony chloride is most important oxohalide of S. It can be prepared by the reaction.
SO2 + PCl5 SOCl2 + POCl3
It is a colourless fuming liquid (bp 80°C). It is readily hydrolyzed by water,
SOCl2 + H2O ↑SO2 + 2HCl↑
 Group – 16 (VIA) O, S, Se, Te, Po  407

The products are gaseous and easily removed. Therefore, SOCl2 is often used to prepare anhydrous
metal chlorides.
Fe(OH)3 + 3SOCl2 FeCl3 + ↑3SO2 + 3HCl↑
CrCl3.6H2O + 6SOCl2 CrCl3 + 12HCl↑ + 6SO2↑
It is also used to replace -OH gr by –Cl form an alcohols (or acid).
R – OH + SOCl2 R – Cl + SO2↑ + HCl↑

Structure of SF4, SF6 and SOX2

Table 17.7
Molecule Structure Shape
WES
) )
SF4 6 Distorted Td
 )
)
2K )
) )
SF6 6 Oh
) )
)
7G

SOX2 6 Δ Py.
2 ;

The S – O bond in SOX2 has multiple bond nature. Its bond order depends on the electronegativity
of the halogen. The S – O bond has highest bond order in SOF2. It is because the high electronegativity
of F causes larger contraction of 3d orbitals of S. Which facilitates dπ – pπ bonding (O has filled
p – orbitals).

Molecular parameters in SOX2

Table 17.8
Parameter OSF2 OSCl2 OSBr2
Bond order (S – O) Decreases

Bond distance (S – O) Increases

408  Basic Concepts of Inorganic Chemistry

Oxides
The binary compounds of oxygen are called oxides. They are formed by almost every element. The bond
nature in oxides ranges from ionic (Na2O, CaO etc) to covalent (CO2, B2O3, SiO2 etc.).
The formation of O–2 ion from dioxygen is highly endothermic, that is, requires a large amount of
energy,
½ O2(g) O(g) ΔH = 248 KJmol–1
O(g) + 2e O(g)–2 ΔH = 752KJmol–1
However, many ionic oxides are formed due to high lattice energy of the compound, e.g., CaO, ZnO
etc.
Non-metal oxides are covalent. Some are discrete molecular species (CO2, SO2, CO, NO2, etc) whereas
some are macromolecular (B2O3, SiO2 etc.).

Classification of oxides
On the basis of
(i) The oxidation state of oxygen.
(ii) The acid–base nature.

Oxidation states of oxygen and oxides

Three types are found
(i) Normal oxides (O–2):  They have oxygen in -2 oxidation states, e.g., CaO, Na2O, FeO, MnO2 etc.
(ii) Peroxides (O2–2 unit):  They have the unit O2–2 i.e., oxygen in –1 oxidation state.
Ionic as well as covalent peroxides are formed.

1D2
6U2
,RQLFSHUR[LGHV
%D2
 
+2
+26±2±2+
 2 &RYDOHQWSHUR[LGHV

&+
 ±&±2±2+
Peroxides are oxidizing agents and ionic paroxides give H2O2 with water or dil. acid.
Na2O2 + 2H2O 2NaOH + H2O2
BaO2 + 2HCl BaCl2 + H2O2
(iii) Superoxides (O -2 ) :  They contain the unit (O -2 ) i.e., oxygen in –1/2 oxidation state.

The ion O2– has 17 electrons (odd number). Therefore, superoxides are paramagnetic and coloured (due
to unpaired electron). Superoxides are fomed by K, Rb and Cs only.

.2
5E2 <HOORZWR2UDQJHFU\VWDOOLQHVROLGV
&V2
 Group – 16 (VIA) O, S, Se, Te, Po  409

Superoxides are stronger oxidant than peroxides. They are decomposed by water or dil. acids to H2O2
and O2.
2KO2 + 2H2O 2KOH + H2O2 + O2

Acid–Base nature and oxides

Basic oxides contain O–2 discrete ion in solid state. They are formed by metals in their low oxidation state
(+1, +2, +3), e.g., Na2O, CaO, FeO, Cr2O3 (Cr+3 and O–2).
Soluble metal oxides produce hydroxide with water due to hydrolysis of O–2 ion.
O–2 + H2O 2HO– (K > 1022)
Na2O + H2O 2Na(OH)

Acid oxides
An oxide which forms an acid with water is termed as acidic oxide. They are mainly formed by non-metals
and are covalent (CO2, SO2, NO2, P4O6 etc.).
CO2 + H2O H2CO3
P4O6 + 6H2O 4H3PO3
Transition metals in their high oxidation state form acidic oxides,

9
92EDVLF
9
9
92DFLG

&U2
&U  EDVLF
&U2
 DFLG
&U2
Acidic and basic oxides combine to form salt.
CaO + SiO   ∆   CaSiO
2 3

FeO + SiO2  ∆   FeSiO3 ΔG(25°C)

Na2O + SiO2  ∆   Na2SiO3 → -175KJ
6Na2O + P4O10  ∆   4Na3(PO4) → -371KJ
Na2O + SO3  ∆   Na2SO4 → -522KJ
Na2O + Cl2O7  ∆   2NaClO4 → -587KJ
The stability of the salt depends on the gap in acidic and basic nature of the oxides. The larger the gap
stabler is the salt. It is seen in the above reaction (values of ΔG).
So,
Cu2O
FeO + SiO   ∆   FeSiO and not the Cu – silicate.
2 3
410  Basic Concepts of Inorganic Chemistry

Similarly,
FeO + CaO + SiO2    CaSiO3 and not FeSiO3

Amphoteric oxides
Elements having relatively less metallic nature form amphoteric oxide (Al, Sn, Pb, Zn etc.) Example, Al2O3,
SnO, PbO, ZnO etc.
They behave as bases towards strong acids and acidically towards strong bases.
Al2O3 + 6HCl 2AlCl3 + 3H2O
Al2O3 + 2HO– + 3H2O 2Al(OH)4–
ZnO + H2SO4 ZnSO4 + H2O
ZnO + 2HO– + H2O Zn(OH)4–
The only non-metal oxide, H2O, is amphoteric.

Neutral oxides
The non-metal oxides N2O, NO and CO are neutral.
In addition to the above types there are
(i) Non-stoichiometiric oxides, and
(ii) Mixed metal oxides.

Non–stoichiometirc oxides
Oxides in which metal and oxygen do not maintain whole number ratio are called non-stoichiometric oxides.
They are formed by transition metals and some lanthanides. For example, Fe (11) oxides is generally FeO0.9
to FeO0.95.

Mixed metal oxide

They contain different metal ions or the same metal in different oxidation states. Some common types are
(i) Spinels: M+2, M2+3O4, Example,
Fe3O4 ≡ FeO.Fe2O3
Co3O4 ≡ CoO. Co2O3
(ii) Ilmente: FeTiO3
It is FeO.TiO2 and is a mineral of Ti.
(iii) Perovskite: CaTiO3
It is also a mineral of Ti. It is CaO.TiO2.
All the oxides of the above type adopt specific crystal structure.
(iv) Some mixed oxides containing Al2O3 and traces of some transition metals are very important, e.g., Ruby
– Al2O3.Cr2O3, Blue sapphire – Al2O3 (Fe2+, Fe3+, Ti+4) oxides.

Oxides of group – 16
Common oxides formed by the elements of this group are M O2 and M O3.
 Group – 16 (VIA) O, S, Se, Te, Po  411

Table 17.9
Oxides Oxidation S Se Te
state of M
MO2 +4 SO2 SeO2 TeO2

MO3 +6 SO3 SeO3 TeO3

Sulphur dioxide (SO2) can be prepared by a number of methods viz.,

(i) S + O2 SO2
(ii) Metal – sulphite + dil. acid SO2
Na2SO3 + 2HCl 2NaCl + H2O + SO2↑
(iii) Metal – thiosulphate + dil. acid SO2 + S
Na2S2O3 + 2HCl 2NaCl + H2O + S↓ + SO2↑
(iv) By roasting M – sulphide
ZnS + 3/2O2 ZnO + SO2↑

PbS + 3/2O2 PbO + SO2

Sulphur dioxide is a triangular planar molecule with S in sp2 hybrid state.

6

Figure 17.6
The SO2 molecule is angular in shape with OSO angle of ~119°. Both the S – O bonds are equal (1.43Å).
The bond is short which suggests pπ – pπ as well as pπ – dπ bonding. The vacant d – orbirals at S and filled
p – orbital at O – atom overlap to form pπ – dπ bond.
Selenium dioxide (SeO2) is solid and has polymeric zig-zag chain structure,

2 2 2 2
6H 6H 6H

2 2 2

Figure 17.7
SeO2 is used as an oxidizing agent in organic chemistry.
O   O
|| ||
CH3 – CHO + SeO2 → H – C – C – H + Se + H2O
412  Basic Concepts of Inorganic Chemistry

2 2
6H2 
2 QLQK\GULQH

2 2

Figure 17.8
TeO2 forms an ionic crystal. The dioxides differ in their reactions with water,
62 
+ DT +62  ĀDT ZLWKKDUGO\DQ\+  62  
)UHHDFLGLVXQVWDEOHDQGQRWLVRODEOH

6H2 
:DWHU )RUPVVHOHQLRXVDFLG+  6H2  ,WPD\EH
REWDLQHGDVFU\VWDO

7H2 
,QVROXEOHLQZDWHU

The aq. solution of SO2 has the following equilibria.

SO2 + H2O H+ + HSO3– K1 = 1.3 x 10–2
HSO3– H+ + SO3–2 K2 = 5.6 x 10–8
Although H2SO3 does not exist, two series of salts, the bisulphites (NaHSO3) and sulphites Na2SO3 are
known. Only NH4+ and alkali metal (except Li) bisulphites are known in solid state. All bisulphites are water
soluble.

Trioxides (MO3)
The MO3 are prepared as:
92
62ò262
RU 
 3WFDWDO\VW

6LOHQW
6H26H2
HOHFWULFGLVFKDUJH 
 6WURQJǻ
+7H27H2+2

The conversion of SO2 to SO3 is favored thermodynamically (ΔG° = -6.7mol–1) but the reaction is very slow
due to high activation energy. Therefore, catalytic oxidation is required. The reaction, with V2O5 as catalyst,
proceeds as:
SO2 + O2– + 2V+5 2V+4 + SO3

2V+4 + ½O2 2V5+ + O–2

SO2 + ½O2 SO3

 Group – 16 (VIA) O, S, Se, Te, Po  413

The trioxides are acid anhydrides.

SO3 + H2O H2SO4

SeO3 + H2O H2SeO4 (selenic acid)

TeO3 + 3H2O H6TeO6 [or Te(OH)6]

Telluric acid

The formula of telluric acid is Te(OH)6. It is due to large size of Te. The acid, Te(OH)6 has octahedral
structure.

2+
+2 2+
7H
+2 2+
2+
Figure 17.9

Gaseous SO3 has triangular planar structure with sp2 S – atom.

Figure 17.10

All S – O bonds are equal (1.41Å), intermediate between S – O single and S – O double bonds. The S
– O bond has contribution from pπ – pπ as well as dπ – pπ bonding. At room temperature SO3 is solid. Solid
SO3 has either linear chain structure or cyclic trimeric structure.
2 2
2 6 2 6 2 /LQHDUFKDLQVWUXFWXUH
2 2
2 2
6
2 2
2 &\FOLFWULPHU
2
6 6
2 2 2

Figure 17.11
414  Basic Concepts of Inorganic Chemistry

Oxo acids
Sulphur, Se and Te form oxo acids. But S acids are important and numerous.
Oxo-acids of S.

Table 17.10
Name Formula Structure
Acids having no S – S bond

2 2

Pyrosulphuric acid H2S2O7 +2 6 2 6 2+

2  2
Acids having S – S bond

2+

Thiosulphuric acid H2S2O3 +2 6 6

2
2 2


Dithionous acid H2S2O4a +2 6 6 2+
2 2
Pyrosulphurous acid H2S2O5 a
+2 6 6  2+

2



2 2

Dithionic H2S2O6 +2 6 6 2+

2 2


2 2

Polythionic acid HO3S(S)xSO3H +2 6 6 [ 6 2+

2  2

Peroxo acids ( i.e., O – O bond) 2

+2 62 2 2 +
Peroxomono sulphuric +2 26 2 2 +
H2SO5
acid (Caro’s acid)
2 
  2  2

Peroxodisulphuric acid 
H2S2O8 +2 62 2 2 62 2+
(Marshall’s acid) 

+2 26 2  2 26 2+

2  2
 Group – 16 (VIA) O, S, Se, Te, Po  415

Note:
(i) Acids marked ‘a’ are not known in free state.
(ii) All S – oxoacids are diprotic.
(iii)
All acids have Td structure.
(iv)
In peroxo acids O – atoms forming peroxide link are in –1 oxidation state i.e., central O – atoms in
Marshall’s acids have –1 oxidation state.
(v) In peroxo acids oxidation number of S is +6.

Sulphuric acid
It is most important acid of S. It is manufactured by
(i) Lead chamber process,
(ii) Contact process.

Lead chamber process

In this process SO2 is oxidized to SO3 in the presence of NO catalyst. SO3 is then dissolved in water to form
H2SO4.
S or FeS2 SO2

NO + ½ O2 NO2
SO2 + NO2 SO3 + NO

SO3 + H2O H2SO4

This method produces dil. H2SO4, ~65% H2SO4. It is concentrated by Cascade process. This method has
many difficulties:
(i) In low concentration of water, SO3 forms a mist like material which is difficult to dissolve.
(ii) In case of low concentration of water vapour, chamber crystals are formed, HO – SO2 – ONO i.e.,
nitrososulphuric acid. This method is now obsolete.

Contact process
This method is now widely used. SO2 is oxidized to SO3 in the presence of V2O5 catalyst. SO3 is dissolved in
conc. H2SO4 to form pyrosulphuric acid H2S2O7. It is called fuming sulphuric acid or oleum. It is diluted with
water to prepare conc. H2SO4.
V 2O 5
SO2 + ½ O2   
SO3 (Heterogeneous catalysis)
P ~ 1.5
T ~ 450oC
H2SO4 + SO3     H2S2O7 (Oleum)
H2S2O7 + H2O    2H2SO4

• Pure acid is colourless liquid.

• It is highly viscous liquid due to extensive intermolecular H – bonding.
• Conc. H2SO4 is called ‘Oil of Vitriol’.
• It self ionizes as
2H2SO4    HSO4– + H3SO4+
Therefore, the acid is good conductor of electricity.
416  Basic Concepts of Inorganic Chemistry

• Conc. acid is a powerful dehydrating agent, and dehydrates variety of substances.

Conc. H2SO4
HCOOH    CO + [H2O.H2SO4]
Δ
• This reaction may be used to prepare CO.
CuSO4.5H2O + H2SO4 CuSO4 + [5H2O. H2SO4]
Sugars and organic hydroxy acid are charred by conc. H2SO4
C6H12O6 + H2SO4 6C + [ 6H2O. H2SO4]
Black

• Conc. H2SO4 acts as an oxidizing agent (not strong). It oxidizes

H2SO4
C    CO2
H2SO4
Cu    Cu+2
H2SO4
S    SO2    + SO2
H2SO4
HBr    Br2
H2SO4
HI    I2

In all the above reactions H2SO4 is reduced to SO2 i.e., SO4–2 is actual oxidant.
Cu Cu+2 + 2e
SO4–2 + 2e + 4H+ SO2 + 2H2O

Cu + SO4–2 + 4H+ Cu+2 + SO2 + 2H2O

• Electrolysis of conc. H2SO4 gives peroxydisulphuric acid, H2S2O8 at anode.
Electrolysis
2H2SO4    H2 + H2S2O8
(Cathode) (Anode)
The persulphate ion S2O8–2 ion is a powerful oxidant.
S2O8–2 + 2e + 4H+ 2H2SO4 E° = 2.10V.
It oxidizes
Mn+2(aq)    MnO­–4(aq)
(Colourlsss) (Purple)
I–    I2
Cr+3    Cr2O7–2
(Green) (Orange)

Ag+    Ag+2
 Group – 16 (VIA) O, S, Se, Te, Po  417

• Conc. H2SO4 forms chlorosulphonic acid and sulphuryl chloride with PCl5.
S2SO4 + PCl5 HOSO2.Cl + POCl + HCl
HSO3Cl + PCl5 Cl.SO2Cl + POCl3 + HCl
This reaction shows that the two OH groups are attached to SO2 in H2SO4.
Main use of H2SO4 is as reagent and in industry.

S – N compounds 6 6
Many chain and ring compounds containing S and N are known, such as
S4N4, tetrasulphur tetranitride. 1 1 1 1
CCl 4
6S2Cl2 + 16NH3 fi S4N4 + 12NH4Cl + 8S
6 6
The molecule S4N4 has cradle like structure.
dS ----- S = 2.58Å G 66 c
G 61  c
dS ---- N = 1.78Å
The weak S ----- S bonding makes S4N4 a cage type molecule. Figure 17.12

Practice Questions

A. Explain the following. (n) Sulphuric acid (H2SO4) and telluric acid
(a) Although O2 has even number of electrons [Te(OH)6] differ in stochiometry, acidity
it is paramagnetic. and structure.
(b) There is colour change when S is heated at (o) Viscosity of liquid sulphur is maximum at
different temperatures. around 200°C.
(c) Sodium sulphite decolourizes bromine B. Fill in the blanks.
water. (a) For the preparation of H2S in the laboratory
(d) SF4 is hydrolyzed in water but not SF6. ______________ apparatus is used.
(e) The bond angle in H3O+ (~115°) is much (b) The manufacture of H2SO4 by the contact
larger than NH3 (~107°). process uses ___________ as catalyst.
(f) The bond angle in (CH3)2O (~1110) is much (c) Sulphur acts as __________________
smaller than in (SiH3)2O (~ 150°). agent in vulcanization of rubber.
(g) Oxidation and oxygenation reactions. (d) Oxygen gas is absorbed by
(h) Oxygen is diatomic (O2) gas and sulphur is ____________________________.
S8 and solid. (e) The bleaching action of O3 is due to _____
(i) Unlike SO2, SeO2 is a solid that has chain and that of SO2 is due to __________.
structure. (f) The structure of solid SO3 is either
(j) The bond multiplicity of S – O bond __________or _______________.
decreases in the series OSF2 > OSCl2 > (g) Ozone has dipole moment due to
OSBr2. ___________ and ___________.
(k) The bond angle in H2O (~105°) is greater (h) The viscosity of liquid S at 200°C is
than in H2S (~92°). _________ due to ________­­___.
(l) H2S is stronger acid than H2O. (i) Passing H2S through dil. HNO3 produces
(m) Gaseous and solid SO3 differ in structure. ____________ form of sulphur.
418  Basic Concepts of Inorganic Chemistry

(j) Viscous nature and high boiling point of (d) Sulphur is boiled with lime water.
conc. H2SO4 is due to ________________. (e) H2S is passed in conc. H2SO4.
C. What happens when? (f) Sodium thiosulphate is added slowly to
(a) SO2 is passed through aq. solution of copper AuCl3.
sulphate in the presence of potassium (g)  Ammonium sulphate is heated with a
thiocyanate. mixture of NO and NO2.
(b) SO2, water vapour and air are passed over (h) Ammonium persulphate, (MH4)2S2O8, is
heated sodium chloride. treated with MnSO4 in water.
(c) Sulphur is heated with conc. H2SO4.

Objective-Type Questions

  1. Sodium thiosulphate is prepared by   7. The correct order of electron attachment

(a) Boiling Na2SO3 solution with S in alkaline enthalpy of O, S and Se is
medium. (a) O > S > Se (b) S > Se > O
(b) Boiling Na2SO3 solution with S in acid (c) S > O > Se (d) Se > S > O
medium.   8. Chlorine gas is passed in an aq. solution of
(c) Neutralizing H2S2O3 solution with NaOH. Na2S2O3, the product is
(d) Reducing Na2SO4 with H2S. (a) Na2SO3, S, HCl
  2. Marshall’s acid is (b) Na2O4, S, HCl
(a) H2S2O5 (b) H2S2O8 (c) NaClO2, S, HCl
(c) H2SO4 (d) H2S2O7 (d) Na2S, S, HCl
  3. Which of the following give SO2 and S with dil.
  9. The geometry and dipole moment of O3 are
acid?
(a) Linear and zero
(a) Na2SO3 (b) Na2S2O3
(c) Na2S (d) Na2SO4 (b) Angular and zero
  4. Shape of O3 is (c) Angular and non-zero
(a) Angular (d) Linear and non-zero
(b) Triangular planar 10. In the persulphate dianion (S2O82–)
(c) Linear (a) All S – O bonds are non – equivalent
(d) Tetrahedral (b) Four S – O bonds are equivalent
  5. Catalyst now used in contact process is (c) Six S – O bonds are equivalent
(a) Oxides of nitrogen (d) All S – O bonds are equivalent
(b) Vanadium pentaoxide 11. Which of the following reactions should be
most favoured thermodynamically?
(c) Finely divide nickel
(a) 2Na2O + SiO2 → Na4SiO4
(d) Vanadium monoxide
(b) Na2O + P4O10 → Na3PO4
  6. Group–16 elements form hydrides of the type
(c) Na2O + SO3 → Na2SO4
MH2, (M = O, S, Se, Te). Their correct stability
order is (d) Na2O + Cl2O7 → NaClO4
(a) H2O > H2S > H2Se > H2Te 12. There is O – O bond in
(a) S2O32– (b) S2O42–
(b) H2Te> H2Se > H2S > H2O
(c) S2O72– (d) S2O82–
(c) H2Te > H2O > H2Se > H2S
13. When chlorosulphonic acid is treated with
(d) H2S > H2O > H2Te > H2Se 100% H2O2, the product is
 Group – 16 (VIA) O, S, Se, Te, Po  419

(a) H2S2O8 (b) H2S2O7 21. Identify the correct order of increasing
(c) H2S2O5 (d) H2SO5 solubility.
14. There is no S – S bond in (a) Na2S < ZnS < CuS
(a) S2O72– (b) S2O52– (b) CuS < ZnS < Na2S
(c) S2O42– (d) S2O32– (c) ZnS < CuS < Na2S
15. The oxidation number of S in H2S, S2F2 and S8 (d) Na2S < CuS < ZnS
respectively are 22. Two salts M and N are treated separately wit
(a) 0, +1 and –2 (b) –2, +1 and 0 dil HCl. They liberated two gases A and B
(c) 0, + and +2 (d) –2, +1 and +2 respectively. The gas A turns lead acetate paper
black and B decolourises acidic KMnO4. The
16. Hydrolysis of one mole of peroxydisulphuric
salts M and N respectively are
acid produces
(a) Na2SO4 and Na2SO3
(a) Two types of peroxymonosulphuric acid
(b) Na2S and Na2S2O3
(b) Two moles of sulphuric acid
(c) Na2S2O3 and Na2S
(c) One mole of peroxymonosulphuric acid
and one mole of sulphuric acid. (d) Na2S and Na2SO4
23. The gaseous mixture N2O and O2 is used as
(d) One mole H2O2, one mole sulphuric acid
and one mole peroxymonosuophuric acid (a) Anesthetic
17. Number of atoms in α-sulphur is (b) Fuel
(a) 6 (b) 8 (c) Oxidzing agent
(c) 4 (d) Infinite (d) None of these
24. H2S acts as
18. Which of the following has peroxy bond?
(a) Oxidizing agent
I  H2SO5
(b) Reducing agent
II  H2S2O3
(c) Both oxidizing and reducing agent
III  H2S2O7
(d) None of these
IV  H2S2O8
25. The oxidation states of S in H2SO5 , H2SO3 and
(a) I, II (b) II, III H2S2O8 respectively are
(c) III, IV (d) I, IV (a) +5, +3 and +6
19. Molecular iodine oxidizes S2O32– ion into (b) +6, +3 and +6
(a) SO32– (b) SO42– (c) +6, +4 and +6
–
(c) S4O62 (d) S2O52– (d) None of these
20. The number of S – S bonds in SO3 trimer, S3O9 26. The correct order of dS—O in (I) SO2,
is (II) SO3, (III) SO24- is
(a) Zero (b) One (a) I > II > III (b) III > I > II
(c) Two (d) Three (c) II > III > I (d) I > III > II

Answers

1. (a) 2. (b) 3. (b) 4. (a) 5. (b) 6. (a) 7. (b) 8. (b) 9. (c) 10. (c)
11. (d) 12. (d) 13. (d) 14. (a) 15. (b) 16. (c) 17. (b) 18. (d) 19. (c) 20. (a)
21. (b) 22. (b) 23. (a) 24. (b) 25. (c) 26. (b)
18
Group 17 (VIIIA) Halogens
F, Cl, Br, I and At

Introduction
The elements F, Cl, Br, I and At (Astatine) are called halogens (Greek, ‘Halos’–salt and ‘gene’ – born, i.e.,
salt forming).

Table 18.1
Elements Atomic Number Electron Configuration
Fluorine (F) 9 2
[He] 2s22p5
Chlorine (Cl) 17 10
[Ne] 3s23p5
Bromine (Br) 35 18
[Ar] 3d104s24p5
Iodine (I) 53 36
[ Kr] 4d105s25p5
Astatine (At) 85 54
[Xe] 4f14 5d106s26p5

All the elements of this group are non-metallic. Iodine is solid and has some metallic lusture.
Astatine (At) is radioactive and does not occur in nature. It can be made by nuclear reaction,
209
83
Bi + He2+ → 211
85
At + 2 n (i.e., α, n reaction)
The t 1 of 211At is 7.5 hrs. The longest lived isotope is 210At ( t 1 ≈ 8.3h).
2 2

Physical state
All elements exist as diatomic molecules, F2, Cl2, Br2 and I2 and are coloured. But the elements differ in
physical states at room temperature.

Table 18.2
Molecule Physical state Colour
F2 Gas Light yellow
Cl2 Gas Greenish yellow
Br2 Liquid Red brown
I2 Solid Black solid
Violet (vapour)
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  421

The change in physical state gas → liquid → solid is due to increase in van der Waals force. This weak
force depends on the number of electrons in a chemical species. As atomic number increases from F(9) to
I(53), the number of electrons also increases. This increase causes increase in van der Waals force from
fluorine to iodine. Therefore, F and Cl are gases, Br is liquid and iodine is solid.

The colour of halogens is due to charge transfer,

;± . (actually the electro transition is n → π*
;
transition).

Table 18.3
Property Fluorine Chlorine Bromine Iodine
Atomic radius (Å) 0.72 0.99 1.14 1.33
Ionic radius, X–(Å) 1.36 1.84 1.95 2.16
Ionization energy
ev. 17.4 13.01 11.8 10.44
KJmol–1 1681 1256 1143 1009
Electron affinity 333 349 325 296
Electronegativity 4.0 3.0 2.8 2.5
Bond length, (X – X) (Å) 1.43 1.99 2.28 2.66
Heat of dissociation, X – X i.e.,
126 210 158 118
bond energy, KJmol–1
Std. electrode Pot, E° (V) +2.87 +1.4 +1.09 +0.62
½X2 + e → X–
The above table shows that the general properties vary regularly in this group (like group 1).
(i) Properties which decrease down the group:
Table 18.4
Property F Cl Br I
Ionization energy Decreases
Electronegativity Decreases
E° Decreases
Oxidizing power Decreases

(ii) Properties which increase down the group:

Table 18.5
Property F Cl Br I
Atomic radius Increases
Ionic radius Increases
Bond length (X – X) Increases
mp Increases
bp Increases
Reducing power, X– Increases
F– Cl– Br– I–

(iii) Electron affinity does not vary regularly. The order is Cl > F > Br > I.
422  Basic Concepts of Inorganic Chemistry

Lower Ea of F is due to its small size. In F the electron is added in 2p orbital. As the shell is small, electron–
electron repulsions in it is relatively large. Therefore, the electron being added to F experiences great repulsion
and so Ea is smaller than Cl. The degree of repulsion is seen in the expansion of size of F– compared to F,
rF ~ 0.71Å and rF– ≈ 1.33Å i.e., an increase of about 87%.
(iv) The X – X bond energy also does not vary regularly. The order is
Cl2 > Br2 > F3 > I2
In spite of shortest bond in F2 its dissociation energy is low. It is due to small size of F – atom. the F2 molecule

is )±)
i.e., three lps at each F – atom
As size of F is small, repulsion between lps at two F – atoms is very large. This repulsion weakens the
bond and dissociation energy is low.

Special properties of Fluorine

Fluorine is peculiar in its properties.
(i) It is chemically most reactive of all the elements and combines directly with all the elements except O2,
He, Ne and Ar. It is due to:
(a)  Low F – F bond energy
(b)  High bond energy of F with other elements

Table 18.6  Some bond energies. KJmol–1

X B–X C–X N–X Si – X P–X S–X

F 645 439 272 582 490 326
Cl 444 347 201 391 319 255
Br 368 276 - 310 264 213
I 272 238 - 234 184 -

(c) The high hydration energy of F– due to smallest size of F–. AgF is soluble in water due to high
hydration energy of F–. Other silver halides (AgX, X = Cl, Br, I) are insoluble in water.
(d) Reaction of F with chemical substances is highly exothermic.
MgO + F2   MgF2 + ½O2 + Q

Al2O3 + 3F2   2AlF3 + 3/2O2 + Q

(ii) Presence of very strong H – bond in HF, - - - H – F - - - H – F - - -.
(iii) Fluorinated hydrocarbons are very inert, e.g., polytetrafluoroethene (PTEE). It is used as a coating for
non-stick cook wares.

Oxidation state and bonding

Fluorine is the most electronegative element (XF = 4.0) and so it shows only oxidation state of – 1, (not
positive oxidation state). Other halogens show oxidation states from –1 to +7.
Chlorine shows ⊕ive oxidation with F and O, Bromine with Cl, F, O and N and I with F, Cl, Br, N and O.
The common oxidation states are 0, +1, +3, +5 and +7.
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  423

Table 18.7
Oxidation state F Cl Br I
NaCl NaBr NaI
–1 NaF HF
HCl HBr HI
0 F2 Cl2 Br2 I2
+1 HOCl HOBr HOI
+3 – HOClO HOBrO HOIO
+5 – HOClO2 HOBrO2 HOIO2
+7 – HOClO3 HOBrO3 HOIO3

Halogens are one electron short than noble gas configuration. Therefore, they can achieve stable
configuration:
(i) By gain of one electron to form X–
½ F2 + e   F– (≡ Ne)
½ Cl2 + e   Cl– (≡ Ar) etc.
In the above situation ionic compounds are formed.
(ii) By sharing an electron with other elements i.e., monocovalency,
)
+ ) 1 )

)
Figure 18.1
Such compounds are polar covalent.

Formation of X2 (X = F, Cl, Br, I)

F2
(i) Fluorine is most oxidizing and therefore, common oxidizing agents fail to oxidize F– to produce F2.
However, the following reaction can produce F2.
K2MnF6 + 2SbF5   2KSbF6 + MnF3 + ½ F2
In this reaction the stronger Lewis acid SbF5 displaces weak acid (MnF4) from its salt (K2MnF6). But
MnF4 is unstable and decomposes into MnF3 and F2.
(ii) Fluorine is generally prepared in large quantity by electrolysis of a mixture of fused anhydrous HF and
KF. The liquid contains K+. HF2– (HF2– is stable due to H – bonding).
The electrolytic cell is made of steel or monel metal.
The electrodes are:
Anode – copper impregnated graphite.
Cathode – Fe
KHF2 → liquid, K+, H+, 2F–.
Cathode reaction 2H+ +   H2
–
Anode reaction 2F   F2 + 2e
424  Basic Concepts of Inorganic Chemistry

Chlorine (Cl2), Bromine (Br2) and Iodine (I2)

(i) All these three halogens can be prepared by heating respective halides with MnO2 and conc. H2SO4. This
is laboratory method for X2.
NaX + MnO + H SO ∆ X (X = Cl, Br, I)
2 2 4 2

2NaX + MnO2 + 3H2SO4 ∆ MnSO4 + 2NaHSO4 + X2 + 2H2O

or
MnO2 + 2e + 4H+ Mn+2 + 2H2O

2Cl– Cl2 + 2e
–
MnO2 + 2Cl + 4H +
Mn+2 + Cl2 + 2H2O
(ii) Lower atomic number halogen oxidizes halide ion having higher atomic number to form X2.
Thus,
(a)  F2 oxidizes Cl– to Cl2, Br– to Br2 and I– to I2
F2 + 2X–   2F– + X2 (X = Cl, Br, I)
(b)  Cl2 oxidizes Br– to Br2 and I– to I2
Cl2 + 2X–   2Cl– + X2 (X = Br, I)
(c)  Br2 oxidizes I– to I2
(d) Br2 + 2I–   2Br– + I2

Manufacture of Cl2
There are many methods:
(i) As a by-product in the manufacture of NaOH by the electrolysis of brine.
(ii) As a by-product in the isolation of Na by the electrolysis of fused NaCl.
(iii) Deacon’s process: In this method HCl is oxidized with air in the presence of CuCl2 catalyst to produce
Cl2.
CuCl2
4HCl + O2 2H2O + 2Cl2
~ 400oC
(Air)

(iv) Weldon’s process: This process involves oxidation of conc. HCl with pyrolusite (MnO2). The reaction
takes place on heating.
4HCl + MnO ∆ MnCl + 2H O + Cl
2 2 2 2

This method is inferior to Daecon’s process.

(v) Nitrosyl chloride process: When NaCl is treated with conc. HNO3, Cl2 and NOCl are formed.
NaCl + 4HNO3 HCl + NaNO3] x3

HNO3 + 3HCl NOCl + Cl2 + 2H2O

3NaCl + 4HNO3 3NaNO3 + NOCl + Cl2 + 2H2O
The gaseous mixture Cl2 + NOCl is oxidized with O2
2NOCl + O2   2NO2 + Cl2
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  425

The product (NO2 and Cl2) is liquefied and Cl2 is distilled out. The NO2 is converted into HNO3 which is used
again.
4NO2 + O2 + 2H2O   4HNO3
Manufacture of Br2
(i) From carnalite
Carnalite (KCl, MgCl2.6H2O) contains MgBr2 in small quantities. Fractional crystallization of a solution
of carnaltie produces crystal of KCl. The mother liquor contains MgCl2 and MgBr2. When Cl2 is passed
in this hot solution vapours of Br2 are produced. It is carried up by steam into condensers, where liquid
bromine is obtained.
Any uncondensed bromine is absorbed in iron filings forming ironbromide.
MgBr2 + Cl2   MgCl2 + Br2
Condensed
Br2 + Water vap liquid Br2

(ii) From sea water

Sea water, the most important source of Br2, contains MgCl2 and MgBr2 in minute quantities.
  Brine is acidified and saturated with Cl2 gas. Bromine is set free. It is absorbed in NaOH. When this
solution is acidified, bromine is liberated.
MgBr2 + Cl2   MgCl2 + Br2
6NaOH + 3Br2   5NaBr + NaBrO3 + 3H2O
5NaBr + NaBrO3 + 3H2SO4   3Na2SO4 + 3H2O + ↑3Br2

Manufacture of iodine
(i) From sea weed
Sea weeds contain iodine (~0.5%) in the form of iodide. Dried sea weeds are burnt to ash. This ash is
called ‘Kelp’. It contains iodine as iodide.
  Kelp is extracted with water and filtered. When the filtrate is evaporated chlorides, carbonates and
sulphates of alkalimetals crystallize out. The mother liquor is distilled with MnO2 and H2SO4. The iodine
is collected in aludels (stoneware receivers).
2NaI + MnO2 + 3H2SO4   MnSO4 + 2NaHSO4 + I2
I –∆ I
2(VAP) 2(S)

(ii)  From caliche (chile salt petre) (NaNO3.NaIO3)

It is the main source of iodine. It contains iodine as NaIO3
Calich solution on fractional crystallization gives ppt. of NaNO3. When it is heated with calculated
amount of NaHSO3, I2 separates out in vapour state.
IO3– + 3HSO3– 3HSO4– + 6H+ + I –

IO3– + I– + 6H+ I2 (Vap) + 3H2O

Iodine vapour is absorbed in KI solution. It is steam distilled to get pure iodine.

I2 + KI KI3 Steam I
Distilled 2(s)
Pure
426  Basic Concepts of Inorganic Chemistry

Reactions of X2 (X = F, Cl, Br, I)

• Fluorine is most reactive of all the elements.
• It combines with all elements directly except He, Ne and Ar.
• It does not show positive oxidation state as it is the most electronegative element (χF = 4.0).
• It is an extremely strong oxidizing agent (E° = 2.87), such strong that it can cut through a wall like a hot
knife through butter.
• Cl and Br are very comparable in their reaction.
• Iodine is less reactive.
• Reactivity order F > Cl > Br > I.

Important reactions

Table 18.8
Reactants Reaction Comment
Water + F2 H2O + F2 → 2HF + ½O2 F oxidizes water to O2. This reaction is
also possible with Cl but is extremely slow
(activation energy factor).
Water + X2 H2O + X2 → HX + HOX It is disproportionation of halogen, occurs
(X = Cl, Br) to a very small extent, Cl and Br are
actually hydrated in water, Cl2.8H2O,
Br2.8H2O.
Water + I2 -- Practically no reaction iodine is insoluble
in water. I2 is soluble in KI solution due to
the reaction KI + I2 → KI3
NaOH + F2 2NaOH + 2F2 OF2 is storng oxidizing agent and used as
↓ rocket fuel.
2NaF + H2O + OF2
NaOH + X2 (i) dil. and cold NaOH Both are disproportionsation reactions.
(X = Cl, Br, I) 2NaOH + X2
↓
NaX + NaOX + H2O
(ii) hot conc. NaOH
6NaOH + X2
↓
5NaX + NaO3X + 3H2O
or
XO– + H2O + 2e → X– + 2HO–] x2
XO– + 4HO– → XO3– + 4e + 2H2O

3XO– → 2X– + XO3

NH3 + X2 (i) with excess NH3 NF3 is stable. NCl3 is explosive and
(X = F, Cl, Br) 8NH3 + 3X2 → N2 + 6NH4X unstable. NBr3 does not exist at room
temperature.
(ii) with excess X2
NH3 + 3X2 → NX3 + 3HX
(Continued)
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  427

Reactants Reaction Comment

H2 + X2 H2 + X2 → 2HX Reaction with F is explosive. Cl reacts in

(X = F, Cl, Br, I) sun light. Br reacts on heating. I reacts in
the presence of a catalyst (Pt.)
SO2 + X2 SO2 + X2 + 2H2O X2 is oxidizing agent and SO2 is reducing
(X = F, Br, I) ↓ agent in this reaction.
H2SO4 + 2HX
or
X2 + 2e → 2X–
SO2 + 2H2O → SO4–2 + 2e + 4H+

X2+ SO2 + 2H2O → 2X– + SO4–2 + 4H+

SO2 + X2 SO2 + X2 → SO2X2 It is a colourless liquid fuming in most air.

(X = F, Cl) Sulphuryl halide

H2S + X2 H2S + X2 → 2HX + S H2S is reducing agent and X2 is oxidizing

X = Cl, Br, I) agent.

Metal + X2 M + X2 → M - halide Metal halides are ionic to covalent.

Conc. H2SO4+ I2 I2 + 5H2SO4 Cl and Br are not oxidized.

↓(boil)
2HIO3 + 5SO2 + 4H2O
or
I2 + 6H2O → 2IO3– + IOe + 12H+
SO4–2 + 2e + 4H+ → SO2 + 2H2O]x5

I2+5SO4–2+8H+→2IO3–+5SO2+4H2O

Conc. HNO3+I2 I2+10HNO3→2HIO3+10NO2+4H2O Cl and Br are not oxidized.

Na2S2O3 + I2 2Na2S2O3 + I2 → Na2S4O6 + 2NaI I2(brown sol.) is decolourized by

(hypo) or hypo. This reaction is used in volumetric
I2 + 2e → 2I– analysis, iodometry (estimation of Cu in
2S2O3–2 → S4O6–2 + 2e CuSO4).

I2 + 2S2O3–2 → S4O6–2 + 2I–

Hydrogen halides, HX (X = F, Cl, Br, I)

Hydrogen halides are covalent diatomic molecules in the gas phase. Hydrogen fluorides in highly associated
molecules through hydrogen bonding. It has effect on its mp, bp and ionization constant in water. All the
halides are acidic in aquous solution and are hydra acids.
428  Basic Concepts of Inorganic Chemistry

Common properties

Table 18.9
Property HF HCl HBr HI

Physical state Liquid Gas Gas Gas

ΔGf Kcal 65 23 13 6.2
Bond energy
135 103 86 71
(KCalmol–1)
Thermal Decreases
stability
mp °C –83 –114.8 –87 –50.7
bp C
°
19.5 –85 –66.8 –35.4
Acidity of aq. Increases
sol.
Ka in water 7.0 x 10–4 107 109 1011

Note
(i) HF is liquid due to extensive hydrogen bonding and so has highest bp.
(ii) ΔGf decreases due to long weaker H – X bond.
(iii) Bond energy decreases from HF to HI due to longer H – X bond with increase in the size of X.
(iv) Bond energy is lowest in H – I. So, it ionizes most and is strongest acid.
Acidity order HF < HCl < HBr < HI

HF
It is prepared by heating CaF2 with conc. H2SO4.
CaF2 + H2SO4   2HF + CaSO4
Successive washing, cooling and fractional distillation give 99.9% HF.

Properties
(i) Gaseous HF is very toxic substance.
(ii) It is highly fuming liquid (bp = 19.5°C).
(iii) It is very soluble in water but the aq. solution is weakly acidic. It is due to high H – F bond strength.
HF + (x + y)H2O   H+(H2O)x + F–(H 2O)y
(iv) It is very corrosive and attacks glass
SiO2 + 4HF   SiF4 + 2H2O
2HF + SiF4   [SiF6]2– + 2H+
Therefore, HF is handled in Cu or Monel metal apparatus.

Uses
(i) In the production of fluorides.
(ii) For etching glass and metals.
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  429

(iii) To produce freons.

(iv) In uranium processing (separation of 235U from 238U, UF6 is used as it is volatile).
(v) To produce synthetic cryolite.
(vi) Aqueous HF is used for pickling steel.
HCl
It can be prepared by heating a soluble chloride with conc. H2SO4.
NaCl + H2SO4 Low NaHSO4 + HCl↑
Temp.
A coating of insoluble NaHSO4 develops on NaCl which prevents further reaction. But at high
temperature (~550°C) Na2SO4 is formed and reaction proceeds.
NaCl + NaHSO4   Na2SO4 + HCl↑
In laboratory HCl can be prepared by treating NH4Cl with conc. H2SO4.
This reaction is smooth as NH4HSO4 soluble.
2NH4Cl + H2SO4   (NH4)2SO4 + 2HCl↑
On large scale HCl is produced by burning H2 in Cl2.
H + Cl ∆ 2HCl
2 2

This HCl is of high purity.

It is also produced in large quantity in the chlorination of organic compounds.

Properties
(i) Pure dry HCl gas is covalent and shows no acidic property.
(ii) HCl is very soluble in water and solution is strong acid. Pure acid is colourless but common grade is
yellowish due to the presence of Fe(111).
(iii) Hydrochloric acid forms a constant boiling mixture (bp 110°C) containing 20% acid by weight.
(iv) Many metals dissolve in HCl and form chlorides.
2Al + 6HCl   2AlCl3 + 3H2
Fe + 2HCl   FeCl2 + H2
All of the chlorides are soluble except AgCl, PbCl2 and Hg2Cl2.

Uses
(i) In the production of Cl2 and chlorides.
(ii) In the preparation of aquaregia, (3HCl + HNO3).
(iii) As a lab reagent.
(iv) The largest use is for pickling metals, (i.e., removing oxide film from the surface).
(v) In the production of dyestuffs and in the sugar industry.

HBr and HI
HBr and HI can not be prepared like HCl. It is because conc. H2SO4 is strong enough an oxidizing agent to
oxidize HBr to Br2 and HI to I2.
2X– X2 + 2e (X = Br and I)
SO4–2 + 2e + 4H+ SO2 + 2H2O
– –2
2X + SO4 + 4H+ X2 + SO2 + 2H2O
430  Basic Concepts of Inorganic Chemistry

HBr
(i) It can be prepared by the hydrolysis of PBr3.
2P + 3Br2 2PBr3
2PBr3 + 6H2O 2H3PO3 + 6HBr
2P + 3Br2 + 6H2O 2H3PO3 + 6HBr
This reaction is brought about by adding bromine, dropwise to a paste of red P and water.
(ii) A bromide on reaction with H3PO4 (a non-oxidizing acid) forms HBr.
NaBr + H3PO4 NaH2PO4 + HBr
(H3PO4 is not an oxidizing agent so HBr is not oxidized to Br2).
HI
(i) It is prepared by heating red P, I2 and water.
2P + 3I2 2PI3
2PI3 + 6H2O 2H3PO3 + 6HI
2P + 3I2 + 6H2O 2H3PO3 + 6HI
(ii) It is also prepared by heating KI and H3PO4 (a non-oxidizing acid)
3KI + H3PO4 K3PO4 + 3HI
(iii) When a mixture of H2 and I2 is heated in the presence of Pt – catalyst, HI is formed.
H +I Pt/∆ 2HI
2 2

Properties
(i) Strongest acid among HF, HCl, HBr and HI.
Acidity order HI > HBr > HCl > HF
(ii) It is strongest reducing agent among HX.
HI reduces Cu2+ to Cu+, e.g.,
CuSO4 + 2HI CuI2 + H2SO4
2CuI2 Cu2I2 + I2
CuSO4 + 2HI Cu2I2 + I2 + H2SO4
This reaction takes place because I– is reducing and reduces Cu+2 to Cu+. This reaction does not take
place with HCl and HBr because Cl– and Br– are not so reducing that they can reduce Cu+2 (CuCl2 and
CuBr2 are stable and CuI2 does not exists).
Uses
(i) In pharmaceutical industry.
(ii) In photography.
(iii) As a reducing agent.

Tests of HI
(i) Forms yellow ppt. with AgNO3 solution
AgNO3 + HI AgI + HNO3
(Yellow ppt.)
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  431

This ppt. is insoluble in NH4OH solution.

(ii) HI forms violet vapours when wormed with conc. H2SO4.
(iii) When Cl2 gas is passed in starch +HI, blue solution results. It is due to oxidation of I– to I2 and adsorption
of I2 in starch channel.
Halides
Binary compounds of halogens are known as halides. Metals and non-metals both form halides.
2Fe + 3Cl2 2FeCl3
2P + 3Br2 PBr3
2Al + 3F2 2AlF3
They form the following classes:
(i) Ionic halides
(ii) Molecular (or covalent) halides.
(iii) Complex halides.

Ionic halides
Most halides of metals in +1, +2 and +3 oxidation states are mainly ionic. Thus,
(i) Alkali metals,
(ii) Alkaline earth metals (except Be)
(iii) Some d – elements and
(iv) Most of the lanthanides
form ionic halides.

Covalent nature in ionic halides

As the charge to radius ratio of Mn+ increases, covalent nature develops in the halides.
For example,
(i) Among KCl, CaCl2, SeCl3 and TiCl4, KCl is completely ionic whereas TiCl4 is a covalent halide.
(ii) For metals which show variable oxidation states, halides in lower oxidation state are more ionic and in
higher oxidation state are more covalent,
SnCl2 → Ionic PbCl2 → Ionic
SnCl4 → Covalent PbCl4 → Covalent
UF4 → Ionic solid UF6 → Covalent gaseous
(iii) Chlorides, bromides and iodides of Ag+, Cu+, Hg+ have enough covalent nature. It is because these metal
ions are small and more polarizing (18e core).
(iv) For halides of a metal covalent bond nature follows the order:
Iodide > Bromide > Chloride > Fluoride
It is because large anions are more polarizable.
So, CaI2 > CaBr2 > CaCl2 > CaF2 Covalent nature decreases.

Solubility of ionic halides

(i) Most of the ionic halides are water soluble. The solubility order being
Iodide > Bromide > Chloride > Fluoride
It is because solubility controlling factor (for ionic halides) is lattice energy which increases as the ionic
radii decrease. The above solubility order is true for alkali, alkaline earth and lanthanide halides.
432  Basic Concepts of Inorganic Chemistry

(ii) The chlorides, bromides and iodides of Ag+, Cu+, Hg+ and Pb+2 are insoluble in water (AgF is soluble due
to very high hydration energy of small F– ion).
(iii) Fluorides of Li, Ca, Sr and Ba are sparingly soluble.

Molecular halides
Non-metals and metals in high oxidation states (+5 and +6) form molecular halides.
BF3, PF3, PCl5, SF6 Non-metal molecular halides
VCl5, UF6, WF6 Metal molecular halides
They are basically covalent and are gases, liquids or volatile solids.

Halide BF3 PCl3 PCl5 UF6

Physical state Gas Liquid Solid Solid

Within the molecule there is covalency (strong force) but between the molecules weak van der Waals
forces exist (hence gas, volatile liquid or solid).
Stability order found in such halides is:
M – F > M – Cl > M – Br > M – I (the bond energy factor).

Molecular fluorides
Fluorine is most oxidizing. Therefore, highest oxidation states of elements are found in fluorides, e.g., SF6,
IF7, WF6, OsF6, UF6 etc., these are generally gases, volatile liquids or solids. The intermolecular forces in
such compounds are only weak van der Waals forces. It is because polarizability of fluorine is very low (F is
very small) and no other suitable outer vacant orbitals exist for other type of bonding.
The M – F bonds are very strong and short. Two factors are responsible,
(i) Polarity of the bond and
(ii) Back bonding, when the central atom has vacant p or d – orbital (B, Si, P, S etc.).

Reactivity
(i) Fluorides are generally less reactive (strong M–F bond, NF3, CF4, SF6 etc).
(ii) A very common reaction of molecular halides is their easy hydrolysis.
PBr3 + 3H2O   H2PO3 + 3HBr
SiCl4 + 4H2O   Si(OH)4 + 4HCl
BCl3 + 3H2O   B(OH)3 + 3HCl
TiCl4 + 2H2O   TiO2 + 4HCl
(iii) When the central atom has its maximum covalency, the halide is inert, (CCl4, SF6).

Structural feature  &O &O &O

$O $O
Many molecular halides are polymeric. It is due to the formation of halide &O &O &O
bridges. Al2Cl6, (BeF2)x, (BeCl2)x etc. Figure 18.2
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  433

Halide complexes
All the halide ions are ligands. They are be formed by reaction between a halide acting as a Lewis acid with
a halide ion acting as a ligand.
PCl5 + Cl–   PCl6–
AlCl3 + Cl–   AlCl4–
FeCl3 + Cl –   FeCl4–
BF3 + F–   BF4–
SiF4 + 2F–   SiF62–
CoCl2 + 2Cl–   CoCl 24 -
They are known in solution as well as in crystalline salts. For example, BF4– is stable in solution whereas
BCl4 and BBr4– are stable in crystalline salts of large cations (lattice energy is responsible).
–

General oder of stability is F > Cl > Br > I.

Many complex halogeno anions are known only in dry state or in non-aquous medium (e.g., NiCl42–).
In many cases steric factor decides stability e.g.,
FeCl4­–, CoCl 24 - , SiCl4 are stable whereas the stable fluoro species are FeF63–, CoF 36- , SiF62– etc.
Halogeno anions are important in many ways:
(i) They are intermediates in many organic reactions where Lewis acids take part e.g., in Friedel–Crafts
reaction AlCl3, BF3 are catalyst and AlCl4– is intermediate.
(ii) Halide complex formation can be used for the separation of metal ions, (Co2+ and Ni2+). They can be
separated by passing a strong HCl solution through an ion–exchange resin. Co2+ forms chlorocomplex
in aq. medium but not Ni2+.
(iii) Large complex halo anions can be used to precipitate salts, e.g., NO+2 BF4–, C6H5N2+ BF4– etc.
(iv) They can be common source material for many elements to prepare their compounds, e.g., chloroplatinic
acid, H2PtCl6.

Preparation of Anhydrous halides

(i) Direct reaction of element with halogen.
2Al + 3Cl ∆ 2AlCl
3 3

2Fe + 3Cl2 ∆ 2FeCl3

Reactivity order of halogen, F > Cl > Br > I.
(ii) Dehydration of halide hydrate. The hydrates can be dehydrated by thionyle chloride (SOCl2) or with
2,2 – dimethoxy propane.
CrCl3.6H2O + 6SOCl2   CrCl3 + 12HCl↑ + 6SO2↑
CH3C(OHe)2CH3
Mgcl2.6H2O MgCl2 + 6(CH3)2CO + 12CH3OH
(iii) Anhydrous fluorides
Fluorine is most oxidizing and it is difficult to work with elemental F many times. Therefore, many
fluorinating agents are used. Example,
IF5, IF7, BrF5, ClF3, XeF2, BiF5, UF6 etc.

Halogen oxides
The halogen oxides are the binary XmOn compounds in which X = Cl, Br, I.
434  Basic Concepts of Inorganic Chemistry

Fluorine is more electronegative than oxygen. Therefore, the binary oxygen compounds of fluorine are
oxygen fluorides not fluorine oxides. So, not discussed here. Important oxides of halogens are given below:

Table 18.10

Halogen +1 +4 +5 +7
Cl Cl2O ClO2 -- Cl2O7
Br Br2O BrO­2 -- --
I -- -- I2O5 --

Dichlorine monoxide (Cl2O)

It is prepared on a laboratory scale (or commercially) by heating fresh yellow HgO with Cl2 gas (or Cl2
dissolved in CCl4).
2HgO + 2Cl2   HgCl2.HgO + Cl2O
Cl2O is a yellow–brown gas (25°C). It is endothermic compound and explodes on heating.
It dissolves readily in water forming an orange solution,
Cl2O + H2O ≡ 2HOCl
Most of the Cl2O is used to produce hypochlorites [NaOCl or Ca(OCl2)2]. These are used as:
(i) Bleaching agent for wood pulp and fabrics.
(ii) Disinfectants.
2
The Cl2O molecule is bent (111°) with Cl – O = 1.71Å
&O &O
Chlorine dioxide (ClO2)
It is highly reactive and can explode violently. Therefore, it is prepared where and as required (i.e., insitu). It
is produced by reducing KClO3 with moist oxalic acid at 90°C.
H2O/90°C
2KClO3 + 2(COOH)2 (COOK)2 + 2ClO2 + CO2 + 2H2O
Commercially, ClO2 is made by reduction of NaClO3 with SO2 in H2SO4 (in the presence of Cl– ions)
2NaClO3 + SO2 + H2SO4   2ClO2 + 2NaHSO4
ClO2 is yellowish gas at room temperature. It is used to produce NaClO2 which is used for bleaching textile
and paper.
2ClO2 + 2NaOH + H2O2   2NaClO2 + O2 + 2H2O

Structure
The molecule, ClO2 is angular (118°) with Cl – O = 1.47Å. It is odd electron molecule (19 electrons) but has
no tendency to dimerize like NO2. It may be due to delocalization of the odd electron.

Dichlorine heptoxide, Cl2O7

It is the most stable and is the only exothermic oxide of chlorine. It is formed by dehydration of HClO4 with
P4O10 at – 10°C.
P4O10
2HClO4 Cl2O7 + [P4O10.H2O]
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  435

Cl2O7 is a colourless liquid. It dissolves in water forming HClO4. It has the structure O3Cl – O – ClO3 with a
ClOCl angle 118.6° at the central oxygen.
Bromine oxides are not well characterized.

Iodine pentaoxides I2O5

It is white crystalline hygroscopic solid. It is produced by heating HIO3 at ~170°C.
2HIO ∆ IO +HO
3 2 5 2

I2O5 is most stable of the halogen oxides (stable upto ~ 300°C). I2O5 reacts as an oxidizing agent (H2S → SO2,
NO → NO2, CO → CO2). The redox reaction with CO is quantitative.
5CO + I2O5   5CO2 + I2
The liberated iodine is determined volumetrically with standard sodium thiosulphate (Na2S2O3).
This method finds use in analyzing exhaust gas from car engines or gases from blast furnances.
With F2, is forms IF5,
2I2O5 + IOF2   4IF5 + 5O2

Structure
2 2
I2O5 has IO3 pyramids sharing one O – atom, i.e., O2IOIO2. , 2 ,
2 2
It has strong intermolecular I - - - O interactions leading to three-dimensional structure.

Oxo acids
The known oxo acids of halogens are given below:


2[LGDWLRQVWDWHRI
)OXRULQH &KORULQH %URPLQH ,RGLQH
KDORJHQ
    
+2) +2&O +2%U +2, 
 D +2&O2 +2%U2   

 +2&O2  +2%U2  +2,2   


+2,2
 +2&O2  +2%U2  
+2  ,2


Note
(i) The oxidation number of +1 can not be assigned to F in HOF as F is most electronegative of all the
elements.
(ii) Acids marked ‘a’ are known only in solution.
(iii) Perchloric acid (HOClO3) can be prepared anhydrous.
(iv) Iodic (HOIO2) and periodic (HOIO3) acids are known in solid state.
436  Basic Concepts of Inorganic Chemistry

Acid strength
(i) Acid strength of HOX, HOXO, HOXO2 and HOXO3 As the number of free O – atoms increases, acid
strength increases. Thus increasing order of acid strength is HOX < HOXO < HOXO2 < HOXO3 (X = the
same halogen).

  It can be explained considering effective negative charge per O – atom on the conjugate bases.

Table 18.11
Acid HOX HOXO HOXO2 HOXO3
Conjugate base XO– XO2– XO3– XO4–
Negative charge per –1 –1/2 –1/3 –1/4
O – atom

The extent of negative charge on each O – atom shows that H+ is strongly attracted by XO– and least
strongly attracted by XO4–. So, the acid strength order is HOX < HOXO < HOXO2 < HOXO3. This order
shows that as oxidation number of halogen increases, acid strength increases (for the same halogen).
PKa HOCl HOClO HOClO2 HOClO3
7.5 1.97 ~ –1 ~ – 10
(ii) Strength of paraperiodic acid [(HO)5IO]. The oxidation state of iodine in this acid is +7 but it is a very
weak acid. It is because negative charge per O – atom in IO6–5 is –5/6 (.– 1).
(iii) Acid strength of
(a) HOCl, HOBr and HOI
As X – O bond polarity increases H – O bond becomes stronger and ionisation of the acid is suppressed.
Therefore, with decrease in the electronegativity of the halogen acid strength decreases.
HOCl > HOBr > HOI
Decreasing order of acid
strength

Similar trend is followed by HOXO2 and HOXO3 (X = Cl, Br, I) series. That is,

HOClO 2 > HOBrO2 > HOIO2 Acid strength

And decreases
HOClO 3 > HOBrO3 > HOIO 3

Oxidizing power
(i) HOX acids (X = Cl, Br, I)
These acids are good oxidzing agents, and oxidizing power decreases as HOCl > HOBr > HOI. It can be
seen in their std potentials.
1
HOX + e + H+ → X + H 2O Cl Br I
2 2
E° (V) 1.63 1.59 1.45

(ii) HOXO3 acids

These acids are strong oxidizing agents and oxidizing power follow the order HOBrO3 > HOIO3 >
HOClO3. It is clear from their E° for the given reaction E° (volts).
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  437

–
XO 4 + 2H+ + 2e → XO3– + H2O Cl Br I
E° (V) 1.23 1.76 1.64

The high oxidizing power of BrO4– may be related to its being thermodynamically less stable than either
ClO4 or IO4–. Lesser thermodynamic stability of BrO4– may be related with weaker Br – O bonds. The Cl – O
–

bond is stronger due to (d – p)π bonding and I – O bonds gets strength due to (f – p) overlap contribution. For
BrO4– (d – p)π bonding is less effective due to large size of 4d orbitals of Br.

Comparison of ClOn– anions

The ClOn– (n = 1, 2, 3, 4) ions are not similar.

Bond properties

Table 18.12
Anion Bond length (Å) Bond energy KJmol–1 Bond angle
–
ClO 1.70 209.0 --
–
ClO2 1.64 245.0 111°
ClO3– 1.57 243.0 106°
ClO4– 1.45 364.0 109° 28’

Note:
(i) The stability increases in the order, ClO– < ClO2– < ClO3– < ClO4–, as bond energy increases.
(ii) Oxidizing power decreases in the order ClO– > ClO2– > ClO3– > ClO4–. The ClO4– ion shows hardly any
oxidizing activity in solution.
(iii) Hypochlorites show redox reaction in any medium.
(iv) Chlorates in solution oxidize only in acid medium
ClO3– + 6I– + 6H+   Cl– + 3I2 + 3H2O
However, strong oxidants in melts, in alkaline medium also
KClO3 + 3MnO2 + 6NaOH   KCl + 3Na2MnO4 + 3H2O
(v) The acid strength and oxidizing power of HClOn (n = 1, 2, 3, 4) acids are in opposite order.

Table 18.13
Property HOCl HOClO HOClO2 HOClO3
Increases
Acid strength

Oxidizing power Decreases

Preparations of oxo acids

Most of the oxo acids and acid anions of halogens are known only in solution. They can be obtained by
reaction of the free halogens with (i) water or (ii) aq. bases.
438  Basic Concepts of Inorganic Chemistry

X2 + H2O   H+ + X– + HOX

X2 + 2NaOH   NaX + NaOX + H2O

(cold dil.)
3X2 + 6NaOH   5NaX + NaOXO2 + 3H2O
(conc. hot)
(X = Cl, Br, I)
All the above reactions are rapid disproportionation of halogens.
The water solution of halogens contains solvated X2 as well as species produced due to a disporportionation
reaction.
Concentration of X2 in water at 25°C (mol l–1)
Table 18.14
Halogen Cl2 Br2 I2
Total solubility 0.091 0.21 0.0013
conc. X2(aq) 0.061 0.21 0.0013
H+ = [X–] = [HOX] 0.030 1.15 x 10–3 6.4 x 10–6

Note:
(i) There is very small concentration of HOBr.
(ii) There is appreciable concentration of HOCl.
(iii) The HOI is negligible in a saturated solution of iodine.

HOF
It is a low temperature compound. It can be prepared by passing F2 over ice and collecting the gas in a trap.
F2 + H2O HOF + HF
HOF is a colourless solid, melts at –117°C. It is unstable and decomposes to HF and O2.

HOX (X = Cl, Br, I)

They can be prepared by the interaction of X2 with HgO in water.
2X2 + 2HgO + H2O   HgO.HgX2 + 2HOX
HOCl is most stable in this group. It can be prepared as:
2Cl2 + 2HgO + H2O   HgO.HgCl2 + 2HOCl
In the vapour phase HOCl is formed in the reaction
H2O(g) + Cl2O(g) 2HOCl(g)
Sodium chlorate (i), NaOCl, is used for bleaching cotton fabric and as domestic bleach (the trade name of
NaOCl is Parazone or Lanry). It is produced commercially by the electrolysis of cold brine, while stirring
vigorously. The reactions are:
Cathode reaction 2H2O + 2e   H2 + 2HO–
Anode reaction 2Cl–   Cl2 + 2e
Cl2 + 2HO–   OCl– + Cl– + H2O
The stirring mixes HO–, formed at the cathode with Cl2 formed at the anode to produce OCl–.
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  439

HOClO (Chlorous acid)

In the series HOXO, HOClO is known but only in solution. It can be made by the raction
Ba(ClO2)2 + H2SO4   BaSO4↓ + 2HOClO
Sodium chlorite may be produced by the reaction
2ClO2 + Na2O2   2NaOClO + O­2
Sodium chlorite is stable in alkaline solution even when boiled. But in acid medium it disproportionate when
heated.
5HOClO   4ClO2 + H+ + Cl– + 2H2O
Chlorites are used as bleaching agents.

Halic acids HOXO2 (X = Cl, Br, I)

All the three halic acids are known. The acids HOClO2 and HOBrO2 are known only in solution and as salts.
Only iodic acid (HOIO2) is stable out of aq. solution. It is a white solid. It can be prepared by oxidizing I2
with conc. HNO3 or O3.
I2 + 10HNO3   2HIO3 + 10NO2 + 4H2O

HOClO2 and HOBrO2

They can be made by treating barium halates with H2SO4.
Ba(ClO3)2 + H2SO4   2HClO3 + BaSO4↓
Ba(ClO3)2 can be prepared by passing Cl2 in Ba(OH)2 solution.
6Ba(OH)2 + 6Cl2   Ba(ClO3)2 + 5BaCl2 + 6H2O
They can also be produced by reactions of X2 with hot aq. base (NaOH)
3X2 + 6HO–   XO3– + 5X– + 3H2O
This reaction is, however, unsuitable for large scale preparations of NaClO3 as only one sixth of the Cl2 can
be converted. Therefore, electrolytic oxidation of brine is used (yield up to 90%).
In practice, electrolysis is followed with vigorous stirring. The reactions are
electrolysis
2Cl– + 2H2O Cl2 + H2 + 2HO–

6NaOH + 3Cl2 NaClO3 + 5NaCl + 3H2O

KClO3 decomposes on heating. The reaction is easy in the presence of the catalyst MnO 2.

400 – 5000 C
(i) 2KClO 3 2KCl + 3O 2
[MnO2 ]
1500 C

Lower
(ii) 4KClOLower
(ii)   4KClO 3KClO 4++KCl
3KClO KCl
Temp. Temp.
3
3 4

Zn(ClO ) 3 )∆
Zn(ClO
3 2 2
Δ 2ZnO +2ZnO
2Cl2 ++5O
2Cl
2 2 + 5O 2

Chlorates are used in matches and fireworks. Sodium chlorate is used as a powerful weed killer.
440  Basic Concepts of Inorganic Chemistry

Perhalic acids HOXO3 (X = Cl, Br, I)

Now all the three perhalic acids are known.

Perchloric acid HOClO3

It can be made by treating anhydrous NaClO4 with conc. HCl
NaClO4 + HCl   HClO4(aq) + NaCl(s)
Commercially NaClO4 is prepared by the electrolysis of aq. NaClO3 (Anode – Pt., Cathode – steel
container)
electrolysis
NaClO3 + H2O NaClO4 + H2
Ammonium perchlorate (NH4ClO4) is an important compound. It is used as an oxidizer in solid rocket
propellants (in missile and space shuttles).
It can be prepared by the reaction
NaClO4 + NH4Cl   NH4ClO4 ↓ + NaCl
Except KClO4, RbClO4 and CsClO4 all other metal perchlorates are water soluble.

Perbromic acid HOBrO3

It is best prepared by oxidation of BrO 3- by F2 in 5M NaOH solution.
BrO3– + F2 + 2HO–   BrO4– + 2F– + H2O
Solution of HBrO4 can be concentrated upto 55% (6M), without decomposition. The hydrates
HBrO4.2H2O can be crystallized.

Periodic acid HOIO3

The common form in aq. solution of this acid is HIO4 and also H5IO6. H5IO6 is called paraperiodic acid (or
orthoperiodic acid). It is a white crystal. It decomposes on heating as
100oC ~200oC
2H5IO6 2HIO4 I2O5 + O2 + H2O
(–4H2O)
–
The IO 4 ion is tetrahedral while (OH)5IO is octahedral. Periodates can be made by oxidizing iodate with Cl2
in alkaline solution.

IO3– + Cl2 + 3HO– H3lO62– + 2Cl–

H3lO32 – + 2H+ H5lO6

100°c
2H5lO6 2HlO4 + 4H2O

The white crystalline acid can be obtained from strongly acid solution. This strong acid can oxidize Mn+2
to MnO4– rapidly and quantitatively. It is a good reagent to oxidize vicinal polyols to carbonyl compounds.

&± 2+ +,2 & 2

+,2
&± 2+ & 2

Figure 18.3
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  441

Structure of oxo anions

Table 18.15
Anions XO– XO2– XO3– XO4–

Total valence electrons 14 20 26 32

No. of bonds (= no. of bps) 1 2 3 4

Electrons for bonds 8 16 24 32

Lone pairs (14–8)/2=3 (20–16)/2=2 (26–24)/2=1 0

Total electron pairs 1+3 = 4 2+2 = 4 3+1=4 4=0=4

Structure Td Td Td Td
Shape Linear Angular Δ pyramidal Td

;2Ā ;2  Ā ;2  Ā ;2  Ā
2

; ; ; ;
2 2 2 2 2 2

2 2 2
/LQHDU  $QJXODU  ǻ3\UDPLG 7HWUDKHGUDO
Figure 18.4
Interhalogen compounds
Halogens form many compounds between themselves. They are called interhalogen compounds. The
following types are known:
1. Neutral molecules: These are all binary compounds of the type XX/n. Where X and X/ are different
halogen atoms, X/ being more electronegative and n is 1, 3, 5 or 7. Most of these compounds contain F
but IF is not stable.

Table 18.16

XX/ ClF(g) BrF(g) BrCl(g) ICl(S) IBr(S)

XX/3 ClF3(g) BrF3(l) ICl3(S) IF3(S)
XX/5 ClF5(g) BrF5(l) IF5(l)
XX/7 IF7(g)

(g = gas, l = liquid, s = solid)

As all valence electrons are paired either as bond pairs or lone–pairs, these compounds are
diamagnetic.
442  Basic Concepts of Inorganic Chemistry

Structure and shape

Table 18.17

Molecules Bond Lone pairs Total electron Structure Shape

pairs pairs

 ;



;
XX/3 3 2 5  T – shaped
;
 ;
WES 


;
;   ;

;
XX/5 5 1 6  Square pyramid
;  ;

2K 

; ;
;


; ;
XX/7 7 0 7   Pentagonal bipyramid
;
;

SES 

2. Interhalogen cations: These compounds are either homonuclear, e.g., I2+, Cl3+ or heteronuclear ClF2+,
BrF4+ etc. There is one ternary cation IBrCl+.

Table 18.18  Interhalogen cations

Triatomic Pentaatomic Heptaatomic

ClF2+ I2Cl+ ClF4+ ClF6+

IBr2+ BrF4+ BrF6+

BrF2+ I2Br+ IF4+ IF6+

ICl2+
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  443

Structure and shape

Table 18.19

Cations Bond pairs Lone pairs Total electron pairs Structure Shape
Triatomic [XX 2] / +
2 2 4 Td Angular
Pentaatomic [XX/4]+ 4 1 5 tbp T-shaped
Heptaatomic [XX 6] / +
6 0 6 Oh Oh

The cations may be either paramagnetic (I2+, 13 valence electrons) or diamagnetic (ICl2+, 20 valence
electrons) depending upon valence electrons.
3. Interhalogen anions: Many anions are known, homo and heteronuclear both. The classical anion is
triiodide ion, I3–. Anions are mostly ternary combinations, e.g., IBrCl–, IBrCl3–, ICl3F– etc.
The anions are generally found in crystalline solids with large cations, Tl+(I3–).

Structure and shape

Table 18.20
Anions Bond pairs Lone pairs Total electron pairs Structure Shape

Triatomic I3–,(IBrCl) 2 3 5 tbp Linear

Pentaatomic (ICl4)– 4 2 6 Oh Square planar

Note: ,
– – – –
The I5 , I4Cl and I4Br ions are not octahedral. The I5 ion is angular. , ,
a  
Pseudohalogens and Pseudohalides , ,
–
Many substances have properties either like X2 or X (X = halogen). They are
Figure 18.5
called pseudohalogens and pseudohalides. They contain two or more atoms in
which one at least is N – atom, such as (CN)2, CN–, SCN etc.
Some pseudohalogens and pseudohalides

Table 18.21
Pseudohalogens Pseudohalides
Cyanogen gas (CN)2 Cyanide ion CN–
Thiocyanogen (SCN)2 Cyanamide ion CN 22 -
Azide ion N 3-
Thiocyanate ion SCN–
Cyanate ion OCN–
Fulminate ion ONC–

The cyanogens gas and CN– ion are best-known pseudohalogen and pseudohalide. They behave like X2
and X–, e.g.,
(a) (CN)2 disproportionate in water like X2.
(CN)2 + H2O → HCN + HOCN
444  Basic Concepts of Inorganic Chemistry

Cl2 + H2O → HCl + HOCl

(b) CN– behaves similar to I–.
2Cu (aq)
2+
+ 4CN(aq)– → 2CuCN + (CN)2

2Cu (aq)
2+
+ 4I– → 2CuI + I2
Both the above reactions are reduction of Cu2+ to Cu+ by CN– and I– ions.
(c) The solubility of metal halides and metal cyanides are very similar,
NaX and NaCN → Water-soluble
AgX and AgCN → Water insoluble
(X = Cl, Br, I)
PbCl2 and Pb(CN)2 → Water insoluble
(d) Like halides pseudohalides (CN–, SCN– etc.) are good ligands CuCl 24 - , ZnCl 24 - , Cu(CN) 24 - ,
Zn(CN) 24 - .
(i)   CN– complexes with transition metals and Zn, Cd and Hg.
(ii)   Most of the CN– complexes are ionic [Fe(CN)6]4–, [Ni(CN)4]2–, [Mn(CN)6]4– etc.
(iii)  CN– can stabilize low oxidation states also, e.g., [Ni(CN)4]2–.

Practice Questions

A. Explain the following in short. (d) Cl2 gas is passed in hot conc. NaOH.
(a) The F – F bond energy is lower than Cl – (e) I2 is boiled with conc. HNO3.
Cl although bond length in F2 is smaller. (f) Cl2 is passed over slaked lime [Ca(OH)2].
(b) The H – F bond is most polar among the (g) Iodine solution is treated with Na2S2O3 (or
H – X, but H – F is weakest acid. write chemical reaction for decolourization
(c) Electron affinity of chlorine is greater than of iodine solution by hypo).
fluorine. (h) CuSO4 solution is treated with excess KI.
(d) Cl2 forms I2 on reaction with KI but I2 fails (i) CuSO4 solution is treated with KCN in the
to form Cl2 with KCl. ratio (Cu+2: CN– = 1: 2)
(e) I2 is insoluble in water but dissolves in a (j) SO2 gas is passed in a solution of sodium
solution of KI. iodate.
(f) F2O2 has very short O – O bond (1.217Å) (k) Chlorine gas is bubbled through a solution
compared to H2O2 (1.84Å). of ferrous bromide.
(g) All the X2 molecules are coloured (X = F, (l) Sodium chloride is heated with solid
Cl, Br, I). K2Cr2O7 and conc. H2SO4.
(h) F2 is gas but I2 is solid. C. Fill in the blanks
(i) AgF is soluble but AgCl is insoluble in (a) Hypo __________ acid is not known at
water. room temperature (HOX, X = F, Cl, Br, I).
(j) When Cl2 reacts with NaOH the products (b) Hydrohalic acid, which dissolves glass, is
vary with temperature. _____________________.
B. What happens when .......? (c) Chlorous acid is a _________________
(a) NH3 is reacted with excess Cl2. acid than hypo chlorous acid.
(b) NaBr is heated with conc. H2SO4. (d) Reaction of perchloric acid with P4O10
(c) NaI is treated with H3PO4. gives ___________________.
 Group 17 (VIIIA) Halogens F, Cl, Br, I and At  445

(e) Chlorine water with KI produces (i) Iodine is practically insoluble in water but
______________ coloured solution. its solubility increases in an aq. solution of
(f) _____­­______ acid gives hypo __________ potassium iodide due to the formation of
ion (hydrobromic, hypobromous, perbro- ________.
mic, bromide, bromite, perbromate). (j) KI in CCl4 produces __________________
(g) Silver fluoride is ____________________ coloured solution with chlorine water.
______________ in water. (k) Iodine reacts with hot conc. NaOH
(h) When an aq. solution of NaF is solution. The products are NaI and
electrolyzed, the gas liberated at anode is ___________________.
___________________.

Objective-Type Questions

  1. Which of the following has highest bond   7. Bromine can be prepared in the laboratory by
energy? (a) Heating KBr with HCl
(a) F2 (b) Cl2 (b) Heating KBr with MnO2 and conc.
(c) Br2 (d) I2 H2SO4.
  2. The correct order of electron attachment (c) Hydrolyzing PBr3 with water.
enthalpy is (d) Passing I2 (vap) in a solution of KBr.
(a) F > Cl > Br > I (b) I > Br > Cl > F   8. Iodine is formed when KI is treated with a
(c) Cl > F > Br > I (d) Cl > Br > F > I solution of
  3. Chlorine gas is passed in a hot concentrated (a) FeSo4 (b) NiSO4
NaOH solution. The product is (c) CuSO4 (d) ZnSO4
(a) NaOCl (b) NaOClO   9. When aq. solution of NaI and NaIO3 are mixed
(c) NaOClO2 (d) NaOClO3 in acid medium, the product is
  4. The following acids have been arranged in the (a) I2 (b) HOIO
order of increasing acid strength. Identify the (c) HOI (d) HOIO3
correct order. 10. Chlorine acts as a bleaching agent only in the
(I)  ClOH presence of
(II)  BrOH (a) Pure oxygen (b) Moisture
(III)  IOH (c) Dry air (d) Sunlight
(a) I < II < III (b) III < II < I 11. Which of the following statements is correct for
(c) II < I < III (d) III < I < II TlI3?
  5. Among the oxy acids of chlorine ClOnH (n = 1, (a) It contains Tl3+ and Br– ions.
2, 3, 4) HOCl is strongest oxidizing agent. It is (b) It is a covalent compound
because (c) It contais Tl•+, I– and lattice I2 molecules.
(a) Oxidation number of Cl in it is lowest (d) It contains Tl+, and I3–.
(b) The Cl – O bond is weakest in it. 12. When iodine is dissolved in CCl4, the colour
(c) Cl is joined with least number of O – that results is
atoms. (a) Bluish green (b) Violet
(d) The ion ClO– is linear in shape. (c) Brown (d) Yellow
  6. The catalyst used in the Deacon’s process for 13. When concentrated HNO3 reacts with iodine,
the large-scale preparation of Cl2 from HCl is the product is
(a) Cu – Zn alloy (b) CuCl2 (a) HOI (b) HOIO
(c) Cu2S (d) CuO (c) HOIO2 (d) HOIO3
446  Basic Concepts of Inorganic Chemistry

14. Hydrogen bond is strongest in (c) Cl – Cl > Br – Br > F – F > I – I

(a) F – H --- N (d) Br – Br > Cl – Cl > F – F > I – I
(b) F – H --- O 21. Euchlorine is mixture of
(c) F – H --- F (a) Cl2 and ClO2
(d) All are equally strong (b) Cl2 and SO2
15. Iodine reacts with hypo to give (c) Cl2 and CO2
(a) Na2SO3 (b) Na2SO4 (d) Cl2 and CO
(c) Na2SO5 (d) Na2S4O6 22. Which of the following reactions is possible?
16. The correct order of oxidizing power is (a) 2NaCl + I2 → 2NaI + Cl2
(a) HOCl > HOClO > HOClO2 > HOClO3 (b) 2NaCl + Br2 → 2NaBr+ Cl2
(b) HOClO3 > HOClO2 > HOClO > HOCl (c) 2NaBr + Cl2 → 2NaCl + Br2
(c) HOClO2 > HOClO3 > HOCl > HOClO (d) 2NaBr + I2 → 2NaI + Br2
(d) HOCl > HOClO2 > HOClO > HOClO3 23. When NaCl (or KCl) is heated with solid
HO– K2CrO7 and conc. H2SO4, the product is
17. The reaction 3ClO (aq)
-
  ClO 3(aq)
-
+ 2Cl (a) Chromous chlorine
-
, is an example of
(aq) (b) Chromic Chloride
(a) Decomposition reaction (c) Chromyl chloride
(b) Reduction reaction (d) Chromyl sulphate
(c) Disporportination reaction 24. The reaction, 2ClO 3- + I2 → 2IO 3- + Cl2
(d) Oxidation reaction
18. Chlorine gas is passed on wet blue litmus. The (a) is not possible
colour is (b) is possible
(a) Red (c) depends upon the temperature
(b) Yellow (d) depends upon the state of products
(c) Colourless 25. Chlorine gas is passed in aquous KI solution.
The colour of solution is
(d) No colour change
19. Which of the follwing is not a pseudohalide? (a) Violet (b) Red
(a) SCN– (b) OCN– (c) Light brown (d) Blue
26. The salt K.ICl2 on heating gives
(c) CNO– (d) RCOO–
20. The correct X – X bond dissociation energy is (a) KCl, ICl (b) KI, Cl2
represented by (c) KCl, I2 (d) KI, KCl, Cl2
(a) F – F > Cl – Cl > Br – Br > I – I [Hint: Alkali metal halide is move stable when
(b) I – I > Br – Br > Cl – Cl > F – F either the halogen or the metal is small].

Answers

1. (b) 2. (c) 3. (c) 4. (b) 5. (b) 6. (b) 7. (b) 8. (c) 9. (a) 10. (b)
11. (d) 12. (b) 13. (c) 14. (c) 15. (d) 16. (a) 17. (c) 18. (c) 19. (d) 20. (c)
21. (a) 22. (c) 23. (c) 24. (b) 25. (c) 26. (a)
 19
Group – 18, The
Noble Gases

Helium, Ne, Ar, Kr, Xe and Rn are noble gases and elements of group 18 (or zero group). They are minor
constituents of the atmosphere. Sir William Ramse first isolated Ne, Ar, Kr and Xe. He also established He.
It is found in stars, in radioactive minerals and some natural gasses. Its origin is entirely from the decay of
thorium and uranium isotopes, which emit α-particles. The last member of the group Rn is radioactive (all
isotopes). These gases are obtained by fractionation of liquid air.

Properties
Table 19.1
Elements Out electron Radii (Å) Ionization energy Volume % in atmosphere
configuration KJmol−1 (x 10−14)
He 1s2 1.20 2369 5.2
Ne 2s 2p
2 6
1.60 2078 18.2
Ar 3s23p6 1.91 1519 9340.0
Kr 4s24p6 2.00 1349 11.4
Xe 5s 5p
2 6
2.20 1169 0.08
Rn 6s26p6 – 1036 –

Note
(i) Ar is most abundant and Kr is least

Atomicity
All noble gases are monoatomic. It is due to closed-shell electron configuration. Monoatomic nature can be
explained by
(a) CP/CV ratio or
(a) Molecular orbitals model
The CP/CV ratio for monoatomic gases is 1.66. For all noble gas this ratio is almost equal to 1.66. Hence, all
are monoatomic.
Molecular orbital model also explains their monoatomic nature.
448  Basic Concepts of Inorganic Chemistry

He is 1s2. If it forms He2 the MO diagram is

V V

±
%2  
V V 
%H %H
V V
Figure 19. 1

Thus, there is no bond between He and He. It is, therefore, monoatomic. For others also, as the valence
shell is closed, octet bond order will become zero. It shows their monoatomic nature.

Radii
All noble gases are monoatomic. There radii is non-bonded radii i.e., van der Waals’ radii. Therefore, they
have large atomic radii. The radii of halogens are covalent radii. Therefore, in each period, radii of noble gas
atom is larger than its preceding halogen. It is opposite to the trend found upto group 17.

Table 19.2
Noble gases
Halogen Gr – 17 Radii (Å) Radii (Å)
Gr - 18
F 0.71 Ne 1.60
Cl 0.99 Ar 1.91
Br 1.14 Kr 2.00
I 1.33 Xe 2.20

Water Solubility
Noble gases are more soluble in water than that of N2 or O2. The solubility of noble gases increases with
increase in atomic number. The solubility is due to dipole induced dipole interaction. As polarizabillity of an
atom (or ion) depends on its size, the larger the noble gas atom more polarizable it is. Therefore, solubility
increases down the group.

Special properties of He
He has some peculiar properties. Such as:
(i) It has lowest bp (4K) of any known substance.
(ii) It has no triple point that is, there is no combination of temperature and pressure at which solid, liquid
and gas co-exist at equilibrium.
(iii) It cannot be solidified at atmospheric pressure.
(iv) Its zero point energy is very high.
Liquid He has two forms—He(I) at 4.2K and He(II) at around 2.2K. The change from He(I) to He(II) is
followed with many remarkable changes:
 Group – 18, The Noble Gases  449

(i) He(II) is super conductor.

(ii) Its thermal conductivity is enormously large (800 times more than Cu).
(iii) Its viscosity is negligible. Liquids having such a low viscosity are known as super fluids. Because of this
property, He(II) is also called fourth state of matter.

Uses of Noble Gases

(i) The main use of He is as the cryoscopic liquid.
(ii) Neon is used for discharge lighting tubes (orange glow of ‘neon’ signs).
(iii) Argon is mainly used to create inert atmosphere (in laboratory apparatus, in welding and in electric
bulb, in G – M counter).
(iv) Radon is used as a source of α-particle in the treatment of cancer.

Compounds of Noble Gases

1.  Clathrate compounds
2.  True chemical compounds

Clathrate
Clathrates (Latin – Clathratus meaning ‘enclosed’) are species which contain atoms or molecules trapped in
the cavities of a host lattice. They contain neither ionic nor covalent bonds. The van der Waals’ type force
is responsible for their stability. Most of the clathrates have host which are H – bonded structure, Example,
water – clathrate, quinol – clathrate etc.
10–40 Atom
Kr + p – C6H4(OH)2 crystal.
The clathrate is shown below:

2
+ 2
2
+
$U
2
+ 2 +
2
+
Figure 19.2

He and Ne do not form clathrate because they are small enough to be trapped.
Xe compounds
The first true chemical compound of Xe was prepared by Niel Bartlett (Canada – 1962). Dioxygen reacts with
PtF6 (a strong oxidizing agent) to form a red solid.
O2 + PtF6   O 2 [PtF6]
+ −

O2 and Xe have almost equal first ionization energy (~12 ev). This led Bartlett to think that Pt F6 should
also react with Xe. He tried the reaction and got a yellowish solid.
Xe + PtF6    Yellow solid
450  Basic Concepts of Inorganic Chemistry

The yellow solid has complex constitution [XeF]+ [Pt2F11]−, but simply may be represented as Xe+
[PtF6]−. Later on, it was also found that F2 reacts with Xe. It forms three types of compounds:
1.  Fluorides,
2.  Oxyfluorides
3.  Oxides and Oxoanions
However, oxygen does not react directly with Xe. The oxygen derivatives are obtained from fluorides.
Some compounds having Xe – Cl and Xe – N bonds are also reported.

Xe fluorides
Xenon reacts directly with fluorine (only). The products depend on respective amounts of Xe and F2 and
temperature also. The reactions are generally carried out in sealed tubes.

;H) 
'SUHVVXUH


;H)  ;H) 
'SUHVVXUH


;H) 
'SUHVVXUH
Figure 19.3

• These three fluorides are crystalline volatile substances which sublimes at room temperature but can be
kept in nickel containers.
• The fluorides are strong oxidizing agents.
XeF2 + 2HCl   Xe + Cl2 + 2HF
XeF4 + 4KI   Xe + 2I2 + 4KF
XeF2 + Ce2(SO4)3 + SO -42   Xe + 2Ce(SO4)2 + F2
• They are good fluorating agents also.
2SF4 + XeF4   2SF6 + Xe

Pt + XeF4   PtF4 + Xe
)
;H) ;H+)

The fluorides differ in reaction with water.

(a) XeF2 is water soluble and undergoes slow oxidative hydrolysis.
2XeF2 + 2H2O   2Xe + O2 + 4HF
(b) XeF4 reacts with water violently giving XeO3.
3XeF4 + 6H2O   2Xe + XeO3 + /2O2 + 12HF
3
 Group – 18, The Noble Gases  451

In this reaction, XeF4 disproportionates as well as H2O is partly oxidized.

(c) XeF6 also reacts violently to give XeO3
XeF6 + 6H2O   XeO3 + 12HF
  XeO3 is a white deliquescent solid which is dangerously explosive. But with small amount of
water XeF6 forms XeOF4.
XeF6 + H2O   XeOF4 + 2HF
•  XeF6 is extremely reactive and reacts even with quartz (SiO2) to form a colorless liquid XeOF4.
2XeF6 + SiO2   2XeOF4 + SiF4
•  XeO3 reacts with NaOH solution (pH > 10) to form sodium xenate ion
XeO3 + NaOH   HXeO 4 + Na
- +

•  The xenate ion, HXeO -4 , slowly disproportionate in basic medium to Xe and perxenate ion
2 HXeO -4 + 2HO− fi Xe + XeO 64 - + O2 + 2H2O
  The perxenate solutions are yellow and are powerful and rapid oxidants.

Some Xe compounds
Table 19.3
Compound Form MP(°C) Structure Shape

XeF2 Colourless 129 Trigonal Linear

crystal bipyramid
XeF4 Do 117 Octahedral Sq. planer
XeF6 Do 49.6 Pentagonal Distorted Oh.
bipyramid
XeO3 Do Explodes Tetrahedral Trigonal
pyramid
XeO4 Colourless gas – 39.5 Tetrahedral Tetrahedral
XeOF4 Colourless – 46 Octahedral Square
liquid pyramid
XeO2F2 – – Trigonal Distorted Td.
bipyramid
XeO3F2 – – Do Trigonal
bipyramid

XeO 64 - Colourless salt – Octahedral Octahedral

Note:
1. In tbp structure lp and O – atom occupy equatorial positions
2. In octahedral structure, lp occupy axial position.
452  Basic Concepts of Inorganic Chemistry

Structures
Table 19.4
Molecule Structure
)

XeF2 ;H

) )
XeF4 ;H
) )
)
)
XeF6 ;H )
)
)
)

;H
XeO3
2
2
2
2
) )
XeOF4 ;H
) )

)
2
XeO2F2 2 ;H

)
2
XeO3F2 2 ;H
2
)
 Group – 18, The Noble Gases  453

Practice Questions

A. Explain the following in brief: (e) XeF4 is square planar, from VSEPR model.
(a) Noble gases are monoatomic. (f) He is found in certain minerals.
(b) Solubility of noble gases increases in water B. Complete the following equation:
with increase in atomic number.
(c) In each period, atomic radius of noble gas (a) XeF4 + H2O  
is highest (or atomic radius of Ne is larger (b) SiO2 + XeF6  
than F). (c) XeF4 + SF4  
(d) Clathrates are not true chemical (d) HXeO -4 + HO−  
compounds. (e) Ba2XeO6 + H2SO4  

Objective-Type Questions

  1. Shape of XeOF4 is   6. In the structure of XeO2F2

(a) Trigonal bipyramid with lp at axial (a) lp and O – atoms are at equatorial positions
position. (b) lp and F – atoms are at equatorial positions
(b) Square pyramid with lp at axial positon. (c) O – atom and F – atoms are at equatorial
(c) Distorted square pyramid with lp at axial positions
position. (d) F atoms are at equatorial positions and lp is
(d) Square pyramid with lp at square plane. at the axial position
  7. Which of the following noble gas is used in G –
  2. Which of the following liquids has the property
M counter?
of a superfluid?
(a) Ne (b) Ar
(a) Liquid NH3
(c) Kr (d) Xe
(b) Liquid N2   8. Which of the following noble gases is not
(c) Liquid O2 expected to form a clathrate?
(d) Liquid He(I) (a) Ne (b) Ar
  3. Which of the following noble gas is not found (c) Kr (d) Xe
in atmosphere?   9. Which of the following statements is not correct
(a) He (b) Ar for liquid He(II)?
(c) Xe (d) Rn (a) Its thermal conductivity is very low.
  4. The inert gas which is most abundant is (b) It is a superconductor.
(a) Ne (b) Ar (c) It has no triple point.
(c) Kr (d) Xe (d) Its viscosity is negligible.
  5. The hybridization of Xe in XeO2F2 is 10. XeF6 reacts with excess water to give
(a) sp3 (b) sd3 (a) XeO4 (b) XeO3
(c) XeOF4 (d) XeO 64 -
(c) sp3d (d) sp3d2

Answers

1. (c) 2. (d) 3. (d) 4. (b) 5. (c) 6. (a) 7. (b) 8. (a) 9. (a) 10. (b)