Chapter

18
s and p-Block Elements

Alkali Metals and Their Compounds (ii) Being highly electropositive in nature, it is not possible to apply
the method of displacing them from their salt solutions by any other
The group 1 of the periodic table contains six elements, namely element.
lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) and (iii) The aqueous solutions of their salts cannot be used for
francium (Fr). All these elements are typical metals. Francium is radioactive extraction by electrolytic method because hydrogen ion is discharged at
with longest lived isotope 223 Fr with half life period of only 21 minute. cathode instead of an alkali metal ions as the discharge potentials of alkali
metals are high. However, by using Hg as cathode, alkali metal can be
These are usually referred to as alkali metals since their hydroxides form
deposited. The alkali metal readily combines with Hg to form an amalgam
strong bases or alkalies.
from which its recovery difficult. The only successful method, therefore, is
(1) Electronic configuration the electrolysis of their fused salts, usually chlorides. Generally, another
metal chloride is added to lower their fusion temperature.
Elements Discovery Electronic configuration ( ns 1 )
Fused NaCl : NaCl   Na   Cl –
fusion

3 Li
Arfwedson (1817) [He]2 2 s 1 Electrolysis : Anode : 2Cl   Cl 2  2e 
Davy (1807) of fused salt: Cathode : 2 Na   2e   2 Na
11 Na [Ne]10 3 s 1
(4) Alloys Formation
Davy (1807) [Ar]18 4 s 1 (i) The alkali metals form alloys among themselves as well as with
19 K

Bunsen (1861) other metals.

37 Rb [Kr]36 5 s 1 (ii) Alkali metals also get dissolved in mercury to form amalgam
Bunsen (1860) [Xe] 54 6 s 1 with evolution of heat and the amalgamation is highly exothermic .
55 Cs
Physical properties
Fr Percy (1939) [Rn]86 7 s 1
87 (1) Physical state
(2) Occurrence : Alkali metals are very reactive and thus found in (i) All are silvery white, soft and light solids. These can be cut with
combined state some important ores of alkali metals are given ahead. the help of knife. When freshly cut, they have bright lustre which quickly
(i) Lithium : Triphylite, Petalite, lepidolite, Spodumene [LiAl(SiO ) ], 3 3 tarnishes due to surface oxidation.
Amblygonite [Li(Al F)PO ] 4
(ii) These form diamagnetic colourless ions since these ions do not
(ii) Sodium : Chile salt petre (NaNO ), Sodium chloride (NaCl),
3 have unpaired electrons, (i.e. M has ns configuration). That is why alkali
+ 0

Sodium sulphate (Na SO ), Borax (Na B O 10H O), Glauber salt (Na SO .10H O)
2 4 2 4 7 2 2 4 2 metal salts are colourless and diamagnetic.
(iii) Potassium : Sylime (KCl), carnallite (KCl.MgCl .6H O) and 2 2 (2) Atomic and ionic radii
Felspar (K O.Al O .6SiO )
2 2 3 2 (i) The alkali metals have largest atomic and ionic radii than their
(iv) Rubidium : Lithium ores Lepidolite, triphylite contains 0.7 to 3% successive elements of other groups belonging to same period.
Rb O
2
(ii) The atomic and ionic radii of alkali metals, however, increases
(v) Caesium : Lepidolite, Pollucite contains 0.2 to 7% Cs O down the group due to progressive addition of new energy shells.
2

(3) Extraction of alkali metals : Alkali metals cannot be extracted by No doubt the nuclear charge also increases on moving down the
the usual methods for the extraction of metals due to following reasons. group but the influence of addition of energy shell predominates
Li Na K Rb Cs Fr
(i) Alkali metals are strong reducing agents, hence cannot be
Atomic radius (pm) 152 186 227 248 265 375
extracted by reduction of their oxides or other compounds.
Ionic radius of M+ 60 95 133 148 169 –
ions (pm) K Cr O is orange because of orange coloured Cr O ion, KMnO is violet
2 2 7 2 7
2-

(3) Density because of violet coloured MnO ion. 1-

(i) All are light metals, Li, Na and K have density less than water. (7) Hydration of Ions
Low values of density are because these metals have high atomic volume (i) Hydration represents for the dissolution of a substance in water
due to larger atomic size. On moving down the group the atomic size as to get adsorb water molecule by weak valency force. Hydration of ions is
well as atomic mass both increase but increase in atomic mass the exothermic process (i.e energy is released during hydration) when ions
predominates over increase in atomic size or atomic volume and therefore on dissolution water get hydration.
the ratio mass/volume i.e. density gradually increases down the groups
(ii) The energy released when 1 mole of an ion in the gaseous state
(ii) The density increases gradually from Li to Cs, Li is lightest
is dissolved in water to get it hydrated is called hydration energy
known metal among all.

Li = 0.534, Na = 0.972, K = 0.86, Rb = 1.53 and Cs = 1.87 M (g)  Aq  M  (aq) ; H  – ve .
g/ml at 20 C.0

(iii) Smaller the cation, greater is the degree of hydration. Hydration

(iii) K is lighter than Na because of its unusually large atomic size. energy is in the order of, Li > Na > K > Rb > Cs + + + + +

(iv) In solid state, they have body centred cubic lattice.

(iv) Li being smallest in size has maximum degree of hydration and
+

(4) Melting point and Boiling point that is why lithium salts are mostly hydrated, LiCl. 2H O also lithium ion 2

(i) All these elements possess low melting point and boiling point in being heavily hydrated, moves very slowly under the influence of electric
comparison to other group members. field and, therefore, is the poorest conductor current among alkali metals
Li Na K Rb Cs Fr ions It may, therefore, be concluded that it is the degree of hydration as
melting point (K) 453.5 370.8 336.2 312.0 301.5 – well as the size of ion is responsible for the current carried by an ion.
boiling point (K) 1620 1154.4 1038.5 961.0 978.0 – Relative ionic radii Cs+ > Rb+ > K+ > Na+ > Li+
(ii) The lattice energy of these atoms in metallic crystal lattice Relative hydrated ionic radii Li+ > Na+ > K+ > Rb+ > Cs+
relatively low due to larger atomic size and thus possess low melting point
Relative conducting power Cs+ > Rb+ > K+ > Na + > Li+
and boiling point on moving down the group, the atomic size increases and
binding energy of their atoms in crystal lattice decreases which results (8) Electronegativity, Electro positivity and metallic character.
lowering of melting point. (i) These metals are highly electropositive and thereby possess low
(iii) Lattice energy decreases from Li to Cs and thus melting point values of electronegativities. Metallic character and electro positivity increase
and boiling also decreases from Li to Cs. from Li to Cs (Li < Na < K < Rb < Cs)
(5) Ionisation energy and electropositive or metallic character (ii) Electronegativity of alkali metals decreases down the group as
(i) Due to unpaired lone electron in ns sub-shell as well as due to the trend of numerical values of electronegativity given below on Pauling
their larger size, the outermost electron is far from the nucleus, the removal scale suggests.
of electron is easier and these low values of ionisation energy. (I.E.) Li Na K Rb Cs Fr
(ii) Ionisation energy of these metal decreases from Li to Cs. Electronegativity 0.98 0.93 0.82 0.82 0.79 –
Ionisation energy Li Na K Rb Cs Fr Fr being radioactive elements and thus studies on physical
IE1 520 495 418 403 376 – properties of this element are limited.
IE2 7296 4563 3069 2650 2420 – (9) Specific heat : It decreases from Li to Cs.
A jump in 2nd ionisation energy (huge difference) can be explained Li Na K Rb Cs Fr
as, Specific heat (Cal/g) 0.941 0.293 0.17 0.08 0.049 –
Re movalof Re moval of (10) Conduction power : All are good conductors of heat and
Li :1s 2 2 s1  Li  :1s 2  Li 2  : 1s1 electricity, because of loosely held valence electrons.
2 s electron 1 s electron (11) Standard oxidation potential and reduction properties
Removal of 1s electrons from Li and that too from completely filled
+
(i) Since alkali metals easily lose ns electron and thus they have high 1

configuration requires much more energy and a jump in 2nd ionisation is values of oxidation potential i.e.,
noticed. M  aq  M  (aq)  e
(iii) Lower are ionisation energy values, greater is the tendency to (ii) The standard oxidation potentials of a alkali metals (in volts) are
lose ns electron to change in M ion (i.e. M  M +e ) and therefore stronger is
1 + + –
listed below,
electropositive character. Li Na K Rb Cs
(iv) Electropositive character increases from Li to Cs. +3.05 +2.71 +2.93 +2.99 +2.99
Due to their strong electropositive character, they emit electrons even (iii) More is oxidation potential, more is the tendency to get oxidized
and thus more powerful is reducing nature in aqueous medium that is why
when exposed to light showing photoelectric effect. This property is
alkali metals liberate H from H O and HCl.
responsible for the use of Cs and K in photoelectric cell. 2 2

2 H 2O  2 M  2 MOH  H 2 ; 2 HCl  2 M  2 MCl  H 2

(6) Oxidation number and valency
(iv) However, an examination of ionisation energy for alkali metals
(i) Alkali metals are univalent in nature due to low ionisation energy reveals that Li should have the minimum tendency to lose electron and thus
values and form ionic compounds. Lithium salts are, however, covalent. its reducing nature should be minimum. The greatest reducing nature of Li
(ii) Further, the M ion acquires the stable noble gas configuration. It
+
in aq. medium is accounted due to the maximum hydration energy of Li +

requires very high values of energy to pull out another electron from next ion. For Lithium
to outer shell of M ion and that is why their second ionisation energy is
Li(s)  Li(g) ;
+

H = Heat of sublimation, H
very high. Consequently, under ordinary conditions, it is not possible for 1 s

these metals to form M ion and thus they show +1 oxidation state. 
Li(g)  Li  e ; H = IE
2+

(g) 2 1

(iii) Since the electronic configuration of M ions do not have +

 
unpaired electron and thus alkali metal salts are diamagnetic and colourless. Li (g)  Li (aq); H = – Heat of hydration, H
3 h

Only those alkali metal salts are coloured which have coloured anions e.g.
Li(s)  H 2O  Li (aq )  e ; H  H1  H 2  H 3  H s  IE1  H h whereas Na does so vigorously, K reacts producing a flame and Rb, Cs do
so explosively.
Similarly, for sodium,
1
Na(s)  H 2 O  Na  (aq)  e ; H  H(s)  IE1  H h M  H 2 O  MOH  H2
2
H for Li > H for Na. Therefore, large negative H values are
h h (v) The basic character of oxides and hydroxides of alkali metals
observed in case of Li and this explains for more possibility of Li to get increases from Li to Cs. This is due to the increase in ionic character of
itself oxidized or have reducing nature. alkali metal hydroxides down the group which leads to complete dissociation
(12) Characteristic flame colours : The alkali metals and their salts and leads to increase in concentration of OH ions. –

give characteristic colour to Bunsen flame. The flame energy causes and (2) Hydrides
excitation of the outermost electron which on reverting back to its initial (i) These metals combine with H to give white crystalline ionic
position gives out the absorbed energy as visible light. These colour differ hydrides of the general of the formula MH.
from each other Li –crimson, Na–Golden yellow, K – Pale violet , Rb-Red
violet and Cs –Blue violet. These different colours are due to different (ii) The tendency to form their hydrides, basic character and
ionisation energy of alkali metals. The energy released is minimum in the stability decreases from Li to Cs since the electropositive character
case of Li and increases in the order.
+
decreases from Cs to Li.
Energy released : Li+ < Na+ < K+ < Rb+ < Cs+ 2M+ H  2MH ; Reactivity towards H is Cs < Rb < K < Na < Li.
2 2

 released : Li+ > Na+ > K+ > Rb+ > Cs+ (iii) The metal hydrides react with water to give MOH and H ; MH 2

Frequency released : Li+ < Na+ < K+ < Rb+ < Cs+ + H O  MOH + H
2 2

Chemical properties (iv) The ionic nature of hydrides increases from Li to Cs because of
(1) Formation of oxides and hydroxides the fact that hydrogen is present in the these hydrides as H and the smaller –

cation will produce more polarisation of anion (according to Fajans rule)

(i) These are most reactive metals and have strong affinity for O 2
and will develop more covalent character.
quickly tranish in air due to the formation of a film of their oxides on the
surface. These are, therefore, kept under kerosene or paraffin oil to protect them (v) The electrolysis of fused hydrides give H at anode. 2

 
from air, NaH fused Contains Na and H i.e.,
M  O2  M 2 O  M 2 O2 1
Oxide Peroxide At cathode: Na +e  Na; + –
H2  e At anode: H  
2
(ii) When burnt air (O ), lithium forms lithium oxide (Li O) sodium
(vi) Alkali metals also form hydrides like NaBH , LiAlH which are
2 2

forms sodium peroxide (Na O ) and other alkali metals form super oxide 4 4

good reducing agent.

2 2

(Mo i.e. KO ,RbO or CsO )

2 2 2 2

(3) Carbonates and Bicarbonates

1
2 Li  O 2  Li 2 O ; 2 Na  O 2  Na 2 O 2 (i) The carbonates (M CO ) & bicarbonates (MHCO ) are highly
2 Lithuim oxide
2 3 3

stable to heat, where M stands for alkali metals.

K  O2  KO 2 (ii) The stability of these salts increases with the increasing
Potassium super oxide electropositive character from Li to Cs. It is therefore Li CO decompose on 2 3

The reactivity of alkali metals towards oxygen to form different heating, Li CO  Li O+CO
2 3 2 2

oxides is due to strong positive field around each alkali metal cation. Li +

(iii) Bicarbonates are decomposed at relatively low temperature,

being smallest, possesses strong positive field and thus combines with small 0
anion O to form stable Li O compound. The Na and K being relatively
2–

2
+ +
2 MHCO 3   M 2 CO 3  H 2 O  CO 2
300 C

larger thus exert less strong positive field around them and thus reacts with (iv) Both carbonates and bicarbonates are soluble in water to give
larger oxygen anion i.e, O22 and O12  to form stable oxides. alkaline solution due to hydrolysis of carbonate ions or bicarbonate ions.
(4) Halides
The monoxide, peroxides and superoxides have O and O 22  , O 12 ions 2

respectively. The structures of each are, (i) Alkali metals combine directly with halogens to form ionic halide
... . .. .. ... .. MX .
: O .. .. .. O : [ x O . . O x]2 [:O O:] –
1–

Monoxide (O ) Peroxide (O ) 2
2–
Superoxide (O ) 2
– (ii) The ease with which the alkali metals form halides increases
from Li to Cs due to increasing electropositive character from Li to Cs.
2

The O ion has a three electron covalent bond and has one electron
2
–1

unpaired. It is therefore superoxides are paramagnetic and coloured KO is 2

(iii) Lithium halides however have more covalent nature. Smaller is
light yellow and paramagnetic substance. the cation, more is deformation of anion and thus more is covalent nature
(iii) The oxides of alkali metals and metal itself give strongly alkaline in compound. Also among lithium halides, lithium iodide has maximum
solution in water with evolution of heat covalent nature because of larger anion which is easily deformed by a
1 cation. Thus covalent character in lithium halides is, LiI > LiBr > LiCl > LiF
M  H 2 O  MOH  H2; H  ve (iv) These are readily soluble in water. However, lithium fluoride is
2
sparingly soluble. The low solubility of LiF is due to higher forces of
Li2O  H 2O  2 LiOH; H  ve
attractions among smaller Li and smaller F ions (high lattice energy).
+ –

Na 2 O 2  2 H 2 O  2 NaOH  H 2 O 2(l) ; H  ve (v) Halides having ionic nature have high m.pt. and good conductor
2 KO 2  2 H 2 O  2 KOH  H 2 O2(l)  O2(g) ; H  ve of current. The melting points of halides shows the order, NaF > NaCl >
NaBr > Nal
The peroxides and superoxides act as strong oxidising agents due (vi) Halides of potassium, rubidium and caesium have a property of
to formation of H O 2 2
combining with extra halogen atoms forming polyhalides.
(iv) The reactivity of alkali metals towards air and water increases
from Li to Cs that is why lithium decomposes H O very slowly at 25 C o
KI + I KI ; In KI the ions K and I are present
2 3 3(aq)
+ –

2
 (5) Solubility in liquid NH 3
(10) Complex ion formation : A metal shows complex formation
(i) These metals dissolve in liquid NH to produce blue coloured 3
only when it possesses the following characteristics, (i) Small size (ii)
solution, which conducts electricity to an appreciable degree. High nuclear charge (iii) Presence of empty orbitals in order to accept
(ii) With increasing concentration of ammonia, blue colour starts electron pair ligand. Only Lithium in alkali metals due to small size forms a
changing to that of metallic copper after which dissolution of alkali metals few complex ions Rest all alkali metals do not possess the tendency to form
in NH ceases. complex ion.
3

(iii) The metal atom is converted into ammoniated metal in i.e. M +

Anomalous behaviour of Lithium
(NH ) and the electron set free combines with NH molecule to produce Anomalous behaviour of lithium is due to extremely small size of
3 3

ammonia solvated electron. lithium its cation on account of small size and high nuclear charge, lithium
exerts the greatest polarizing effect out of all alkali metals on negative ion.
Na  (x  y)NH 3  [ Na( NH 3 )x ]  [e(NH 3 )y ] Consequently lithium ion possesses remarkable tendency towards solvation
Ammoniated cation Ammoniated electron and develops covalent character in its compounds. Li differs from other
(iv) It is the ammoniated electron which is responsible for blue alkali metals in the following respects,
colour, paramagnetic nature and reducing power of alkali metals in (1) It is comparatively harder than other alkali metals. Li can’nt be
ammonia solution. However, the increased conductance nature of these stored in kerosene as it floats to the surface, due to its very low density. Li
metals in ammonia is due to presence of ammoniated cation and ammonia is generally kept wrapped in parrafin wax.
solvated electron. (2) It can be melted in dry air without losing its brilliance.
(v) The stability of metal-ammonia solution decreases from Li to Cs. (3) Unlike other alkali metals, lithium is least reactive among all. It
(vi) The blue solution on standing or on heating slowly liberates can be noticed by the following properties,
hydrogen, 2M + 2NH  2MNH + H . Sodamide (NaNH ) is a waxy solid,
3 2 2 2 (i) It is not affected by air. (ii) It decomposes water very slowly to
used in preparation of number of sodium compounds. liberate H . (iii) It hardly reacts with bromine while other alkali metals react
2

(6) Nitrates : Nitrates of alkali metals (MNO ) are soluble in water 3

violently.
and decompose on heating. LiNO decomposes to give NO and O and rest
3 2 2
(4) Lithium is the only alkali metal which directly reacts with N to 2

all give nitrites and oxygen. form Lithium nitride (Li N) 3

2MNO  2MNO + O (except Li)

3 2 2
(5) Lithium when heated in NH forms amide, Li NH while other 3 2

metals form amides, MNH .

4 LiNO 2Li O + 4NO + O 2

(6) When burnt in air, lithium form Li O sodium form Na O and

3 2 2 2

(7) Sulphates
2 2

Na O other alkali metals form monoxide, peroxide and superoxide.

2 2

(i) Alkali metals’ sulphate have the formula M SO . 2 4

(7) Li O is less basic and less soluble in water than other alkali
2

(ii) Except Li SO , rest all are soluble in water.

2 4 metals.
(iii) These sulphates on fusing with carbon form sulphides, M SO + 2 4 (8) LiOH is weaker base than NaOH or KOH and decomposes on
4C  M S + 4CO 2
heating.
(iv) The sulphates of alkali metals (except Li) form double salts with 
2 LiOH  Li 2 O  H 2 O
the sulphate of the trivalent metals like Fe, Al, Cr etc. The double sulphates
crystallize with large number of water molecules as alum. e.g. KSO . Al (SO ) . 24 2 4 2 4 3
(9) LiHCO is liquid while other metal bicarbonates are solid.
3

HO.
2
(10) Only Li CO decomposes on heating
2 3

(8) Reaction with non-metals Li 2 CO 3   Li 2 O  CO 2 .

heat

(i) These have high affinity for non-metals. Except carbon and
Na CO , K CO etc. do not decompose on heating.
nitrogen, they directly react with hydrogen, halogens, sulphur, phosphorus 2 3 2 3

etc. to form corresponding compounds on heating. (11) LiNO and other alkali metal nitrates give different products on
3

0
heating
2Na + H   2NaH
300 C
2
; 2K + H 2KH
2 4LiNO = 2Li O+4NO + O ; 2NaNO = 2NaNO + O
3 2 2 2 3 2 2

2Na + Cl  2NaCl ; 2K + Cl  2KCl

2 2
(12) LiCl and LiNO are soluble in alcohol and other organic 3

solvents. These salts of other alkali metals are, however, insoluble in organic
2Na + S  Na S ; 2K + S  K S
2 2
solvents.
3Na + P  Na P 3
; 3K + P  K P 3
(13) LiCl is deliquescent while NaCl, KBr etc. are not. Lithium
(ii) Li reacts, however directly with carbon and nitrogen to form chloride crystals contain two molecules of water of crystallisation ( LiCl.
carbides and nitrides. 2H O). Crystals of NaCl KBr, KI etc do not conation water of crystallisation.
2

2Li + 2C  LiC ; 6Li + 2N  2 Li N 2 2 3

(14) Li SO does not form alums like other alkali metals.
2 4

(iii) The nitrides of these metals on reaction with water give NH . 3 (15) Li reacts with water slowly at room temperature Na reacts
M N + 3H O  3MOH + NH
3 2 3
vigorously Reaction with K. Rb and Cs is violent.
(9) Reaction with acidic hydrogen : Alkali metals react with acids (16) Li reacts with Br slowly. Reaction of other alkali metals with Br 2 2

and other compounds containing acidic hydrogen (i.e, H atom attached on is fast.
F,O, N and triply bonded carbon atom, for example, HF, H O, ROH, RNH , 2 2
(17) Li CO Li C O , LiF , Li PO are the only alkali metal salts which are
2 3 2 2 4 3 4

CH  CH) to liberate H . 2
insoluble or sparingly soluble in water.
1 1 Diagonal Relationship of Li with Mg
M  H 2 O  MOH  H 2 ; M  HX  MX  H 2 Due to its small size lithium differs from other alkali metals but
2 2
resembles with Mg as its size is closer to Mg Its resemblance with Mg is
1 1
M  ROH  ROH  H 2 ; M  RNH 2  RNHNa  H 2 known as diagonal relationship. Generally the periodic properties show
2 2 either increasing or decreasing trend along the group and vice versa along
the period which brought the diagonally situated elements to closer values. (2) It is used as an alloying metal with
Following are the characteristic to be noted. (i) Pb to give toughened bearings.
Period Group I Group II (ii) Al to give high strength Al-alloy for aircraft industry.
2 Li Be (iii) Mg (14% Li) to give extremely tough and corrosion resistant
3 Na Mg alloy which is used for armour plate in aerospace components.
(1) Both Li and Mg are harder and higher m.pt than the other metals Sodium and its compounds
of their groups.
(1) Ores of sodium : NaCl (common salt), NaNO 3 (chile salt
(2) Due to covalent nature, chlorides of both Li and Mg are
deliquescent and soluble in alcohol and pyridine while chlorides of other petre), Na 2 SO 4 .10 H 2 O (Glauber's salt), borax (sodium tetraborate or
alkali metals are not so. sodium borate, (Na 2 B4 O7 . 10 H 2 O) .
(3) Fluorides, phosphates of Li and Mg are sparingly soluble in water (2) Extraction of sodium : It is manufactured by the electrolysis of
whereas those of other alkali metals are soluble in water.
fused sodium chloride in the presence of CaCl 2 and KF using graphite
(4) Carbonates of Li and Mg decompose on heating and liberate CO 2
anode and iron cathode. This process is called Down process.
Carbonates of other alkali metals are stable towards heat and decomposed
only on fusion. NaCl ⇌ Na   Cl  .
Li CO  Li O + CO ; Mg CO  MgO + CO
2 3 2 2 3 2
At cathode : Na   e   Na ;
(5) Hydroxides and nitrates of both Li and Mg decompose on
heating to give oxide. Hydroxides of both Li and Mg are weak alkali. At anode : Cl   Cl  e  ; Cl  Cl  Cl 2 
4 LiNO  2Li O + 4NO + O 3 2 2 2
Sodium cannot be extracted from aqueous NaCl because

2Mg(NO )  2MgO + 4NO + O EH0 2 O / H 2 0
3 2 2 2
(–0.83V) is more than E Na / Na (–2.71V).
2LiOH  Li O + H O ; Mg(OH)  MgO + H O 2 2 2 2
Anode and cathode are separated by means of a wire gauze to
Hydroxides of other alkali metals are stable towards heat while their prevent the reaction between Na and Cl 2 .
nitrates give O and nitrite. 2
(3) Compound of sodium
2KNO  2KNO + O 3 2 2 (i) Sodium chloride : It is generally obtained by evaporation of sea
(6) Both Li and Mg combine directly with N to give nitrides Li N 2 3
water by sun light. However NaCl so obtained contains impurities like
and Mg N . Other alkali metals combine at high temperature, 6Li + N 
3 2 2
CaSO 4 , CaCl 2 and MgCl2 which makes the salt deliquescent. It is then
2Li N; 3Mg + N  Mg N . Both the nitrides are decomposed by water to give
3 2 3 2
purified by allowing HCl gas to pass through the impure saturated
NH 3
solution of NaCl . The concentration of Cl  ions increases and as a
Li N + 3H O  3LiOH + NH ;
3 2 3 result pure NaCl gets precipitated due to common ion effect.
Mg N + 6H O  3Mg(OH) + 2NH
3 2 2 2 3
(ii) Sodium hydroxide NaOH (Caustic soda)
(7) Bicarbonates of Li and Mg are more soluble in water than Preparation
carbonates whereas carbonates of alkali metals are more soluble. (a) Gossage process :
(8) Both Li and Mg combine with carbon on heating. Na 2CO 3  Ca(OH )2  2 NaOH  CaCO 3
(10 % solution)
2Li + 2C  Li C ; Mg + 2C  Mg C 2 2 2

(b) Electrolytic method : Caustic soda is manufactured by the

(9) The periodic properties of Li and Mg are quite comparable
electrolysis of a concentrated solution of NaCl.
Li Mg
Electronegativity 1.0 1.2 At anode: Cl  discharged; At cathode: Na  discharged
Atomic radii 1.23 1.36 (c) Castner - Kellener cell (Mercury cathode process) : NaOH
obtained by electrolysis of aq. solution of brine. The cell comprises of
Ionic radii 0.60(Li ) 0.65(Mg ) + +2

rectangular iron tank divided into three compartments.

Atomic volume 12.97 c.c 13.97 c.c Outer compartment – Brine solution is electrolysed ; Central
(10) Both have high polarizing power. compartment – 2% NaOH solution and H 2
Polarizing Power = Ionic charge / (ionic radius) . 2

Properties : White crystalline solid, highly soluble in water, It is only

(11) Li and Mg Form only monooxide on heating in oxygen. sparingly soluble in alcohol.
4Li + O  2 Li O ; 2Mg + O  2 MgO 2 2 2
(a) Reaction with salt :
(12) Li SO like MgSO does not form alums.
2 4 4
FeCl3  3 NaOH  Fe(OH )3   3 NaCl
(Insoluble hydroxide)
(13) The bicarbonates of Li and Mg do not exist in solid state, they
exist in solution only. HgCl2  2 NaOH  2 NaCl  Hg(OH )2  H 2 O  HgO 
(14) Alkyls of Li and Mg (R. Li and R.MgX) are soluble in organic unstable yellow
solvent.
(15) Lithium chloride and MgCl both are deliquescent and separate 2
AgNO3  2 NaOH  2 NaNO 3  2 AgOH  Ag2 O   H 2 O
out from their aqueous solutions as hydrated crystals, LiCl. 2H O and MgCl 2 2
Brown

. 2H O. 2 Zn, Al, Sb , Pb, Sn and As forms insoluble hydroxide which

Uses of Lithium dissolve in excess of NaOH (amphoteric hydroxide).
(1) It is used as a deoxidiser in metallurgy of Cu and Ni.
 NH 4 Cl  NaOH   NaCl  NH 3   H 2O
heat
Na 2 CO 3  H 2 O  H 2 CO 3  2 Na   2OH 
Weak acid
(b) Reaction with halogens :
(c) It is readily decomposed by acids with the evolution of CO 2
X 2  2 NaOH (cold)  NaX  NaXO  H 2 O
sod. hypohalite gas.
3 X 2  6 NaOH (hot)  5 NaX  NaXO3  3 H 2O ; (d) Na 2 CO 3  H 2 O  CO 2  2NaHCO 3
(Sod. halate)
Uses : In textile and petroleum refining, Manufacturing of glass,
(X  Cl, Br, I) NaOH soap powders etc.
(c) Reaction with metals : Weakly electropositive metals like Zn, Al (iv) Sodium peroxide (Na O ) 2 2

Preparation : It is manufactured by heating sodium metal on

and Sn etc.
aluminium trays in air (free from CO 2 )
Zn  2 NaOH  Na 2 ZnO2  H 2 
 Na O
2 Na  O 2 (air) 

(d) Reaction with sand, SiO :2
2 2

2 NaOH  SiO2  Na 2 SiO3  H 2O Properties : (a) When pure it is colourless. The faint yellow colour
Sod. silicate(glass) of commercial product is due to presence of small amount of superoxide
(NaO 2 ).
(e) Reaction with CO:
o (b) On coming with moist air it become white due to formation of
150  200 C
NaOH  CO   HCOONa NaOH and Na 2 CO 3 .
5 10 atm Sod. formate

NaOH breaks down the proteins of the skin flesh to a pasty mass, 2 Na 2 O 2  2 H 2 O  4 NaOH  O 2 ;
therefore it is commonly known as caustic soda. 2 NaOH  CO 2  Na 2 CO 3  H 2 O
Caustic property : sodium hydroxide breaks down the proteins of
the skin flesh to a pasty mass, therefore, it is commonly known as caustic (c) It is powerful oxidising agent. It oxidises Cr (III) hydroxide to
soda. sodium chromate, Mn (II) to sodium manganate and sulphides to
Uses : Sodium hydroxide is used : sulphates.
Uses : As a bleaching agent and it is used for the purification of air
(a) in the manufacture of soidum metal, soap (from oils and fats),
rayon, paper, dyes and drugs, in confined spaces such as submarines because it can combine with CO 2
(b) for mercurinzing cotton to make cloth unshrinkable and to give Na 2 CO 3 and oxygen, 2CO 2  2 Na 2 O 2  2 Na 2 CO 3  O 2 .
(c) as a reagent in the laboratory. (v) Micro cosmic salt [Na (NH ) HPO . 4H O]
4 4 2

(iii) Sodium carbonate or washing soda, Na 2 CO 3 Prepared by dissolving equimolar amounts of Na 2 HPO4 and
It exists in various forms, namely anhydrous sodium carbonate Na CO 2 2
NH 4 Cl in water in 1 : 1 ratio followed by crystallization
(soda-ash); monohydrate Na 2 CO 3 .H 2 O (crystal carbonate); hyptahydrate NH 4 Cl  Na 2 HPO4  Na( NH 4 )HPO4  NaCl
Na 2 CO 3 .7 H 2 O and decahydrate Na 2 CO 3 .10 H 2 O (washing soda or sal  Crystallization
soda). Na(NH 4 )HPO4 .4 H 2 O
(Colourless crystal)
Preparation : (a) Solvay process : In this process, brine (NaCl) ,
NH 3 and CO 2 are the raw materials. Chemical properties :
On heating M.C.S, NaPO3 is formed. NaPO3 forms coloured
NH 3  CO 2  H 2 O  NH 4 HCO 3
beads with oxides of transition metal cloudy SiO 2
oC
30
NH 4 HCO 3  NaCl   NaHCO 3   NH 4 Cl 
Na( NH 4 )HPO4  NaPO3  H 2 O  NH 3
250 oC (Sodium meta
2 NaHCO 3    Na 2 CO 3  H 2 O  CO 2 phosphate)


2 NH 4 Cl  Ca(OH )2  CaCl 2  2 H 2 O  2 NH 3 NaPO3  CuO  CuNaPO 4
slaked (Trans parent (blue bead)
glassy bead)
lime
NaPO3  CoO  CoNaPO4 (blue bend)
CaCl 2 so formed in the above reaction is a by product of solvay
process. NaPO3  MnO  NaMnO4 (blue bead)
Properties Uses : (a) For the formation of sodium meta phosphate and copper
dry air sodium phosphate
(a) Na 2 CO 3 .10 H 2 O   Na 2 CO 3 .H 2 O  9 H 2 O
(decahydra te) (Monohydrate) (b) It is used for the detection of colured ion
(c) It is espacially used for testing silica with which a cloudy bead

Na 2CO 3 . H 2O 
 Na 2CO 3 containing floating properties of silica is obtained.
It does not decompose on funrther heating even to redness (m.pt. (vi) Sodium bi Carbonate (NaHCO , Baking soda) 3

853°C) Preparation : It is an inter mediate compound in manufacture of

(b) It is soluble in water with considerable evolution of heat. sodium carbonate by the solvay’s process
 NaCl  NH 3  CO 2  H 2  NaHCO 3  NH 4 Cl (v) Radium : Pitch blende (U O ); (Ra in traces); other radium rich
3 8

minerals are carnotite [K UO )] (VO ) 8H O and antamite [Ca(UO ) ]

2 2 4 2 2 2 2

o
50 100 C
Properties: 2 NaHCO 3    Na 2 CO 3  H 2 O  CO 2 (3) Extraction of alkaline earth metals
(i) Be and Mg are obtained by reducing their oxides carbon,
It is amphiprotic HCO 3  H  ⇌ H 2 CO 3
BeO + C  Be + CO ; MgO + C  Mg + CO
HCO 3 ⇌H  
CO 32  (ii) The extraction of alkaline earth metals can also be made by the
reduction of their oxides by alkali metals or by electrolysing their fused
Uses : (a) Baking powder contains NaHCO 3 , Ca(H 2 PO4 )2 and salts.
starch. (4) Alloy formation : These dissolve in mercury and form amalgams.
Improved Baking powder contains 40% starch 30% NaHCO 3 , Physical properties
20% NaAl(SO 4 )2 and 10% CaH 2 (PO4 ) (1) Physical state : All are greyish-white, light, malleable and ductile
(b) In pharmacentical industry (Antacids etc.) metals with metallic lustre. Their hardness progressively decrease with
(c) Fire extingerishers. increase in atomic number. Although these are fairly soft but relatively
harder than alkali metals.
(vii) Sodium Sulphate Na SO or salt cake
2 4

Preparation : It is the by-product of HCl industry (2) Atomic and ionic radii
(i) The atomic and ionic radii of alkaline earth metals also increase
2 NaCl  H 2 SO 4  Na 2 SO 4  HCl down the group due to progressive addition of new energy shells like alkali
metals.
Properties : When aqueous solution of Na 2 SO 4 is cooled below
Be Mg Ca Sr Ba Ra
o
32 C Glauber’s salt (Na 2 SO 4 .10 H 2 O) gets crystallised and if cooled Atomic radius (pm) 112 160 197 215 222 –
o Ionic radius of M2+ 31 65 99 113 135 140
to 12 C , Na 2 SO 4 7 H 2 O crystals are formed.
ion (pm)
Na 2 SO 4 .10 H 2 O   Na 2 SO 4  10 H 2 O
(indry air) (ii) The atomic radii of alkaline earth metals are however smaller
than their corresponding alkali metal of the same period. This is due to the
Uses : Na 2 SO 4 finds use in paper industry detergent and glass fact that alkaline earth metals possess a higher nuclear charge than alkali
manufacturing. metals which more effectively pulls the orbit electrons towards the nucleus
Alkaline Earth Metals and Their Compounds causing a decrease in size.
The group 2 of the periodic table consists of six metallic elements. (3) Density
These are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), (i) Density decreases slightly upto Ca after which it increases. The
barium (Ba) and radium (Ra). These (except Be) are known as alkaline earth decrease in density from Be to Ca might be due to less packing of atoms in
metals as their oxides are alkaline and occur in earth crust. solid lattice of Mg and Ca.
(1) Electronic configuration Be Mg Ca Sr Ba Ra
1.84 1.74 1.55 2.54 3.75 6.00
Element Electronic configurations ( ns 2 )
(ii) The alkaline earth metals are more denser, heavier and harder than
4 Be [He] 2 s 2 alkali metal. The higher density of alkaline earth metals is due to their
smaller atomic size and strong intermetallic bonds which provide a more
12 Mg [ Ne ] 3 s 2
close packing in crystal lattice as compared to alkali metals.
20 Ca [ Ar] 4 s 2 (4) Melting point and Boiling point
Sr (i) Melting points and boiling points of alkaline earth metals do not
38 [Kr] 5 s 2 show any regular trend.
56 Ba [ Xe ] 6 s 2 Be Mg Ca Sr Ba Ra
melting points (K) 1560 920 1112 1041 1000 973
88 Ra [Rn]7 s 2 boiling point (K) 2770 1378 1767 1654 1413 –
(ii) The values are, however, more than alkali metals. This might due
Radium was discovered in the ore pitch blende by madam Curie. It is to close packing of atoms in crystal lattice in alkaline earth metals.
radioactive in nature.
(5) Ionisation energy and electropositive or metallic character
(2) Occurrence : These are found mainly in combined state such as (i) Since the atomic size decreases along the period and the nuclear
oxides, carbonates and sulphates Mg and Ca are found in abundance in charge increases and thus the electrons are more tightly held towards
nature. Be is not very abundant, Sr and Ba are less abundant. Ra is rare nucleus. It is therefore alkaline earth metals have higher ionisation energy in
element. Some important ores of alkaline earth metals are given below, comparison to alkali metals but lower ionisation energies in comparison to
(i) Baryllium : Beryl (3BeO.Al O .6SiO ); Phenacite (Be SiO )
2 3 2 2 4 p-block elements.
(ii) Magnesium : Magnesite (MgCO ); Dolomite (CaCO . MgCO ); 3 3 3 (ii) The ionisation energy of alkaline earth metals decreases from Be
Epsomite(MgSO . 7H O); Carnallite
4 2
(MgCl .KCl. 6H O); Asbestos 2 2 to Ba.
[CaMg (SiO ) ]
3 3 4
Be Mg Ca Sr Ba Ra
(iii) Calcium : Limestone (CaCO ); Gypsum : (CaSO .2H O), Anhydrite 3 4 2 First ionisation energy (k J mol-1) 899 737 590 549 503 509
(CaSO ); Fluorapatite [(3Ca (PO ) CaF )] Phosphorite rock [Ca (PO ) ]
4 3 4 2. 2 3 4 2 Second ionisation energy (kJ mol-1) 1757 1450 1146 1064 965 979
(iv) Barium : Barytes (BaSO ) ; witherite (BaCO ) 4 3
 (iii) The higher values of second ionisation energy is due to the fact of alkali metals e.g MgCl and CaCl exists as Mg Cl .6H O and CaCl 6H O
2 2 2 2 2. 2

that removal of one electron from the valence shell, the remaining electrons which NaCl and KCl do not form such hydrates.
are more tightly held in which nucleus of cation and thus more energy is (iv) The ionic mobility, therefore, increases from Be to Ba , as the 2+ 2+

required to pull one more electron from monovalent cation. size of hydrated ion decreases.
(iv) No doubt first ionisation energy of alkaline earth metals are (8) Electronegativities
higher than alkali metals but a closer look on 2nd ionisation energy of alkali (i) The electronegativities of alkaline earth metals are also small but
metals and alkaline earth metals reveals that 2nd ionisation energy of alkali are higher than alkali metals.
metals are more (ii) Electronegativity decreases from Be to Ba as shown below,
Li Be Be Mg Ca Sr Ba
1st ionisation energy (kJ mol–1) 520 899
Electronegativity 1.57 1.31 1.00 0.95 0.89
2nd ionisation energy (kJ mol–1) 7296 1757
This may be explained as, (9) Conduction power : Good conductor of heat and electricity.
(10) Standard oxidation potential and reducing properties
2s1 
 Li +: 1s2 

removal of 2 s removal of 1 s
Li : 1s2, Li2+ : 1s1
electron electron (i) The standard oxidation potential (in volts) are,
Be : 1s2 , 2s2 
 Be+ : 1s2, 2s1 
 Be2+ : 1s2 Be Mg Ca Sr Ba
removal of 2 s removal of 2 s
electron electron 1.69 2.35 2.87 2.89 2.90
The removal of 2 electron from alkali metals takes place from 1s sub
nd

(ii) All these metals possess tendency to lose two electrons to give
shell which are more closer to nucleus and exert more nuclear charge to M ion and are used as reducing agent.
2+

hold up 1s electron core, whereas removal of 2nd electron from alkaline (iii) The reducing character increases from Be to Ba, however, these
earth metals takes from 2s sub shell. More closer are shells to the nucleus, are less powerful reducing agent than alkali metals.
more tightly are held electrons with nucleus and thus more energy is
(iv) Beryllium having relatively lower oxidation potential and thus
required to remove the electron.
does not liberate H from acids.
(v) All these possess strong electropositive character which increases 2

from Be to Ba. (11) Characteristic flame colours

(vi) These have less electropositive character than alkali metals as The characteristic flame colour shown are : Ca - brick red; Sr –
the later have low values of ionisation energy. crimson ; Ba-apple green and Ra- crimson.
(6) Oxidation number and valency Chemical Properties
(i) The IE of the these metals are much lower than IE and thus it
1 1
(1) Formation of oxides and hydroxides
appears that these metals should form univalent ion rather than divalent (i) The elements (except Ba and Ra) when burnt in air give oxides of
ions but in actual practice, all these give bivalent ions. This is due to the ionic nature M O which are crystalline in nature. Ba and Ra however give
2+ 2-

fact that M ion possesses a higher degree of hydration or M ions are

2+ 2+
peroxide. The tendency to form higher oxides increases from Be to Ra.
extensively hydrated to form [M(H O) ] , a hydrated ion. This involves a large
2 x
2+

2M + O  2MO (M is Be, Mg or Ca )
amount of energy evolution which counter balances the higher value of 2

second ionisation energy. 2M + O  MO 2

(M is Ba or Sr)
2

M M , H = IE + E 2+ (ii) Their less reactivity than the alkali metals is evident by the fact
1 2

that they are slowly oxidized on exposure to air, However the reactivity of
M + H O  [M(H O) ] ; H = – hydration energy.
2+

x 2 2 x
2+

these metals towards oxygen increases on moving down the group.

(ii) The tendency of these metals to exist as divalent cation can thus
(iii) The oxides of these metals are very stable due to high lattice
be accounted as,
energy.
(a) Divalent cation of these metals possess noble gas or stable
configuration. (iv) The oxides of the metal (except BeO and MgO) dissolve in water
to form basic hydroxides and evolve a large amount of heat. BeO and MgO
(b) The formation of divalent cation lattice leads to evolution of
possess high lattice energy and thus insoluble in water.
energy due to strong lattice structure of divalent cation which easily
compensates for the higher values of second ionisation energy of these (v) BeO dissolves both in acid and alkalies to give salts i.e. BeO
metals. possesses amphoteric nature.
(c) The higher heats of hydration of divalent cation which accounts BeO+2NaOHNa BeO +H O ; BeO+2HClBeCl +H O
2 2 2 2 2

for the existence of the divalent ions of these metals in solution state. Sod. beryllate Beryllium chloride

(7) Hydration of ions (vi)The basic nature of oxides of alkaline earth metals increases from
(i) The hydration energies of alkaline earth metals divalent cation Be to Ra as the electropositive Character increases from Be to Ra.
are much more than the hydration energy of monovalent cation. (vii)The tendency of these metal to react with water increases with
Mg+ Mg2+ increase in electropositive character i.e. Be to Ra.
Hydration energy or Heat of hydration (kJ mol–1) 353 1906 (viii) Reaction of Be with water is not certain, magnesium reacts
The abnormally higher values of heat of hydration for divalent only with hot water, while other metals react with cold water but slowly
cations of alkaline earth metals are responsible for their divalent nature. and less energetically than alkali metals.
MgCl formation occurs with more amount of heat evolution and thus MgCl
2 2
(ix) The inertness of Be and Mg towards water is due to the
is more stable. formation of protective, thin layer of hydroxide on the surface of the metals.
(ii) The hydration energies of M ion decreases with increase in ionic 2+
(x) The basic nature of hydroxides increase from Be to Ra. It is
radii. because of increase in ionic radius down the group which results in a
Be2+ Mg2+ Ca2+ Sr2+ Ba2+ decrease in strength of M –O bond in M –(OH) to show more dissociation 2

Heat of hydration kJ mol–1 2382 1906 1651 1484 1275 of hydroxides and greater basic character.
(iii) Heat of hydration are larger than alkali metals ions and thus (xi) The solubility of hydroxides of alkaline earth metals is relatively
alkaline earth metals compounds are more extensively hydrated than those less than their corresponding alkali metal hydroxides Furthermore, the
solubility of hydroxides of alkaline earth metals increases from Be to Ba. Be (4) Halides
(OH) and Mg (OH) are almost insoluble, Ca (OH) (often called lime water)
2 2 2 (i) The alkaline earth metals combine directly with halogens at
is sparingly soluble whereas Sr(OH) and Ba (OH) (often called baryta 2 2 appropriate temperatures forming halides, MX . These halides can also be 2

water) are more soluble. prepared by the action of halogen acids (HX) on metals, metal oxides,
The trend of the solubility of these hydroxides depends on the values hydroxides and carbonates.
of lattice energy and hydration energy of these hydroxides. The magnitude M + 2HX  MX + H ; MO + 2HX  MX + H O 2 2 2 2

of hydration energy remains almost same whereas lattice energy decreases

M(OH) + 2HX MX +2H O
appreciably down the group leading to more –Ve values for H down 2 2 2

MCO + 2HX  MX + CO + H O
solution

the group. 3 2 2 2

Beryllium chloride is however, conveniently obtained from oxide

H solution
= H lattice energy
+ H hydration energy

870 1070 K
More negative is H more is solubility of compounds. BeO  C  Cl 2   BeCl 2  CO
solution

(xii) The basic character of oxides and hydroxides of alkaline earth (ii) BeCl is essentially covalent, the chlorides MgCl , CaCl , SrCl and
2 2 2 2

metals is lesser than their corresponding alkali metal oxides and hydroxides. BaCl are ionic; the ionic character increases as the size of the metal ion
2

(xiii) Aqueous solution of lime water [Ca(OH) ] or baryta water 2

increases. The evidence is provided by the following facts,
[Ba(OH)] are used to qualitative identification and quantative estimation of
2
(a) Beryllium chloride is relatively low melting and volatile whereas
carbon dioxide, as both of them gives white precipitate with CO due to 2
BaCl has high melting and stable.
2

formation of insoluble CaCO or BaCO 3 3 (b) Beryllium chloride is soluble in organic solvents.
Ca(OH)2 + CO2  CaCO3 + H2O ; Ba(OH)2 + CO2  BaCO3 + H2O (iii) The halides of the members of this group are soluble in water
(white ppt) (white ppt)
and produce neutral solutions from which the hydrates such : MgCl 6H O, 2 2

SO also give white ppt of CaSO and BaSO on passing through lime
2 3 3
CaCl .6H O. BaCl 2H O can be crystallised. The tendency to form hydrated
2 2 2 2

water or baryta water. However on passing CO in excess, the white 2

halides decreases with increasing size of the metal ions.
turbidity of insoluble carbonates dissolve to give a clear solution again due (iv) BeCl is readily hydrolysed with water to form acid solution,
2

to the formation of soluble bicarbonates, BeCl + 2H O Be (OH) + 2HCl.

2 2 2

CaCO  H O + CO  Ca(HCO )3 2 2 3 2 (v) The fluorides are relatively less soluble than the chlorides due to
(2) Hydrides high lattice energies. Except BeCl and MgCl the chlorides of alkaline earth 2 2

(i) Except Be, all alkaline earth metals form hydrides (MH ) on 2
metals impart characteristic colours to flame.
heating directly with H . M+ H  MH . CaCl2 SrCl2 BaCl2
2 2 2

(ii) BeH is prepared by the action of LiAlH On BeCl Brick red colour Crimson colour Grassy green colour
2 4 2

2BeCl + LiAlH  2BeH + LiCl + AlCl . Structure of BeCl : In the solid phase polymeric chain structure with 2

2 4 2 3
three centre two electron bonding with Be-Cl-Be bridged structure is shown
(iii) BeH and MgH are covalent while other hydrides are ionic.
2 2
below,
(iv) The ionic hydrides of Ca, Sr, Ba liberate H at anode and metal
at cathode.
2

202 PM Cl Cl Cl
CaH fusion
2
Ca + 2H 2+ –
Be 98o Be 263 pm Be
82o
Anode : 2H H + 2e Cathode : Ca + 2e Ca –

2
– 2+ –
Cl Cl Cl
(v) The stability of hydrides decreases from Be to Ba. In the vapour phase it tends to form a chloro-bridged dimer which
(vi) The hydrides having higher reactivity for water, dissolves readily dissociates into the linear triatomic monomer at high temperature at nearly
and produce hydrogen gas. 1200 K.
CaH + 2H O Ca(OH) + 2H  (5) Solubility in liquid ammonia : Like alkali metals, alkaline earth
2(s) 2 2 2

metals also dissolve in liquid ammonia to form coloured solutions When

(3) Carbonates and Bicarbonates
such a solution is evaporated, hexammoniate, M(NH ) is formed.
(i) All these metal carbonates (MCO ) are insoluble in neutral 3
3 6

medium but soluble in acid medium. These are precipitated by the addition (6) Nitrides
of alkali metal or ammonium carbonate solution to the solution of these (i) All the alkaline earth metals direct combine with N give nitrides, 2

metals. MN.
3 2

(NH ) CO + CaCl 2NH Cl + CaCO

4 2 3 2 4 3
(ii) The ease of formation of nitrides however decreases from Be to
Na CO + BaCl 2NaCl + BaCO Ba.
(iii) These nitrides are hydrolysed water to liberate
2 3 2 3

(ii) Alkaline earth metal carbonates are obtained as white

precipitates when calculated amount of carbon dioxide is passed through NH , M N + 6H O 3M(OH) + 2NH
3 3 2 2 2 3

the solution of the alkaline metal hydroxides. (7) Sulphates

M(OH) + CO MCO + H O 2 (aq) 2 (g) 3(s) 2 (l) (i) All these form sulphate of the type M SO by the action of H SO 4 2 4

and sodium or ammonium carbonate is added to the solution of the on metals, their oxides, carbonates or hydroxides.
alkaline earth metal salt such as CaCl . 2
M + H SO  MSO + H ; MO+H SO  MSO +H O
CaCl + Na CO  CaCO +2 NaCl
2 4 4 2 2 4 4 2

2 (aq) 2 3 (aq) 3(s) (aq)

MCO + H SO  MSO + H O+CO
(iii) Solubility of carbonates of these metals also decreases
3 2 4 4 2 2

downward in the group due to the decrease of hydration energy as the M(OH) + H SO  MSO + 2H O 2 2 4 4 2

lattice energy remains almost unchanged as in case of sulphates. (ii) The solubility of sulphates in water decreases on moving down
(vi) The carbonates of these metals decompose on heating to give the group BeSO and MgSO are fairly soluble in water while BaSO is
4 4 4

the oxides, the temperature of decomposition increasing from Be to Ba. completely insoluble. This is due to increases in lattice energy of sulphates
Beryllium carbonate is unstable. down the group which predominates over hydration energy.
(iii) Sulphate are quite stable to heat however reduced to sulphide
MCO3   MO  CO 2
Heat
on heating with carbon.
 MSO + 2C  MS+2CO 4 2
Due to its small size Be differs from other earth alkaline earth
metals but resembles in many of its properties with Al on account of
(8) Action with carbon : Alkaline metals (except Be, Mg) when diagonal relationship.
heated with carbon form carbides of the type MC These carbides are also 2
(1) Be and Al have almost same and smaller size and thus favour for
2+ 3+

called acetylides as on hydrolysis they evolve acetylene.

covalent bonding.
MC + 2H OM(OH) + C H
2 2 2 2 2
(2) Both these form covalent compounds having low m. pt and
(9) Action with sulphur and phosphorus : Alkaline earth metals soluble in organic solvent.
directly combine with sulphur and phosphorus when heated to form (3) Both have same value of electronegativity (i.e. 1.5).
sulphides of the type MS and phosphides of the type M P respectively. 3 2 (4) The standard O.P of these elements are quite close to each other
M + S  MS ; 3M + 2P  M P 3 2
; Be =1.69 volts and Al = 1.70 volts.
2+ 3+

Sulphides on hydrolysis liberate H S while phosphides on hydrolysis 2

(5) Both become passive on treating with conc. HNO in cold. 3

evolve phosphine. (6) Both form many stable complexes e.g. (BeF ) , (AlH ) . 3
–

4
–

MS + dil. acid  H S ; M P + dil. acid  PH 2 3 2 3

(7) Like BeO, Al O is amphoteric in nature. Also both are high
2 3

Sulphides are phosphorescent and are decomposed by water melting point solids.
2MS + 2H O M(OH) + M(HS) Al O + 2NaOH  2NaAlO + H O
2 3 2 2
2 2 2

Al O + 6HCl  2AlCl + 3H O
(10) Nitrates : Nitrates of these metals are soluble in water On 2 3 3 2

heating they decompose into their corresponding oxides with evolution of a (8) Be and Al both react with NaOH to liberate H forming beryllates 2

mixture of nitrogen dioxide and oxygen. and alluminates.

Be + 2NaOH  Na BeO +H
1 2 2 2

M ( NO 3 )2  MO  2 NO 2   O 2 2Al + 6NaOH 2Na AlO + 3H

2 3 3 2

(9) Be C and Al C both give CH on treating with water.

2 4 3 4

(11) Formation of complexes Be C+ 2H OCH + 2BeO

2 2 4

(i) Tendency to show complex ion formation depends upon smaller

Al C + 6H O3CH + 2Al O
size, high nuclear charge and vacant orbitals to accept electron. Since 4 3 2 4 2 3

alkaline metals too do not possess these characteristics and thus are unable (10) Both occur together in nature in beryl ore, 3BeO. Al O 6SiO . 2 3. 2

to form complex ion. (11) Unlike other alkaline earths but like aluminium, beryllium is not
(ii) However, Be on account of smaller size forms many complex
2+ easily attacked by air (Also Mg is not attacked by air)
such as (BeF ) , (BeF ) . 3
1-

4
2- (12) Both Be and Al react very slowly with dil. HCl to liberate H . 2

Anomalous behaviour of Beryllium (13) Both Be and Al form polymeric covalent hydrides while hydrides
Beryllium differs from rest of the alkaline earth metals on account of of other alkaline earth are ionic.
its small atomic size, high electronegativity Be exerts high polarizing effect 2+
(14) Both BeCl and AlCl are prepared is similar way.
2 3

on anions and thus produces covalent nature in its compounds. Following BeO+ C+ Cl BeCl + CO
are some noteworthy difference of Be from other alkaline earth metals,
2 2

(1) Be is lightest alkaline earth metal. Al O + 3C +3Cl  2AlCl + 3CO

2 3 2 3

(2) Be possesses higher m.pt. and b.pt than other group members. (15) Both BeCl and AlCl are soluble in organic solvents and act as
2 3

(3) BeO is amphoteric in nature whereas oxides of other group catalyst in Friedel –Crafts reaction.
members are strong base. (16) Both Be (OH) and Al (OH) are amphoteric whereas hydroxides of
2 3

(4) It is not easily effected by dry air and does not decompose water other alkaline earths are strong alkali.
at ordinary temperature. (17) The salts of Be and Al are extensively hydrated.
(18) BeCl and AlCl both have a bridged polymeric structure.
(5) BeSO is soluble in water. 2 3

(19) Be and Al both form fluoro complex ions [BeF ] and [AlF ] in 2– 3–

(6) Be and Mg carbonates are not precipitated by (NH 4 )2 CO 3 in

4 6

solution state whereas other members of 2nd group do not form such
presence of NH Cl. 4
complexes.
(7) Be and Mg salts do not impart colour to flame. Magnesium and its compounds
(8) Be does not form peroxide like other alkaline earth metals. (1) Ores of magnesium : Magnesite (MgCO3 ), Dolomite
(9) It does not evolve hydrogen so readily from acids as other (MgCO3 .CaCO 3 ) , Epsomite (epsom salt) (MgSO4 .7 H 2 O) Carnallite
alkaline earth metals do so. (MgCl2 . KCl . 6 H 2 O) Asbestos (CaMg3 (SiO3 )4 ), Talc
(10) It has strong tendency to form complex compounds. (Mg2 (Si2 O5 )2 . Mg(OH )2 ) .
(11) Be N is volatile whereas nitrides of other alkaline earth metals
3 2
(2) Extraction of magnesium : It is prepared by the electrolysis of
are non-volatile.
fused magnesium chloride which in turn is obtained from carnallite and
(12) It’s salts can never have more than four molecules of water of magnesite.
crystallization as it has only four available orbitals in its valence shell.
Carnallite (MgCl2 .KCl.6 H 2 O) can’t be directly converted into
(13) Berylium carbide reacts water to give methane whereas
magnesium carbide and calcium carbide give propyne and acetylene anhydrous MgCl2 by heating because all the water of crystallisation
respectively. cannot be removed by heating. Moreover, strong heating may change it to
Be C+4H O2Be(OH) + CH
2 2 2 4
MgO .
Mg C + 4H O  2Mg(OH) + C H
2 3 2 2 3 6

MgCl2  2 H 2 O  MgO  2 HCl  H 2 O
CaC + 2H O  Ca(OH) + C H
2 2 2 2 4 In Dow’s process, magnesium chloride is obtained from sea water as
Diagonal relationship of Be with Al MgCl2 .6 H 2 O . It is rendered anhydrous by heating it in a current of dry
 HCl gas. The anhydrous magnesium chloride is fused with NaCl (to 120 oC 1 1
provide conductivity to the electrolyte and to lower the fusing temperature CaSO 4 . 2 H 2 O    CaSO 4 . H 2 O  1 H 2 O
Gypsum Plaster of 2 2
of anhydrous MgCl2 ) and then electrolysed at 700 o C . paris
(3) Compounds of magnesium Plaster of paris :
(i) Magnesia (MgO) : It is used as magnesia cement. It is a mixture 1 Hardening
CaSO 4 . H 2 O   CaSO 4 . 2 H 2 O 
H 2O
 CaSO 4 .2 H 2 O
of MgO and MgCl2 . It is also called Sorel's cement. 2 Setting orthorhomb ic Monoclinic(gypsum)
Plaster of paris
(ii) Magnesium hydroxide : It aqueous suspension is used in o
Medicine as an antacid. Its medicinal name is milk of magnesia. CaSO 4 .2 H 2 O   CaSO 4 (anhydrous)
200 C

Gypsum dead burnt plaster

(iii) Magnesium sulphate or Epsom salt (MgSO4 . 7 H 2 O) : It is
isomorphous with ZnSO 4 . 7 H 2 O. It is used as a purgative in medicine, as Gypsum when heated to about 200 o C is converted into anhydrous
a mordant in dyeing and as a stimulant to increase the secretion of bile. calcium sulphate. The anhydrous form (anhydrite) is known as dead burnt
plaster because it does not set like plaster of paris when moistened with water.
(iv) Magnesium chloride (MgCl2 .6 H 2 O) : It is a deliquescent solid.
(v) Calcium Hydroxide Ca(OH )2 (slaked lime)
Hydrated salt on heating in air undergoes partial hydrolysis.
Heat CaO  H 2 O  Ca(OH )2
MgCl2 . 6 H 2 O  Mg(OH )Cl  HCl  5 H 2 O .
Ca(OH )2  CO 2  CaCO3  Ca(HCO3 )2
Calcium and its compounds
(1) Ores of calcium : Lime stone or marble or chalk Suspension of Ca(OH )2 in water is called milk of lime.
(CaCO 3 ), Gypsum (CaSO 4 . 2 H 2 O), Dolomite (CaCO 3 . MgCO3 ), Ca(OH)2  Cl 2  CaOCl 2  H 2 O
Fluorspar (CaF2 ), phosphorite Ca 3 (PO4 )2 . Calcium phosphate is a (vi) Cement : (a) It is essentially a mixture of lime stone and clay. It
constituent of bones and teeth. is also called Portland cement because in presence of water it sets to a hard
(2) Manufacture : It is manufactured by the electrolysis of a molten stone-like mass resembling with the famous Portland rock, a famous
building stone of England. The approximate composition of cement is
mixture of calcium chloride containing some calcium fluoride. Calcium
chloride is obtained as a by product of the solvay process. Calcium oxide (CaO) 50 – 60 %
(3) Compounds of calcium Silica (SiO 2 ) 20 – 25%
(i) Calcium oxide or Quick lime or Burnt lime (CaO) : It's aqueous
suspension is known as slaked lime. Alumina ( Al 2 O 3 ) 5 – 10%

hissingsound Magnesia (MgO) 1 – 3%

CaO  H 2 O    Ca(OH )2  Heat,
slaked Ferric oxide (Fe 2 O 3 ) 1 – 3%
lime
The above compounds are provided by the two raw materials,
When exposed to oxy-hydrogen flame, it starts emitting light called namely lime stone (which provides CaO ) and clay which provides
lime light.
SiO 2 , Al 2 O 3 and Fe 2 O 3 . In cement, almost entire amount of lime is
CaO is used as basic flux, for removing hardness of water, as a
present in the combined state as calcium silicates (2CaO.SiO2 and
drying agent (for NH 3 gas) for preparing mortar (CaO+ sand +water).
3CaO.SiO 2 ) and calcium aluminates (3CaO. Al 2 O 3 and
Mortar : Mortar used in making buildings is a mixture of lime (CaO)
4 CaO. Al 2 O 3 ) .
and sand in the ratio 1 : 3 with enough water to make a thick paste. When
the mortar is placed between bricks, it slowly absorbs CO from the air and
2
(b) Cement containing excess amount of lime cracks during setting;
the slaked lime revers to CaCO .
3
while cement containing less amount of lime is weak in strength.
Ca(OH)2 (s)  CO 2 (g)  CaCO 3 (s)  H 2 O(l) (c) Cement with excess of silica is slow-setting and that having an
Although the sand in the mortar is chemically inert, the grains excess of alumina is quick-setting.
are bound together by the particles of calcium carbonate and a hard (d) Cement containing no iron oxide is white but hard to burn.
material results. Cement is manufactured by two processes, viz, wet and dry.
(ii) Calcium chloride (CaCl 2 .6 H 2 O) : Fused CaCl 2 is a good A small amount (2–3%) of gypsum is added to slow down the
dessicant (drying agent). It can't be used to dry alcohol or ammonia as it setting of the cement so that it gets sufficiently hardened. Setting of
forms additional products with them. cement is an exothermic process and involves hydration of calcium
(iii) Calcium carbonate (CaCO ) :
3
aluminates and calcium silicates.
Ca(OH )2  CO 2  CaCO 3  H 2 O .
Boron Family
It is insoluble in water but dissolves in the presence of CO 2 due to
the formation of calcium bicarbonate. Group 13 of long form of periodic table (previously reported as
group III A according to Mendeleefs periodic table) includes boron ( B) ;
CaCO 3  H 2 O  CO 2  Ca(HCO 3 )2 aluminium (Al) , gallium (Ga), indium (In) and thallium (Tl) Boron is the
It is a constituent of protective shells of marine animals. first member of group 13 of the periodic table and is the only non-metal of
this group. The all other members are metals. The non-metallic nature of
(iv) Gypsum (CaSO 4 . 2 H 2 O) : On partially dehydrates to produce boron is due its small size and high ionisation energy. The members of this
plaster of paris. family are collectively known as boron family and sometimes as aluminium
family.
 (1) Electronic configuration more effectively pulled the nucleus. This results in less availability of ns 2

electrons pair for bonding or ns electron pair becomes inert. The inert 2

Element Electronic configuration ( ns 2 np 1 ) pair effect begins after n  4 and increases with increasing value of n.
(iv) The tendency to form M ion increases down the gp. Ga < Tl + +1 +1

5B
2 1
[He] 2 s 2 p (10) Hydrated ions : All metal ions exist in hydrated state.
(11) Ionisation energy
13 Al [ Ne ] 3 s 2 3 p 1 (i) Inspite of the more charge in nucleus and small size, the first
ionisation energies of this group elements are lesser than the corresponding
31 Ga [ Ar] 3d 10 4 s 2 4 p 1 elements of s block. This is due to the fact that removal of electron from a
p-orbitals (being far away from nucleus and thus less effectively held than s-
49 In [Kr] 4 d 10 5 s 2 5 p 1 orbitals) is relatively easier than s-orbitals.
(ii) The ionisation energy of this group element decrease down the
81 Tl [ Xe] 4 f 14 5 d 10 6 s 2 6 p 1 group due to increases in size like other group elements.
(iii) However, ionisation energy of Ga are higher than that of Al
(2) Occurrence : The important of this group elements are given because of smaller atomic size of Ga due to less effective shielding of 3d
below, electrons in Ga. Thus valence shell exert more effective nuclear charge in Ga
to show higher ionisation energies.
Boron : Borax (Tincal) (NaBO.10HO), Colemanite (CaBO5HO)
(12) Electropositive character
2 4 7 2 2 6 1 2

Boracite (2MgBO.MgCl), Boronatro calcite (CaBO.NaBO.8H O),

3 8 51 2 4 7 2 2
(i) Electropositive character increases from B to Tl.
Kernite (Na B O 4H O), Boric acid
2 4 7. 2
(H BO ) 3 3
(ii) Boron is semi metal, more closer to non-metallic nature whereas
rest all members are pure metals.
Aluminium : Corundum (Al O ), Diaspore (Al O .H O), Bauxite (Al O 2 3 2 3 2 2 3.
(iii) Furthermore, these elements are less electropositive than s-block
2H O), and Cryolite (Na AlF ).
2 3 6
elements because of smaller size and higher ionisation energies.
Physical properties (13) Oxidation potential
(1) A regular increasing trend in density down the group is due to (i) The standard oxidation potentials of these element are quite high
increase in size. and are given below,
B Al Ga In Tl
(2) Melting points do not vary regularly and decrease from B to Ga
and then increase. E0op for M  M3++ 3e – +1.66 +0.56 +0.34 +1.26
E0op for M  M+ + e – +0.55 – +0.18 +0.34
(3) Boron has very high melting point because it exist as giant
covalent polymer in both solid and liquid state. (ii) However Boron does not form positive ions in aqueous solution
and has very low oxidation potential.
(4) Low melting point of Ga (29.8 C) is due to the fact that consists 0

(iii) The higher values of standard oxidation potentials are due to

of only Ga molecule; it exist as liquid upto 2000 C and hence used in high
2
0

higher heats of hydration on account of smaller size of trivalent cations.

temperature thermometry.
(iv) Aluminium is a strong reducing agent and can reduce oxides
(5) Boiling point of these elements however show a regular decrease which are not reduced even by carbon. This is due to lower ionisation energy
down the group. of aluminium than carbon. The reducing character of these elements is Al > Ga > In
(6) The abrupt increase in the atomic radius of Al is due to greater > Tl.
screening effect in Al (it has 8 electrons in its penultimate shell) than in B (14) Complex formation : On account of their smaller size and
(it has 2 electrons in its penultimate shell) more effective nuclear charge as well as vacant orbitals to accept elements,
these elements have more tendency to form complexes than-s block
(7) The atomic radii of group 13 elements are smaller than the
elements.
corresponding s-block elements. This is due to the fact that when we move
along the period, the new incoming electron occupy the same shell whereas Chemical properties
the nuclear charge increases regularly showing more effective pull of (1) Hydrides
nucleus towards shell electrons. This ultimately reduces the atomic size. (i) Elements of group 13 do not react directly with hydrogen but a
number of polymeric hydrides are known to exist.
(8) The atomic radius of Ga is slightly lesser than of Al because in
going from Al to Ga, the electrons have already occupied 3d sub shell in Ga. (ii) Boron forms a large no. of volatile covalent hydrides, known as
The screening effect of these intervening electrons being poor and has less boranes e.g. B H ,B H ,B H ,B H Two series of borones with general formula
2 6 4 10 5 11 6 10

influence to decrease the effective nuclear charge, therefore the electrons in B H and B H are more important.
n n+4 n n+6

Ga experience more forces of attractions towards nucleus to result in lower (iii) Boranes are electron deficient compounds. It is important to
size of Ga than Al note that although BX are well known, BH is not known. This is due of the
3 3

fact that hydrogen atoms in BH have no free electrons to form p–p back
(9) Oxidation state 3

bonding and thus boron has incomplete octet and hence BH molecules 3

(i) All exhibit +3 oxidation state and thus complete their octet either dimerise to form B H having covalent and three centre bonds.
6 6

by covalent or ionic union. (iv) Al forms only one polymeric hydride (AlH ) commonly known as 3 n

(ii) Boron being smaller in size cannot lose its valence electrons to alane It contains Al…..H……Al bridges.
form B ion and it usually show +3 covalence. The tendency to show +3
3+
(v) Al and Ga forms anionic hydrides e.g. LiAlH and LiGa H , 4 4

covalence however decreases down the group even Al shows +3 covalence in 4 LiH  AlCl3   Li[ AlH4 ]  3 LiCl
ether
most of its compounds.
(iii) Lower elements also show +1 ionic state e.g Tl , Ga . This is due + + (2) Reactivity towards air
to inert pair effect. The phenomenon in which outer shell ‘s’ electrons (ns ) 2

penetrate to (n-1) d-electrons and thus become closer to nucleus and are
 (i) Pure boron is almost unreactive at ordinary temperature. It BF having less tendency for hydrolysis as well as Lewis acid nature,
3

reacts with air to form B O when heated It does react with water. Al burns 2 3
is extensively used as a catalyst in organic reactions e.g. Friedel- Crafts
in air with evolution of heat give Al O . 2 3
reaction.
(ii) Ga and In are not effected by air even when heated whereas Tl is (v) Boron atom, in BX , has six electrons in the outermost orbit and
3

little more reactive and also form an oxide film at surface. In moist air, a thus it can accept a pair of electrons form a donor molecule like NH to 3

layer of Tl (OH) is formed. complete its octet. Hence boron halides act as very efficient Lewis acids. The
(iii) Al decomposes H O and reacts readily in air at ordinary 2
relative Lewis acid character of boron trihalides is found to obey the order ;
temperature to form a protective film of its oxides which protects it from BI >BBr >BCl >BF .
3 3 3 3

further action. However, the above order is just the reverse of normally expected
(3) Oxides and hydroxides order on the basis relative electronegativities of the halogens. Fluorine, being
(i) The members of boron family form oxide and hydroxides of the the most electronegative, should create the greatest electron deficiency on
general formula M O and M (OH) respectively. boron and thus B in BF should accept electron pair from a donor very
3

rapidly than in other boron trihalides. But this is not true.

2 3 3

(ii) The acidic nature of oxides and hydroxides changes from acidic
to basic through amphoteric from B to Tl. This anomalous behaviour has been explained on the basis of the
B O and B(OH) > Al O and Al(OH) > relative tendency of the halogen atom to back-donate its unutilised electrons
2 3 3 2 3 3
to the vacant p orbitals of boron atom. In boron trifluoride, each fluorine
(acidic) (amphoteric) has completely filled unutilised 2p orbitals while boron has a vacant 2p
Ga O and Ga(OH) > In O In (OH) > Tl O Tl(OH)
2 3 3 2 3 3 2 3 3
orbital. Now since both of these orbitals belong to same energy level (2p)
(amphoteric) (basic) (strong basic) they can overlap effectively as a result of which fluorine electrons are
transferred into the vacant 2p orbital of boron resulting in the formation of
B(OH) or H BO is weak monobasic Lewis acid.
an additional p–p bond. This type of bond formation is known as back
3 3 3

(iii) Boric acid, B(OH) is soluble in water as it accepts lone pair of 3

bonding or back donation. Thus the B- F bond has some double bond
electron to act as Lewis acid. Rest all hydroxides of group 13 are insoluble in character. Back bonding may take place between boron and of the three
water and form a gelatinous precipitate. fluorine atoms and thus boron trifluoride is regarded as a resonance hybrid
B(OH) + H O B(OH) +H 3 2
1–

4
+ of some structures.
(iv) Al O being amphoteric dissolves in acid and alkalies both.
2 3
Resonance in boron trifluoride is also evidenced by the fact that the
three boron-fluorine bonds are indentical and are shorter than the usual
Al O + 3H SO  Al (SO ) + 3H O
2 3 2 4 2 4 3 2
single boron-fluorine bond As a result of back bonding, the electron
Al2 O 3  2 NaOH  fuse
2 NaAlO3  H 2O deficiency of boron is reduced and hence Lewis acid nature is decreased.
Sodium meta aluminate
The tendency for the formation of back bonding (p- p bond) is
(v) One of the crystalline form of alumina (Al O ) is called 2 3 maximum in BF and decreases very rapidly from BF to BI This is probably
3 3 3

corrundum. It is very hard and used as abrasive. It is prepared by heating due to the fact that overlapping of the vacant 2p orbitals of boron cannot
amorphous form of Al O to 2000 K. 2 3 take place easily with the p-orbitals of high energy levels (3p in Cl, 4p in Br
(4) Action of Acids and 5p in iodine). Thus BI Br and BCl are stronger Lewis acids than the BF
3 3 3 3.

(i) Boron does not react with non oxidizing acids, however, it (vi) Lewis acid character of halides of the group 13 elements
dissolves in nitric acid to form boric acids. decreases in the order, B > Al > Ga > In.
(ii) Al, Ga and In dissolve in acids forming their trivalent cations; (vii) Boron halides form complex halides of the type, [BF ], in which –

however, Al and Ga become passive due to the formation of protective film boron atom extends its coordination number to four by utilising empty p-
of oxides. orbital. It cannot extend its coordination number beyond four due to non
(iii) Thallium dissolves in acids forming univalent cation and availability of d-orbitals. However, the other trihalides of this group form
becomes passive in HCl due to the formation of water insoluble TICl. complex halides of the type (AlF ) , (GaCl ) and (InCl ) , etc where the
6
3–

6
3–

6
3–

central atom extends its coordination number to 6 by the use of d-orbitals.

(5) Action of Alkalies (viii) The fluorides of Al, Ga In and Tl are ionic and have high
(i) Boron dissolves only in fused alkalies, melting points. The high melting points of metal fluorides can be explained
2B + 6NaOH (fused) 2Na BO + 3H on the basis that their cations are sufficiently large and have vacant d-
3 3 2

orbitals for attaining a coordination number of six towards the relatively

(ii) Al and Ga dissolves in fused as well as in aqueous alkalies, 2Al +
small fluorine atom.
2 NaOH + 2H O 2NaAl O + 3H
2 2 2
(ix) Other halides of Al, Ga, In and Tl are largely covalent in
(iii) Indium remains unaffected in alkalies even on heating. anhydrous state and possess low melting point. These halides do not show
(6) Halides backbonding because of increases in the size of the element. However, the
(i) All the group 13 elements from the trihalides, MX on directly 3
make use of vacant p-orbitals by co-ordinate bond i.e. metal atoms complete
combining with halogens. their octet by forming dimers. Thus aluminium chloride, aluminium
bromide and indium iodide exist as dimers, both in the vapour state and in
M + X  MX 2 3
non-polar solvents.
(ii) All the trihalides of group 13 elements are known except Tl (III)
The dimer structure for Al Cl is evidenced by the following facts,
iodide. 2 6

(a) Vapour density of aluminium chloride measured at 400 C 0

(iii) Due to small size and high electronegativity of boron, all boron
corresponds to the formula Al Cl .
halides are covalent and Lewis acids. These exist as monomeric molecules 2 6

having plane triangular geometry (sp hybridization). 2 (b) Bond distance between aluminium chlorine bond forming bridge
is greater (2.21Å) than the distance between aluminum-chlorine bond
(iv) All Boron trihalides except BF are hydrolysed to boric acid. 3
present in the end (2.06 Å). The dimeric structure disappears when the
BX + 3H O B(OH) + 3HX;
3 2
[X=Cl, Br, I] 3 halides are dissolved in water This is due to high heat of hydration which
However, BF forms as addition product with water, 3
split the dimeric structure into [ M(H O) ] and 3X ions and the solution 2 6
3+ –

becomes good conductor of electricity.

BF + H OH [BF OH] HO
H O [BF OH] . + - 2 + -

Al Cl + 2H O 2[Al(H O) ] +6Cl ; Therefore Al Cl is ionic in water.

3 2 3 3 3

3+ –

2 6 2 2 6 2 6
 The dimeric structure may also split by reaction with donor (7) Both form weak acids like H BO and H SiO . 3 3 2 3

molecules e.g. R N. This is due to the formation of complexes of the type

3 (8) Both form binary compounds with several metals to give borides
R NAlCl The dimeric structure of Al Cl exist in vapour state below 473K and
3 3 2 6 and silicide. These borides and silicide react with H PO to give mixture of 3 4

at higher temperature it dissociates to trigonal planar AlCl molecule. 3 boranes and silanes.
Boron halides do not exist as dimer due to small size of boron atom 3Mg+2BMg B ; Mg B +H PO  Mixture of boranes
which makes it unable to co-ordinate four large-sized halide ions.
3 2 3 2 3 4

(Magnesium boride)

(x) BF and AlCl acts as catalyst and Lewis acid in many of the
2Mg + Si  Mg Si ; Mg Si + H PO Mixture of silanes
3 3

industrial process. 2 2 3 4

Anomalous Behaviour of Boron

(magnesium silicide)

Like Li and Be, Boron – the first member of group 13 also shows (9) The carbides of both Boron and silicon (B C and SiC) are very 4

anomalous behaviour due to extremely low size and high nuclear charge/size hard and used as abrasive.
ratio, high electronegativity and non-availability of d electrons. The main (10) Oxides of both are acidic and can be reduced by limited amount
point of differences are, of Mg In excess of Mg boride and silicide are formed.
(1) Boron is a typical non- metal whereas other members are metals. B O +3Mg  3MgO+2B ; SiO +2Mg 2MgO+Si
2 3 2

(2) Boron is a bad conductor of electricity whereas other metals are (11) Both the metals and their oxides are readily soluble in alkalies.
good conductors. 2B + 6NaOH  2Na BO + 3H  3 3 2

(borate)

(3) Boron shows allotropy and exists in two forms – crystalline and
amorphous. Aluminium is a soft metal and does not exist in different Si + 2NaOH + H O  Na SiO + 2H  2 2 3 2

forms. (silicate)

(4) Like other non-metals, the melting point and boiling point of B O + 6NaOH  2Na BO + 3H O
2 3 3 3 2

boron are much higher than those of other elements of group 13. SiO + 2NaOH  Na SiO + H O
2 2 3 2

(5) Boron forms only covalent compounds whereas aluminium and Both borates and silicates have tetrahedral structural units
other elements of group 13 form even some ionic compounds. BO4n  and SiO4n  respectively. Boro silicates are known in which boron
(6) The hydroxides and oxides of boron are acidic in nature whereas replaces silicon in the three dimensional lattice. Boron can however form
those of others are amphoteric and basic. planar BO units.3

(12) Acids of both these elements form volatile esters on heating

(7) The trihalides of boron (BX ) exist as monomers On the other hand,
3
with alcohol in presence of conc. H SO .
aluminium halides exist as dimers (Al X ). 2 4

B(OH) + 3ROHB(OR) + 3H O
2 6

(8) The hydrides of boron i.e. boranes are quite stable while those of 3 3 2

aluminium are unstable. Si(OH) + 4ROH Si(OR) + 4H O

4 4 2

(9) Dilute acids have no action on boron Others liberate H from Boron and its compounds
2

them. Boron is the first member of group –13 (IIIA) of the periodic table.
Boron is a non- metal . It has a small size and high ionization energy due to
(10) Borates are more stable than aluminates.
(11) Boron exhibit maximum covalency of four e.g., BH ion while –
which it can not lose its valence electrons to form B 3 ion. Its compounds
4
especially the hydrides and halides are electron deficient and behave as
other members exhibit a maximum covalency of six e.g., [Al(OH) ] . 6
3-

Lewis acid.
(12) Boron does not decompose steam while other members do so. (1) Ores of boron
(13) Boron combines with metals to give borides e.g. Mg B . Other 3 2 (i) Borax or tincal : Na B O . 10H O 2 4 7 2

members form simply alloys. (ii) Kernite or Rasorite : Na B O . 4H O 2 4 7 2

(14) Concentrated nitric acid oxidises boron to boric acid but no (iii) Colemanite : Ca B O . 5H O 2 6 11 2

such action is noticed other group members. (iv) Orthoboric acid : H BO (It occurs in the jets of steam called 3 3

B + 3HNO H BO + 3NO soffioni escaping from ground in the volcanic region of the Tuscany). Boron
3 3 3 2
is present to a very small extent (0.001%) in earth’s crust.
Diagonal relationship between Boron and Silicon
(2) Isolation : Elemental boron in the form of dark brown powder
Due to its small size and similar charge/mass ratio, boron differs is obtained either by reduction of boric oxide with highly electropositive
from other group 13 members, but it resembles closely with silicon, the metals like K, Mg, Al, Na, etc. in the absence of air and boron halides with
second element of group 14 to exhibit diagonal relationship. Some important hydrogen at high temperature eg.
similarities between boron and silicon are given below, B O + 6K   2B + 3K O
Heat
2 3 2

(1) Both boron and silicon are typical non-metals, having high m.pt.
b.pt nearly same densities (B=2.35gml S=2.34 g//ml). low atomic volumes –1 2BCl + 3H  3
 2B + 6HCl.
2
1270 K

and bad conductor of current. However both are used as semiconductors. By thermal decomposition of boron triiodide over red hot tungsten
filament and boron hydrides for example,
(2) Both of them do not form cation and form only covalent
compounds. 2BI 
3
  2B + 3I ; B H 
W, heat
 2B + 3H
Heat
2 2 6 2

(3) Both exists in amorphous and crystalline state and exhibit (3) Properties : It exists in mainly two allotropic forms i.e.
allotropy. amorphous dark brown powder and crystalline black very hard solid. It
(4) Both possess closer electronegativity values (B=2.0; Si=1.8). occurs in two isotopic forms, i.e., 5 B10 (20% abundance) and 5 B11 (80%
(5) Both form numerous volatile hydrides which spontaneously catch abundance). With air, boron forms B2 O3 and BN at 973K, with halogens,
fire on exposure to air and are easily hydrolysed. trihalides (BX 3 ) are formed, with metals borides are formed. eg.
(6) The chlorides of both are liquid, fume in most air and readily
hydrolysed by water. 4B+ 3O 2  
Heat
2 B2 O3
Boron trioxide
BCl + 3H O  B(OH) + 3HCl
3 2 3

2B + N 2  
Heat
2BN
SiCl + H O Si(OH) + 4HCl
4 2 4
Boron nitride
 2B + 3 X 2  2BX 3
Boron trihalide

3Mg + 2B  
Heat
Mg3 B2 H H H
..
b
t t

Magnesium boride
or B B
Water, steam and HCl have no action on B. oxidising acids (HNO 3 , ..
H 2 SO 4 ) convert boron to H 3 BO3 . H t
H b
H t

B + 3 HNO 3  H 3 BO3 + 3 NO 2 Structure of diborane (B H ) 2 6

2B + 3 H 2 SO 4  2 H 3 BO3 + 3 SO 2
The other boron hydrides are B5 H 9 , B4 H10 , B5 H11 etc.
Fused alkalies (NaOH, KOH) dissolve boron forming borates,
liberating hydrogen. (ii) Boron Halides
Boron reacts with halogens on strong heating to form boron halides
2B + 6KOH   2 K3 BO3 + 3H 2
Fused
.
(4) Uses of Boron : Boron is used in atomic reactors as protective 2B + 3 X 2   2B X 3 (X  F, Cl, Br, I)
Heat

shields and control rods, as a semiconductors for making electronic devices

in steel industry for increasing the hardness of steel and in making light BF3 and BCl 3 are gases, BBr3 is a volatile liquid while BI3 is a
composite materials for air crafts. solid.
(5) Compounds of Boron In these halides, the central boron atom has three shared pairs of
electrons with the halogen atoms. Therefore, these have two electrons less
(i) Boron Hydrides than the octet and are electron deficient compounds. They acts as Lewis
Boron forms hydrides of the types Bn H n  4 and Bn H n  6 called acids.
boranes. Diborane is the simplest boron hydride which is a dimer of BH 3 . F H F H
| | | |
Preparation F  B  : N  H  F  B  N  H
(a) 8 BF3  6 LiH   B2 H 6  6 LiBF4
450 K | | | |
F H F H
(b) 4 BCl 3  LiAlH4  2 B2 H 6  3 AlCl3  3 LiCl Lewis acid Lewis base

(c) In the laboratory, it is prepared by the oxidation of sod. The relative acidic strength of boron trihalides decreases as :
Borohydride with I2 . BI3  BBr3  BCl 3  BF3 .
(iii) Borax ( Na 2 B 4 O7 . 10 H 2 O )
2 NaBH 4  I2   B2 H 6  2 NaI  H 2
Polyether
It occurs naturally as tincal (Suhaga) which contains about 50%
Properties : (a) Since Boron in boranes never complete its octet of borax in certain land, lakes. It is also obtained from the mineral colemanite
electrons hence all boranes are called as electron-deficient compounds or by boiling it with a solution of Na 2 CO 3 .
Lewis acids.
(b) All boranes catch fire in the presence of oxygen to liberated a lot Ca 2 B6 O11  2 Na 2 CO 3  Na 2 B4 O7  2CaCO 3  2 NaBO2
of heat energy. Thus, they can also be used as high energy fuels. Colemanite Borax
Properties : (a) Its aqueous solution is alkaline due to hydrolysis,
B2 H 6  3O2  2 B2 O3  3 H 2 O; H  1976 KJ / mole
(c) Boranes are readily hydrolysed by water. Na 2 B4 O7 + 7 H 2 O  2NaOH+4 H 3 BO3 .
B2 H 6  6 H 2 O  2 H 3 BO3  6 H 2 (b) On heating borax loses its water of crystallization and swells up
to form a fluffy mass. On further heating, it melts to give a clear liquid which
(d) With carbon monoxide solidifies to a transparent glassy bead consisting of sodium metaborate
B2 H 6  2CO (BH 3  CO )2 ( NaBO2 ) and boric anhydride ( B2 O3 ),
(e) Boranes are used for formation of hydroborates or borohydrides  
such as LiBH 4 or NaBH 4 , which are extensively used as reducing Na 2 B 4 O7 .10 H 2 O  Na 2 B 4 O7  2 NaBO2  B 2 O3
10 H 2O Borax bead
agents in organic synthesis. Borax bead is used for the detection of coloured basic radicals under
2 LiH  B2 H 6    2 Li  [BH 4 ]
Diethyl ether the name borax bead test.
Borax bead test : Borax bead is a mixture of NaBO2 and B 2 O 3 .
2 NaH  B2 H 6   2 Na  [BH 4 ]
Diethyl ether
B 2 O 3 on heating combines readily with a number of coloured transition
Structure of diborane : B2 H 6 has a three centre electon pair bond metal oxides such as Co, Ni, Cr, Cu, Mn, etc. to form the corresponding
also called a banana shape bond. metaborates which possess characteristic colours,

(a) B  H t : It is a normal covalent bond (two centre electron pair CoSO 4  CoO  SO 3 ; CoO  B 2 O 3  Co (BO 2 )2
Cobalt meta borate
bond i.e., 2c  2e ). (Blue)

(b) B  H b : This is a bond between three atoms, B  H b  B,

Colours of some important metaborates are : Cupric metaborate,
Cu (BO 2 )2 is dark blue, chromium metaborate, Cr (BO2 )2 is green, nickel
(three centre electron pair bond i.e., 3c  2e ).
metaborate, Ni(BO2 )2 is brown and manganese metaborate, Mn(BO2 )2
Bridged Hydrogen
is pink violet.
Terminal
Hydrogen H t
H b
H t
(c) When heated with C 2 H 5 OH and conc. H 2 SO 4 it gives
volatile vapours of triethyl borate which burns with a green edged flame.
B 97 o
B 120o

Na 2 B4 O7  H 2 SO 4  5 H 2 O  Na 2 SO 4  4 H 3 BO3

H t
H b
H t
 H 3 BO3  3 C 2 H 5 OH  B(OC 2 H 5 )3  3 H 2 O ( Al2 O3 .H 2 O), Alunite or alum stone [K2 SO 4 . Al2 (SO 4 )3 .
Triethyl borate
4 Al(OH )3 ].
This reaction is used as a test for borate radical in qualitative
analysis. (2) Extraction : Aluminium is obtained by the electrolysis of the
Uses : (a) In making optical and hard glasses. (b) In the laboratory oxide (alumina) dissolved in fused cryolite. This involves following steps,
for borax bead test. (c) In softening of water. (d) In the preparation of Purification of ore
medicinal soaps due to its antiseptic character. (i) Baeyer's process
(iv) Boric acid or orthoboric acid ( H 3 BO 3 )  Caustic soda solution
Bauxite   Roasted ore 
Roasted

It is obtained from borax by treating with dil. HCl or dil. H 2 SO 4 , Finely powdered FeO Fe2 O3 High pressure (150 o C, 80 atm)
(red) filtered,Fe 2 O3 as residue
Na 2 B 4 O7  2 HCl  5 H 2 O  2 NaCl  4 H 3 BO3
It can also be obtained from the mineral colemanite by passing Filtrate   Pure Al2 O3 
Filtered
 Al(OH )3
Heat
(Sod. Aluminate) CO 2
SO 2 through a mixture of powdered mineral in boiling water, (ii) Hall's process
Ca 2 B6 O11 + 4 SO 2  11H 2 O  2Ca(HSO 3 )2  6 H 3 BO3
 Na
CO
Bauxite 2 
CO 3
 Solution 2
Properties : (a) It is a very weak monobasic acid, does not act as a (Finely powdered) Fused, extracted with o
50 - 60 C and filtered.
water. Residue Fe 2 O3
proton doner but behaves as a Lewis acid i.e. it accepts a pair of electrons (red) Filtrate(Na 2 CO 3 )

from OH  ion of H 2 O , Precipitate Al(OH)3   Pure Al2 O3

Heat

H 3 BO3  H 2 O [B(OH )4 ]  H  (iii) Serpek's process

It acts as a strong acid in presence of polyhydroxy compounds such Bauxite
 Coke  N
 2
 Silica reduced to  Alumina form AIN
as glycerol, mannitol etc. and can be titrated against strong alkali . (Finely powdered) Heated to
o
Si which volatalises aluminium nitride
(white) 1800 C
(b) With NaOH it forms, sodium metaborate,
H 3 BO3  NaOH  NaBO2  2 H 2 O 
 Pure Al2O3 
Hydrolysis
  Al(OH )3
Heated

(c) With C 2 H 5 OH and conc. H 2 SO 4 , it gives triethyl borate (iv) Hall and Heroult process : It is used for extraction of aluminium.
In this process a fused mixture of alumina (20%), cryolite (60%) and
H 3 BO3 +3 C2 H 5 OH   B(O C 2 H 5 )3 + 3 H 2 O
Conc . H 2 SO 4
fluorspar (20%) is electrolysed using carbon electrodes. Whereas cryolite
(d) Action of heat : The complete action of heat on boric acid may makes Al2 O3 conducting fluorspar decreases the melting point of
be written as, alumina.
H 3 BO3   HBO2
373 K
 
 H 2 B4 O7 
433 K
 B2 O3
Red hot
Aluminium is refined by Hoope's electrolytic process.
Boric acid Metaboric acid Tetra boric acid Boron oxide
(3) Compounds of Aluminium
Structure : In boric acid, planar BO 33
units are joined by hydrogen
bonds to give a layer structure. (i) Aluminium oxide or Alumina ( Al2 O3 ) : It occurs in nature as
Uses : (a) As a food preservative. (b) As a mild antiseptic for eye colourless corundum and several coloured minerals like ruby (red), topaz
wash under the name boric lotion. (c) For the preparation of glazes and (yellow), Sapphire (blue), amethyst (violet) and emerald (green). These
enamels in pottery. minerals are used as precious stones (gems).
(v) Borazine or Borasole or Triborine triamine ( B3 N 3 H 6 ) (ii) Aluminium chloride ( Al2 Cl 6 ) : It is prepared by passing dry
It is a compound of B, N and H. It is a colourless liquid and is also chlorine over aluminium powder.
called inorganic benzene. Al2 O3  3 C  3 Cl 2  2 AlCl3  3 CO (g)
o
2 B2 H 6  6 NH 3   2 B3 N 3 H 6  12 H 2 .
180 C (anhydrous)
It has a six membered ring of alternating B and N atoms, each is It exists as dimer Al2 Cl 6 , in inert organic solvents and in vapour
further linked to a H- atom.
H state. It sublimes at 100 o C under vacuum. Dimeric structure disappears
B when AlCl3 is dissolved in water. It is hygroscopic in nature and absorbs
H—N N—H moisture when exposed to air.
(iii) Thermite : A mixture of aluminium powder and Fe2 O3 in the
H—B B—H
N ratio 1:3. It is used for welding of iron. The reaction between Al and
Fe2 O3 is highly exothermic,
H
(vi) Boron nitride (BN)
Borazine Al  Fe2 O3  Al2 O3  Fe  Heat
It is prepared by treating BCl 3 with an excess of NH and (iv) Aluminium sulphate [Al (SO ) ] : It is used for the preparation of
2 4 3
3

pyrolysing the resulting mixture in an atmosphere of NH at 750°C, alums e.g., potash alum Al2 (SO 4 )3 . K 2 SO 4 . 24 H 2 O . It is also used for
3

making fire proof clothes.

750 o C
BCl 3 + NH 3  [ H 3 N  BCl 3 ] 
 BN + 3HCl . (iv) Alums : In general, the term alum is given to double sulphates
Excess NH 3
of the type M 2 SO 4 .M 2 (SO 4 )3 .24 H 2 O where M is a univalent
It is a colourless, good insulator, diamagnetic and almost unreactive
solid cation like Na  , K  and NH 4 , M  is a trivalent cation like Al 3  , Fe 3 
Aluminium and its compounds and Cr 3  .
(1) Ores of Aluminium : Bauxite ( Al2 O 3 .2 H 2 O), Cryolite Some important points to be noted about the alums are
(Na 3 AlF6 , Felspar (KAlSi3 O8 ), Kaolinite ( Al2 O3 . 2SiO2 .2 H 2 O) , Mica (a) General formula is M 2 SO 4 .M 2 (SO 4 )3 .24 H 2 O
(K 2 O.3 Al2 O3 . 6 SiO2 .2 H 2 O), Corundum ( Al2 O3 ) , Diaspore M  Monovalent metal; M   Trivalent metal
 In alum crystals, 6 water molecules are held by monovalent ion, 6
water molecules are held by trivalent ion, 12 water molecules are held in the
crystal structure.
(b) All alums are isomorphous. Aqueous solutions of alums are
acidic due to cationic hydrolysis of trivalent cation.
(c) Double sulphates of divalent ions and trivalent ions with 24
water molecules in their crystals are known as Pseudoalums. General
formula is MSO 4 .M 2 (SO 4 )3 .24 H 2 O
M  Bivalent metal; M   Trivalent metal
(d) Pseudoalums are not isomorphous with alums.
(e) Feather alum or ‘Hair-salt’ Al 2 SO 4 .18 H 2 O is a native form
of aluminium sulphate.
(f) Potash alum is used for tanning of leather, as mordant in dyeing
and calico printing, for sizing paper, as a syptic to stop bleeding and
purification of water.
Some important alums are
Potash alum K 2 SO 4 . Al 2 (SO 4 )3 .24 H 2 O
Sodium alum Na 2 SO 4 . Al 2 (SO 4 )3 .24 H 2 O
Ammonium alum (NH 4 ) 2 SO 4 . Al 2 (SO 4 )3 .24 H 2 O
Chrome alum K 2 SO 4 .Cr2 (SO 4 )3 .24 H 2 O

Carbon Family
Carbon is the first member of group 14 or IVA of the periodic table.
It consists of five elements carbon (C), silicon (Si), germanium (Ge), tin
(Sn) and lead (Pb). Carbon and silicon are nonmetals, germanium is
metalloid and tin and lead are metals.
(1) Electronic configuration
Elements Electronic configuration ( ns 2 np 2 )

6C [He] 2 s 2 2 p 2

14 Si [ Ne ] 3 s 2 3 p 2

32 Ge [ Ar] 3d 10 4 s 2 4 p 2

50 Sn [Kr] 4 d 10 5 s 2 5 p 2

82 Pb [ Xe] 4 f 14 5 d 10 6 s 2 6 p 2
 Physical properties The electronegativity from silicon onwards is almost is almost
constant or shows a comparatively smaller decreases due to screening
(1) Non-metallic nature : The non-metallic nature decreases along
effects of d electrons in elements from Ge onwards.
10

the group.
(7) Ionisation energy
C Si Ge Sn Pb
(i) The ionisation energy decreases regularly down the group; Pb
Non-metals metalloid metal metal however shows a higher value than Sn due to poor shielding of inner f-
(2) Abundance : Carbon and silicon are most abundant elements in orbitals as a result of which effective nuclear charge experienced by outer
earth’s crust whereas germanium occurs only as traces. Tin and lead also shell electrons becomes more in Pb.
occur in small amounts. Only carbon occurs in free state as coal, diamond Ionisation energy (kJ mol ) -1
C Si Ge Sn Pb
and graphite and in combined state as carbonates, CO petroleum and 2
IE 1086 786 761 708 715
1

natural gas Silicon is the second most abundant element after oxygen in
earth’s crust in form of silicates and silica. Germanium found in traces in IE 2
2352 1577 1537 1411 1450
coal and in certain deposits. It important constituent for making conductors (ii) The first ionisation energies of group 14 elements are higher
and transistors The important ore of tin is tin stone (SnO ) or cassiterite. 2
than their corresponding group 13 elements because of smaller size.
Lead is found is form of galena (PbS) anglesite (PbSO ) and cerussite 4
(iii) The electropositive character of these elements increases down
(PbCO ) The abundance ratio in earth’s crust is given below,
3
the group because of decreases in ionisation energy.
(3) Density : The density of these elements increases down the (8) Oxidation state
group as reported below
(i) Presence of four electrons in outermost shell of these elements
Element C Si Ge Sn Pb reveals that the members of this family can gain four electrons forming M 4+

Density (g/ml) 3.51 (for diamond) 2.34 5.32 7.26 11.34 or M ions to show ionic nature or exhibit tetravalent covalent nature by
4-

2.22 (for graphite) sharing of four electron pairs in order to attain stable configuration.

(4) Melting point and boiling points (ii) The formation of M or M ions require huge amount of energy
4+ 4-

which is normally not available during normal course of reactions, therefore,

(i) The melting point and boiling point of this group members these elements usually do not form M or M ions, but they usually form
4+ 4-

decrease down the group. compounds with covalence of four.

Element C Si Ge Sn Pb (iii) Ge, Sn and Pb also exhibit +2 oxidation state due to inert pair
m.pt(K) 4373 1693 1218 505 600 effect.
b.pt.(K) – 3550 3123 2896 2024 (iv) Sn and Pb show ionic nature.
2+ 2+

(ii) The melting point and boiling point of group 14 elements are (v) The tendency to form +2 ionic state increases on moving down
however, higher than their corresponding group 13 elements. This is due to the group due to inert pair effect.
the formation of four covalent bonds on account of four electrons in their (9) Catenation
valence shells which results in strong binding forces in between their atoms
in solid as well as in liquid state. (i) The tendency of formation of long open or closed atom chains by
the combination of same atoms in themselves is known as catenation.
(5) Atomic radii and atomic volume
(ii) The catenation is maximum in carbon and decreases down the
(i) Both atomic radii and atomic volume increases gradually on group.
moving down the group due to the effect of extra shell being added from
member to member. (iii) This is due to high bond energy of catenation.

C Si Ge Sn Pb (iv) Only carbon atoms also form double or triple bonds involving
p-p multiple bond within itself.
Atomic radius (pm) 0.77 111 122 141 144
Atomic volume (ml) 3.4 11.4 13.6 16.3 18.27 > C = C< ; – C  C –
(ii) The atomic radii of group 14 elements are than their (v) Carbon also possesses the tendency to form closed chain
corresponding group 13 elements due to increase in nuclear charge in the compounds with O, S and N atoms as well as forming p-p multiple
same period. bonds with other elements particularly nitrogen and oxygen e.g. C =O; C=N;
(iii) Some of the ionic radii involving six co-ordination of these C  N; C = S are the functional groups present in numerous molecules due
group elements are given below, to this reason.
C Si Ge Sn Pb (vi) Carbon can form chain containing any number of carbon atoms
Ionic radius (M ) in pm
2+
– – 73 118 119 Si and Ge cannot extend the chain beyond 6 atoms, while Sn and Pb do not
form chains containing more than one or two atoms.
Ionic radius (M ) in pm
++
– 40 53 69 78
(6) Electronegativity : The electronegativity decreases from C to Si (vii) The reason for greater tendency of carbon for catenation than
and then becomes constant. other elements in the group may further be explained by the fact that the C
– C bond energy is approximately of the same magnitude as the energies of
C Si Ge Sn Pb the bond between C and other elements. On the other hand, the Si – Si
Electronegativity on pauling scale 2.5 1.8 1.8 1.7 1.6 bond is weaker than the bond between silicon and other elements.
 Bond Bond energy (k Bond Bond energy (iii) Tin has three crystalline modifications with the following
equilibrium temperature
J/mol) (kJ/mol)
  tin 15.2oC   Sn 161oC   Sn 232oC Liquid tin
C–C 348 Si–Si 180 (Grey) (White) (Rhombic)

The conversion of white tin to grey tin is accompanied by an

C–O 315 Si–O 372
increase in volume and the latter, being very brittle, easily crumbles down
C–H 414 Si–H 339 to powder. This phenomenon is called tin disease tin pest or tin plague.
Chemical properties
C–Cl 326 Si–Cl 360 (1) Hydrides : All the elements of group 14 combine with hydrogen
C–F 439 Si–F 536 directly or indirectly to form the covalent hydrides, MH 4 (M = C, Si, Ge,
Sn or Pb). The number of hydrides and the ease of preparation decrease on
(10) Allotropy going from carbon to lead.
The hydrides of silicon are called silanes having the general formula
The phenomenon of existence of a chemical element in two or more Sin H 2n  2 . The hydrides of germanium are called germanes while those of
forms differing in physical properties but having almost same chemical
tin are called the stannanes. Only lead forms an unstable hydride of the
nature is known as allotropy. If an element or compound exists in two or
formula, PbH4 called the plumbane.
more forms, it is also known as polymorphism e.g. zinc blende and wurtzite
are polymorphs of ZnS. Three hydrides of germanium, i.e., GeH 4 , Ge 2 H 6 and Ge 3 H 8
Kinds of allotropy. Allotropy is of three types : and only two hydrides of tin i.e., SnH 4 and Sn 2 H 6 are well known.
(i) Enantiotropy : When two forms of a solid substance exist (2) Oxides : Carbon forms five oxides CO, CO 2 , C3 O2 (carbon
together in equilibrium with each other at a particular temperature under
normal pressure it is called enantiotropy. suboxide), C5 O 2 and C12 O9 , C3 O2 is the anhydride of malonic acid and

For example, at normal pressure and temperature between CO 2 is the anhydride of H 2 CO 3 (carbonic acid) CO 2 is a non-polar
368.6 K and 285 K , sulphur (solid) exist in two forms (rhombic linear molecule due to maximum tendency of C to form p–p multiple
sulphur), S R and (monoclinic sulphur), S M in equilibrium with each bond with oxygen. Si forms SiO2 . Pb forms a number of oxides. PbO can

other. S R ⇌ S M be obtained by heating Pb(NO 3 )2 ,

2 Pb(NO 3 )2  2 PbO  4 NO 2  O2 .

Heat
(ii) Monotropy : It is the type of allotropy in which only one
allotrope is stable, under normal conditions the other being unstable e.g., The red form of PbO is called litharge and the yellow form is
diamond and graphite, oxygen and ozone etc. massicot. Pb3 O4 (Red lead, or Sindur) is prepared by heating litharge in
(iii) Dynamictropy : It is the type of allotropy in which there is a o

true equilibrium between the two allotropes, one changing into the other at air at 470C, 6 PbO  O2   2 Pb3 O4 , Pb3 O4 is a mixed oxide
470 C

exactly the same rate as the reverse occurs. Both allotropes are stable over a of PbO2 .2 PbO. Pb2 O3 is called lead sesquioxide. GeO 2 , SnO 2 etc. are
wide range of temperature. also network solids.
For example, liquid sulphur exist in two forms, the pale yellow
CO 2 and SiO2 is acidic, GeO 2 is weakly acidic while SnO 2
mobile form called S  and dark viscous form called S  in equilibrium
and PbO2 are amphoteric in nature.
with each other. S  ⇌ S 
All the elements of group 14 except silicon from monoxides e.g.,
With increase in temperature, the later form is formed at the CO, GeO, SnO and PbO. Out of these monoxides only CO is neutral,
expense of the former but when the liquid is cooled, the reverse change
while all other monoxides are basic.
occur. Thus sulphur shows both enantiotropy and dynamictropy.
(3) Halides : Elements of group 14 react with halogens directly to
Cause of allotropy : (i) In general the allotropy among solid
form tetrahedral and covalent halides except C where its halide is produced
substances is due to the difference in crystalline structure. (ii) It may also
by the action of halogens on hydrocarbons. PbBr4 and PbI4 do not
be due to the presence of different number of atoms e.g., O 2 and
O 3 , S 8 , S 2 etc. (iii) It may be due to the difference in nuclear spins e.g., exist because Pb 4  is a strong oxidant and Br  and I  are strong
ortho and para hydrogen. reductants. Hence Pb 4  ion is difficult to survive in presence of strong
Different allotropic forms Except lead, all elements show allotropy. reductants Br  and I  and is immediately reduced to Pb 2 .
(i) Carbon has two crystalline allotropic forms i.e., diamond and (4) Carbides : Carbides are binary compounds of carbon with
graphite. In diamond C atom is sp 3 hybridised and it has a three elements of lower or about equal electronegativity.
dimensional network structure. Since no valence electron is available, hence Preparation : Carbides are generally prepared by heating the
diamond is a bad conductor of electricity. However in graphite C atom is elements orits oxide with carbon or hydrocarbon at very high temperatures.

sp 2 hybridised and has a delocalised  -electron cloud responsible for its Ca  2C  BaC2 ; 2 Li  2C  Li 2 C 2
high electrical conductivity. It may be noted that diamond is
CaO  3C  CaC 2  CO
thermodynamically less stable than graphite at ordinary temperatures.
(ii) Silicon has both crystalline and amorphous forms. 4 Li  C 2 H 2  Li 2 C 2  LiH
 Carbides are classified into three types on the basis of chemical (6) Carbon is not affected by alkalies whereas other members react
bonding. on fusion. For example, silicon form silicates,
(1) Salt like carbides : These carbides are formed by the metals of Si  2 NaOH  1 / 2 O 2  Na 2 SiO3  H 2 .
Sodium silicate
groups IA, IIA, IIIA (except boron), coinage metals, Zinc, cadmium & some
lanthanides. Silicon and its compounds
(i) Acetylides : These are ionic carbides which yield acetylene on Silicon, being a second member of group – 14, has a much larger
hydrolysis. The alkali metals and copper, silver and gold form M C type2 2
size and lower electronegativity than that of carbon. As a result silicon does
not form double bond with itself or with oxygen. Thus SiO bonds are much
compounds. These contain C 22  ions.
stronger than Si – Si and Si –H bonds. Silicon has vacant 3d-orbitals in its
(ii) Methanides : These carbides evolve methane on hydrolysis. valence shell due to which it can extend its covalency from four to five and
Al4 C3 , Be 2 C, Mn3 C etc are some are of methanides. These contains six.
(1) Occurrence : Silicon is the second most abundant element ( 27.7%)
C 4  groups.
in earth’s crust next to oxygen .It does not occur in free state. It occurs mainly in
(iii) Allylides : These carbides evolve allylene (methyl acetylene) on the form of Silica and silicates. Silicates are formed in rocks and clay as silicates
hydrolysis. This type of the carbides is only Mg 2 C 3 it contains C 34  of Mg, Al, K or Fe. e.g. Feldspar ; K 2 Al2 O3 .6 SiO2 , Kaolinite;
discrete groups. Al2 O3 .2SiO2 .2 H 2 O .
(2) Mixed carbides : These carbides yield a mixture of hydrocarbons
on hydrolysis, carbides of iron group, UC2 and ThC 2 belong to this (2) Preparation : Elemental silicon is obtained by reduction of silica
with high purity coke in an electric furnace using excess of silica e.g.
group.
SiO2  2C  Si  2CO
(3) Covalent carbides : The only true covalent carbides are those of
SiC (carborundum) and B4 C, B13 C 2 etc. These are chemicallyinert so Very high purity silicon required for making semiconductors is
become hard. obtained by reduction of highly purified SiCl4 form ( SiHCl3 ) with
On account of hardness, these are used as abrasives. hydrogen followed by purification by zone refining eg.
(4) Metallic or interstitial carbides : If these carbides possess
metallic lustre high electrical conductivity and chemically inert. These are SiCl4  2 H 2  Si  4 HCl ; SiHCl3  H 2  Si  3 HCl
extremely hard like diamond and possess very high melting points.
Ability to form complexes : The ability of group 14 elements to form (3) Properties : (i) Silicon exists in three isotopes 14 Si 29 (most
complexes is highly favoured by a high charge, small size and availability of common), Si 30 with air at high temperature SiO2 form,
14
empty orbitals of the right energy. The compounds in which carbon shows
a covalency of four possess a closed shell electronic configuration of a noble Si + O 2  Si O 2 .
gas and therefore carbon does not form complexes. Silicon and other
heavier elements, however, can form complexes due to the availability of (ii) With steam, Si reacts when heated to redness to liberate
energetically suitable empty d -orbitals and a coordination number of six is hydrogen, Si + 2 H 2 O   Si O 2 + 2 H 2 .
Redness

found in these complexes. For example, in the formation of [SiF6 ]2  , four (iii) With halogens, Si reacts at elevated temperature forming SiX 4
covalent and two co-ordinate bonds are formed as a result of sp 3 d 2 except fluorine which reacts at room temperature.
hybridisation. As such the resulting ion has an octahedral geometry. Thus (iv) Silicon combines with C at 2500K forming Silicon Carbide (SiC)
elements like Si, Ge, Sn and Pb have an ability to increase their co- known as carborundum (an extremely hard substance),
ordination number from four to six. Other examples of hexa co-ordianted Si + C   SiC.
2500 K
species are :
(v) It reacts with metals like Ca, Mg etc in an electric arc furnace to
[GeF6 ]2 , [SnCl 6 ]2 , [PbCl6 ]2 etc. form Silicides ( Ca 2 Si, Mg2 Si etc.)
Anomalous behaviour of Carbon
(vi) Silicon dissolves in hot aqueous alkalies liberating hydrogen, Si
Carbon is found differ in many properties from the rest of the
members of group 14. This is because of the following : (i) Its smallest size + 4NaOH   Na 4 SiO4  2H 2 
Heat

(ii) Its high electronegativity (iii) Its property to catenate (iv) Absence of d- (vii) It also dissolves in fused Na 2 CO 3 displacing carbon
orbitals in it.
Some of the properties in which it differs from other members are, Na 2 SiO 3 C .
(1) The melting and boiling points of carbon are very high as (4) Uses of silicon : (i) It is added to steel as ferrosilicon ( an alloy
compared to the rest to the members of the family. of Fe and Si) to make it acid resistant.
(2) Carbon in its diamond form is one of the hardest substance (ii) It is used in the pure form as a starting material for production
known. of silicon polymers (Silicones).
(3) It has maximum tendency to show catenation. (5) Compounds of silicon
(4) Carbon has high tendency to form P – P multiple bonds with (i) Silicates : Silicates are the metal derivatives of silicic acid (H SiO ).
4 4

other elements like nitrogen, oxygen, sulphur etc. Other members of the The basic of all silicates is the SiO44  anion. In SiO44  anion, Si is sp 3

family form P – d bonds and that also to a lesser extent. hybridised, and it forms four covalent bonds with four negatively charged
(5) CO 2 is a gas while the dioxides of all other members are solids. oxygen atoms. SiO44  anion has a tetrahedral shape.
O– O–

Si Si–

O– O– O– O–
O–
 HF readily dissolves Silica, therefore HF can not be store in glass
bottles which contain Silica.
It is used in large amount to form mortar which is a building
material. It is also used in the manufacture of glass and lenses.
Alkali metal silicates are commonly prepared by fusing metal oxides
or metal carbonates with sand (SiO ) at high temperatures. For examples,
2
(iii) Silicones
sodium silicate can be prepared by fusing sand with sodium carbonate.
Polymeric organo-silicon compounds containing Si  O  Si bonds
Na 2CO 3  SiO2   Na 2 SiO3  CO 2 (g)
Fusion
are called silicones. These have the general formula (R 2 SiO)n . Where R
sand sodium silicate

Table 18.1 Classification of silicates is CH 3 -group (majority cases) or C 6 H 5 -group.

No. of
Silicon Net cha-rge
carners No. of Structure and Anion Preparation : The preparation of silicones is generally carried out by
of SiO com-mon Oxygen
4
in the Example
tetrahe- oxygen
silicate
the hydrolysis of dialkyldichlorosilanes (R 2 SiCl 2 ) or diaryldichlorosilanes
dra atoms Diagram and Description
structure
shared ( Ar2 SiCl 2 ) , which are prepared by passing vapours of RCl or ArCl
Si = +4
O= –8 ortho-
silicates over silicon at 570 K with copper as a catalyst.
Zero Zero Net = –4
Discrete SiO4 4–anion
Mg 2 SiO 4
SiO 44  2 RCl  Si    R 2 SiCl 2
Cu , 570 K

Si = + 8
O = – 14 Pyro-
1 1 Net = –6
R R R
silicates
Island structure (Si 2O7 )6  | | |
 H 2O
Si= +12 R 2 SiCl 2    O  Si  O  Si  O  Si  O 
 HCl
O = –18 Wollas- | | |
2 2 Ring anion Net = –6 tonite
Ca3Si3O9 R R R
(Si 3 O9 )6 
Si =+24 Silicones may be obtained in the form of oils, rubber on resins
O = –36 Beryl, depending upon the extent of polymerisation which depends upon reaction
2 2 Net=–12 Be 3 Al 2
conditions and nature of alkyl groups.
(Si 6 O18 )12  Si 6 O18
Ring anion Properties and Uses : Silicones are water repellent and quite inert
Pyroxenes, chemically. These resist oxidation, thermal decomposition and attack by
Si = +4
e.g., organic reagents. These are also good electrical insulators and antifoaming
O = –6
2 2 MgCa
Net = –2 agents. These have found the following uses :
Si 2 O 6
Chain anion (SiO 32  )n
Asbestos (a) Silicones have been used for making water-proof papers, wools,
textiles, wood etc., after coating these articles with silicones.
Si = +8 (b) The viscosities of silicones do not change with changes in
O = –10 Clays, talc temperature, therefore, these are used as all weather lubricants.
3 3 Net = –2 kaolinite
(Si 2O52  )n (c) As antifoaming agent in industrial processes.
Two dimensional sheet
structure
(d) As a mould releasing agent in rubber industry and foundry. It
Quartz, avoids the sticking of the castings to the mould.
– Si = +4
O = –4 Tridymite (e) For making body implants in cosmetic surgery due to its inert
4 4
and Cristo-
Three dimensional network (SiO 3 )n balite nature.
(ii) Silica or silicon dioxide ( SiO2 ) (f) Silicones are now incorporated in paints for resisting dampness
and for water proofing.
It occurs in nature in various forms such as sand, quartz and flint
.It is also a constituent of various rocks. It is solid at room temperature. It is (g) Due to their water repellent nature and high dielectric constant,
insoluble in water. silicones are used in electrical condensers.
Silica has a three dimensional network structure in which each Si is
(iv) Silica gel : When a mineral acid (Such as HCl) is added to a
bonded to four oxygen atoms which are tetrahedrally disposed around concentrated solution of a silicate, gelatinous white ppt. of hydrated silica
silicon atom. Each O atom is shared by two Si atoms. It may be noted that (silicic acid) separate out.
CO 2 is a gas, while SiO2 is hard solid with very high melting point.
Na 2 SiO3  2 HCl  2 NaCl  SiO2 . xH 2 O
Si O 2 + 4HF  Si F4 + 2 H 2 O The white ppt. thus obtained is heated to lose water. When the
water content is very low, the solid product is called silica gel. It possesses
Si F4 + 2HF 
 H 2 SiF6 excellent absorptive properties due to its porous nature and is used for
(Hydro flouro silicicacid) absorbing moisture and an adsorbent in chromatography.
 (v) Silanes : The hydrides of silicon are called silanes. For example; Na 2 CO 3  SiO2  Na 2 SiO3  CO 2 
SiH 4 Silane, Si 2 H 6 disilane, Si 3 H 8 Trisilane Si 4 H 10 Tetrasilane.
CaO  SiO2  CaSiO3
Silanes are poisonous. These are much less stable than the
corresponding alkanes and are decomposed into elements on heating above On continuously heating the entire amount of CO 2 is driven out
450 o C . Their thermal stability decreases with increase in molecular mass. and clear viscous fused mass is obtained. It is poured into moulds to get
Unlike alkanes, silanes are reducing agents. different types of articles, which are allowed to cool gradually.
(vi) Glass This typed of glass is called soda glass or soft glass which has the
Glass is an amorphous and transparent solid which is obtained by approximate composition, Na 2 SiO3 , CaSiO3 ,4 SiO2 .
solidification of various silicates and borates of potassium and calcium. Various varieties of glass : The different varieties of glasses and their
Preparation : Ordinary glass is a mixture of sodium and calcium special constituents are given below,
silicates and is produced by fusing together a mixture of sodium carbonate,
calcium oxide and silicon dioxide (Silica) in a furnace at about 1700K
Table 18.2
Type of glass Constituents Special use
Soft glass Na 2CO 3 , CaCO3 , SiO 2 Ordinary glass for window panes, test tubes, bottles, etc.

Hard glass K2CO3 , CaCO3 , SiO2 For combustion tubes and chemical glassware

High refractive index glass Lead oxide, K 2CO 3 For making lenses cut glasses
(Flint glass)
Pyrex glass Na 2 CO 3 , Al 2 O 3 , B 2 O 3 or borax, sand For high quality glass apparatus cooking utensils

Crook’s glass K2CO 2 , PbCO3 , CeO 2 , sand Absorbs ultra violet rays, for making lenses

Jena glass Zinc and Barium Boro silicates It is resistant to heat shock and common reagent. It is used for
making good quality of glass wares.

Coloured glass : Addition of transition metal compounds to glass (ii) Roasting : The concentrated ore is heated in a current of air
give coloured glasses . Small amounts of Cr(III), Mn(IV), Co(II) and Fe(III) when impurities like S and As are oxidised to volatile SO 2 and
compounds impart green, violet blue or brown colour respectively As 2 O 3 . Iron pyrites change to their oxides and sulphates.
Table 18.3 (iii) Leaching and washing : The roasted ore is treated with water
Compound added – Colour Compound added – Colour when CuSO 4 and FeSO 4 are washed away from the main ore. Further
imparted imparted lighter ferric oxide is washed away leaving behind heavier ore particles
Cobalt axide ( CoO) – Blue known as black tin containing 60 to 70% SnO 2 .
Chromium oxide ( Cr2 O 3 ) –
Green SnO 2  2C  Sn  2CO
Cuprous oxide ( Cu 2 O ) – Red Auric chloride ( AuCl 3 ) – Ruby CaCO 3  CaO  CO 2 ; CaO  SiO 2  CaSiO3
Flux Slag
Cadmium sulphide (CdS) – Manganese dioxide ( MnO2 ) –
Lemon yellow Molten tin is drawn into blocks. It contains 99.5 percent of tin metal
Purple
and is called block tin.
Etching of glass : Glass is attacked by hydrofluoric acid. This Refining of tin : It is purified by liquation, poling and electrolytic
property is used in the etching of glass. The glass to be etched is coated refining.
with a thin layer of wax and the design to be produced is scratched with a
needle. An aqueous solution of HF is applied to the exposed part. After For very high purity, it is purified by electrolytic method. The
some time it is placed in hot water and wax is removed from the surface. electrolyte consists of tin sulphate containing a small amount of
The marks are engraved on the exposed parts. hydrofluorosilicic acid (H 2 SiF6 ) and sulphuric acid. Impure tin makes
Tin and its Compounds anode while pure tin sheet serves as cathode.
(3) Comounds of Tin
(1) Important ore : Cassiterite (tin stone) SnO 2
(i) Stannic oxide, SnO : It is prepared by heating tin strongly in air.
2

(2) Extraction of tin from tin stone.

Sn  O 2  SnO 2
(i) Concentration : The powdered tin stone is concentrated by
gravity separation and the magnetic impurities like wolframite etc., are It can also be prepared by heating metastannic acid obtained by the
separated from tin stone by magnetic separators. action of conc. HNO 3 on tin.

Sn  4 HNO 3 (conc.)  H 2 SnO 3  4 NO 2  H 2 O

 
H 2 SnO 3  SnO 2  H 2 O SnCl 4  H 2 O  Sn(OH )Cl  HCl
It occurs in nature as tin stone. It is a white solid insoluble in water Sn(OH )Cl  3 H 2 O  Sn(OH )4 or H 2 SnO 4  3 HCl
and is amphoteric in nature. With NaOH it forms Na 2 SnO 3 . It is used
Its hydrolysis is prevented by HCl which forms complex anion
for making enamels and glazes for tiles, pottery etc. it is also used as a
polishing powder. [SnCl 6 ]2 

(ii) Stannous oxide, SnO : It is prepared by heating stannous oxalate (c) It forms double salts with NH 3 , N 2 O, PCl5 e.g.,

SnC 2 O 4  SnO  CO  CO 2 SnCl 4 .4 NH 3 .
It is used as a mordant and tinning agent.
Oxidation of SnO to SnO 2 is checked by CO . It is a grey solid
(vi) Stannous fluoride, SnF : It is obtained by dissolving SnO in
which oxidises readily to SnO 2 when heated in air. 2

HF
2SnO  O 2  2SnO 2 SnO  2 HF  SnF2  H 2 O
It is amphoteric in nature and reacts both with acids and alkalies. It is a white crystalline solid insoluble in water. It is used in tooth
With NaOH it forms Na 2 SnO 2 . pastes to help in controlling dental decay.
Tinning : During cooking, organic acids present in food stuff attack
(iii) Stannous sulphide, SnS : It is insoluble in water but soluble in the household utensils made of copper, brass etc. in the presence of air.
hot conc. HCl . In yellow ammonium polysulphide it gets converted to since tin is not attacked by organic acids, the utensils are protected by
ammonium thiostannate (NH 4 ) 2 SnS 3 . tinning.
Lead
(iv) Stannous chloride, SnCl : When Sn is heated with HCl
2

(conc.) SnCl 2 is formed. (1) Some important ores

Galena;  PbS (Main); Cerussite  PbCO 3
Sn(s)  HCl(Conc.)  SnCl 2 (aq)  H 2 (g)
Anglesite  PbSO4 , lararkite PbO.PbSO 4
On concentrating the resulting solution, crystals of SnCl 2 .2 H 2 O
are obtained. When it is heated, basic tin chloride is obtained. (2) Extraction from galena
 (i) Concentration : The finely powdered ore is concentrated by froth
SnCl 2 .2 H 2 O(s)  Sn(OH )Cl  HCl  H 2 O
floatation process.
To obtain anhydrous SnCl 2 , heat Sn in dry HCl gas. (ii) Reduction process
 (a) Self reduction process
Sn  2 HCl  SnCl 2  H 2
(a) It exists as a anhydrous (white powder, m.p. = 520 K , rhombic  Roasting : The concentrated ore is heated in air. lead sulphide is
partially converted into lead oxide and lead sulphate.
solid) as well as dihydrate SnCl 2 .2 H 2 O (white, m.p.  480 K ,

monoclinic) and is used as a strong reducing agent in conc. HCl in 2 PbS  3O2  2 PbO  2SO 2
laboratory.

PbS  2O2  PbSO4
SnCl 2 also reduces HgCl 2
 Self reduction : The supply of air is cut off and the temperature is
2 HgCl2  SnCl 2  Hg 2 Cl 2  SnCl 4
raised to melt the charge. The galena reduces both PbO and PbSO4 to
Hg 2 Cl 2  SnCl 2  2 Hg  SnCl 4 metallic lead.
(b) It is precipitated as hydroxide by an alkali. 
PbS  2 PbO  3 Pb  SO 2
(c) If forms addition compounds with NH 3 such as SnCl 2 .NH 3 
PbS  PbSO4  2 Pb  2SO 2
and SnCl 2 .2 NH 3 .
(b) Carbon reduction process
(v) Stannic chloride, SnCl : It is obtained by the action of Cl 2 on
 Roasting : The powdered ore is mixed with lime and roasted in
4

molten Sn
excess of air. the impurities like S and As are oxidised to their volatile
Sn  2Cl 2  SnCl 4 oxides while PbS is converted to PbO .
It can also be obained by distilling tin with mercuric chloride.  
S  O2  SO 2 4 As  3O2  2 As2 O3
;
Sn  2 HgCl2  SnCl 4  2 Hg

2 PbS  3O2  2 PbO  2SO 2
(a) It is a colourless fuming liquid (b.p 388 K ) soluble in water.
It is used as a strong reducing agent in laboratory. It is also used as  Smelting : Roasted ore is mixed with coke and lime (flux) and
a mordant in dyeing. smelted in a blast furnance. PbO is reduced to Pb .
(b) It can exist as SnCl 4 .5 H 2 O and with excess water it is  
PbO  C  Pb  CO ; PbO  CO  Pb  CO 2
hydrolysed to form basic chloride and ultimately stannic acid (H 2 SnO 4 ) .
 
CaCO 3  
CaO  CO 2 ; CaO  SiO2  CaSiO3 (iv) Lead chloride, PbCl : It can be prepared by treating a salt of
2

Lime Slag lead with dil. HCl

(iii) Purification : It is purified electrolytically. The electrolyte Pb(NO 3 )2  2 HCl  PbCl2  2 HNO 3
consists of lead silicofluoride (PbSiF6 ) and hydrofluosilicic acid. Impure It can also be obtained by dissolving lead (II) oxide to lead (II)
lead is made anode and sheet of pure lead serves as cathode. carbonate in HCl . It is soluble in hot water but precipitate out in cold
Properties of Lead water. it is soluble in conc. HCl due to the formation of a complex,
With oxygen lead form oxides, with chlorine it forms chloride tetrachloroplumbate (II) ion.
PbCl2 , with sulphur it gives sulphide PbS and with H 2 SO 4 the
PbCl2  2 HCl  H 2 [PbCl4 ]
corresponding sulphate PbSO4 . With NaOH it forms plumbate.
It also reacts with hot lime water to give Pb(OH )Cl which is used
Pb  2 NaOH  Na 2 PbO2  H 2 as white pigment.
(3) Compounds of Lead
PbCl2  Ca(OH )2  Pb(OH )Cl  CaO  HCl
(i) Lead oxide (Litharge), PbO : It is prepared by heating the nitrate.

2 Pb(NO 3 )2  2 PbO  4 NO 2  O2 (v) Lead tetrachloride, PbCl : It is obtained by heating of PbO2
4

It exist in two varieties yellow form (messicol) and red form with conc. HCl .
(litherage). Yellow form is prepared by gently heating lead in air while It is a yellow oily fuming liquid which decomposes into PbCl2 at
fusion yield red form. It is insoluble in water and amphoteric in nature.
373 K .
It dissolves in NaOH to form sod. Plumbite.
PbO  2 NaOH  Na 2 PbO2  H 2 O PbCl4   PbCl2  Cl 2
373 K

It can be reduced with various reducing agents ( C, H 2 , CO etc.) to It also combines with HCl to form complex hexachloroplumbate
lead. (IV) ion.
It is used in paints and varnishes, for making flint glass, for making PbCl4  2 HCl  H 2 [PbCl6 ]
lead (II) salts and for glazing pottery.
(ii) Lead dioxide, PbO : It is prepared by heating
2
Nitrogen Family
Pb3 O4 (2 PbO  PbO2 ) with dilute HNO 3 Nitrogen is the first member of group 15 or VA of the periodic table.
 It consists of five elements nitrogen (N), phosphorus (P), arsenic (As),
Pb3 O4  4 HNO 3  2 Pb(NO 3 )2  2 H 2 O  PbO2
antimony (Sb) and bismuth (Bi). The elements of this group are collectively
It is amphoteric in nature and dissolve in NaOH to form sodium called pnicogens and their compounds as pniconides. The name is derived
plumbate.
from Greek word “Pniomigs” meaning suffocation. Pniconide contain M 3 
2 NaOH  PbO2  Na 2 PbO3  H 2 O species.
It is a powerful oxidising agent. It reacts with conc. HCl on (1) Electronic configuration
warming to give PbCl4
Elements Electronic configuration ( ns 2 np 3 )
PbO2  4 HCl  PbCl4  H 2 O
Warm
7 N [He] 2 s 2 2 p 3
It is a chocolate brown solid insoluble in water and nitric acid. It is a
powerful oxidizing agent. It is amphoteric in nature and is used in lead 15 P [ Ne ] 3 s 2 3 p 3
storage batteries and in safety matches.
(iii) Minium or sindhur or Red lead, Pb O : It is prepared by heating
3 4
33 As [ Ar] 3d 10 4 s 2 4 p 3
PbO in air to above 673 K .
51 Sb [Kr] 4 d 10 5 s 2 5 p 3
6 PbO  O2   2 Pb3 O4
673 K

83 Bi [ Xe] 4 f 14 5 d 10 6 s 2 6 p 3
It is a red crystalline solid insoluble in water.
It is a mixed oxide PbO2  2 PbO and reacts with HNO 3 to Physical properties
form Pb(NO 3 )2 and PbO2 (1) Physical state : Nitrogen– (gas), phosphorus – (solid) (vaporises
2 PbO.PbO2  4 HNO3  Pb(NO 3 )2  2 H 2O  PbO2 easily), As, Sb, Bi–solids.
Nitrogen is the most abundant gas in the atmosphere. It constitutes
It is a strong oxidising agent. It liberates chlorine with conc. HCl
about 78% by volume of the atmosphere. Phosphorus is the most reactive
and O 2 with conc. H 2 SO 4 element in this group and its yellow form is always kept under water.
Pb3 O4  8 HCl  3 PbCl2  4 H 2 O  Cl 2 (2) Atomic radii : Atomic radii increases with atomic number down
the group i.e., from N to Bi due to addition of extra principal shell in each
2 Pb3 O4  6 H 2 SO 4  6 PbSO4  6 H 2 O  O2 succeding elements.
It is used as a protective paint in iron, steel and silver mirrors and in (3) Ionisation energy : The ionisation values of the elements of this
glass industry. group decreases down the group due to gradual increases in atomic size.
 (4) Electronegativity : Generally the elements of nitrogen family have The decreasing order of basic strength of hydrides is as follows :
high value of electronegativity. This value shows a decreasing trend in NH 3  PH3  AsH3  SbH 3  BiH3 .
moving down the group from nitrogen to bismuth.
The increasing order of boiling points is as follows :
(5) Non-metallic and metallic character : Nitrogen and phosphorus
are non-metals, arsenic and antimony are metalloids (semi-metal) and PH3  AsH3  NH 3  SbH 3 .
bismuth a typical metal. NH 3 is thermally most stable and BiH3 is least stable. This is
(6) Molecular state : Nitrogen readily forms triple bond (two p – because in NH 3 , N – H covalent bond is the strongest due to small size of
p bonds) and exists as discrete diatomic gaseous molecule (N  N ) at
N atom. Hence, the decomposition temperature of NH 3 will be the
room temperature. Phosphorus, arsenic and antimony exist in the form of
highest. The increasing order of reducing character is as follows,
discrete tetra atomic molecules such as P4 , As4 , Sb 4 in which the atoms
NH 3  PH3  AsH3  SbH 3  BiH3 .
are linked to each other by single bonds.
(7) Melting and boiling points : The melting points and boiling (2) Halides : The members of the family form trihalides (MX 3 ) and
points of group 15 elements do not show a regular trend. pentahalides (MX 5 ) . The trihalides are sp 3 -hybridized with distorted
M.pt. first increases from N to As and then decreases from As to Bi.
Boiling point increases from N to Sb. Boiling point of Bi is less than Sb. tetrahedral geometry and pyramidal shape while pentahalides are sp 3 d -
(8) Allotropy : All the members of group 15 except Bi exhibit the hybridized and are trigonal bipyramidal in shape. The trihalides are
phenomenon of allotropy. hydrolysed by water and ease of hydrolysis decreases when we move down
the group. Hence, NCl 3 is easily hydrolysed but SbCl 3 and BiCl3 are
(i) Nitrogen exists in two solid and one gaseous allotropic forms.
(ii) Phosphorus exists in several allotropic forms such as white, red, partly and reversibly hydrolysed. NF3 is not hydrolysed due to lack of
scarlet, violet and black form. vacant d-orbital with nitrogen. PF3 and PF5 are also not hydrolysed
(a) White or yellow phosphorus : White phosphorus is prepared because the P – F bond is stronger than P – O covalent bond. The
from rock phosphate Ca 3 (PO4 )2 , SiO2 and coke which are electrically hydrolysis products of the halides are as follows :
heated in a furnace. NCl 3  3 H 2 O  NH 3  3 HOCl

2Ca 3 (PO4 )2  6 SiO2  6 CaSiO3  P4 O10 PCl3  3 H 2 O  H 3 PO3  3 HCl
;
 2 AsCl3  3 H 2 O  As2 O3  6 HCl
P4 O10  10C  P4  10CO
SbCl 3  H 2 O  SbOCl  2 HCl
When exposed to light, it acquires a yellow colour.
BiCl3  H 2 O  BiOCl  2 HCl
(b) Red phosphorus : It is obtained by heating yellow phosphorus,
between 240 –250C in the presence of an inert gas. Yellow phosphorus Their basic character follows this decreasing order as
can be separated from red phosphorus by reaction with NaOH (aq) or KOH NI 3  NBr3  NCl 3  NF3 . Except NF3 , the trihalides of nitrogen are
(aq) when the former reacts and the latter remains unreacted. unstable and decompose with explosive violence. NF3 is stable and inert.
(iii) Arsenic exists in three allotropic forms namely grey, yellow and
NCl 3 is highly explosive. Trifluorides and trichlorides of phosphorus and
black. Antimony also exists in three forms, viz., metallic, yellow and
explosive. antimony act as Lewis acid. The acid strength decreases down the group.
For example, acid strength of tri-chlorides is in the order ;
(9) Oxidation state : The members of the group 15 exhibit a number
PCl3  AsCl3  SbCl 3 .
of positive and negative oxidation states.
(i) Positive oxidation states : The electronic configuration Nitrogen does not form pentahalides due to non-availability of
vacant d-orbitals. The pentachloride of phosphorus is not very stable
(ns 2np 3 ) for the valence shell of these elements shows that these elements because axial bonds are longer (and hence weaker) than equitorial bond.
can have +3 and +5 oxidation states. In moving down this group, the Hence, PCl5 decomposes to give PCl3 and Cl 2 ;
stability of +3 oxidation state increases. It may be pointed out here that
nitrogen does not exhibit an oxidation state of +5, because it fails to expand PCl5 ⇌ PCl3  Cl 2 .
its octet due to nonavailability of vacant d-orbitals.
The unstability of PCl5 makes it a very good chlorinating agent.
(ii) Negative oxidation states : For example oxidation state of
All pentahalides act as lewis acids since they can accept a lone pair of
nitrogen is –3. The tendency of the elements to show –3 oxidation state
electron from halide ion.
decreases on moving down the group from N to Bi.
Solid PCl5 is an ionic compound consisting of
(10) Catenation (self linkage) : Elements of group 15 also show some
tendency to exhibit catenation. This tendency goes on decreasing in moving   
[PCl 4 ] [PCl6 ] , [PCl 4 ] has a tetrahedral structure, while
down the group due to gradual decrease in their bond (M–M) energies. 
[PCl6 ] has an octahedral structure.
Chemical properties
(1) Hydrides : All the members form volatile hydrides of the type Since, PCl5 reacts readily with moisture it is kept in well
AH 3 . All hydrides are pyramidal in shape. The bond angle decreases on stoppered bottles.
moving down the group due to decrease in bond pair–bond pair repulsion. PI5 does not exist due to large size of I atoms and lesser
NH 3 PH3 AsH3 SbH 3 BiH3 electronegativity difference between phosphorus and iodine.
107 o 94 o 92 o 91 o 90 o Down the group, the tendency to form pentahalides decreases due
to inert pair effect. e.g., BiF5 does not exist.
 (3) Oxides : These elements form oxides of the type X 2 O3 , X 2 O4 (2) Commercial preparation : Commercially N 2 is prepared by the
and X 2 O5 . fractional distillation of liquid air.
The acidic strength of oxides : Physical properties : N 2 is a colourless, odourless and tasteless gas.
N 2 O  NO  N 2 O3  N 2 O4  N 2 O5 . It is a non-toxic gas. It’s vapour denstiy is 14. It has very low solubility in
water.
The decreasing order of stability of oxides of group 15 follows as, Chemical properties
P2 O5  As2 O5  Sb 2 O5  Bi2 O5 (1) N 2 is neutral towards litmus. It is chemically unreactive at
The nature of oxides of group 15 elements is as follows, ordinary temp. It is neither combustible nor it supports combustion.
N 2 O3 and P2 O3 (acidic) ; As2 O3 and Sb 2 O3 (amphoteric); (2) The N – N bond in N 2 molecule is a triple bond (N  N )
Bi2 O3 (basic) with a bond distance of 109.8 pm and bond dissociation energy of 946 kJ
mol-1

(4) Oxyacids : N 2 and P4 of this group forms oxyacids which are

(3) Combination with compounds : N 2 combines with certain
discussed further. In this chapter.
compounds on strong heating . eg
Anamalous behaviour of Nitrogen
Nitrogen is known to differ form other members of the family CaC2  N 2   CaCN 2  C
1300 K

Calsium carbide Calsium cyanamide

because of the following facts,
(1) Its small size (2) Its high electronegativity (3) Its high ionisation Al2 O 3  N 2  3 C   2 AlN  3 CO
2100 K
Al. nitride
energy (4) non-availability of d-orbital in the valence shell. (5) Its capacity Aluminium
oxide
to form p-p multiple bonds.
Both these compounds are hydrolysed on boiling with water to give
The main points of difference are, ammonia.
(i) Nitrogen is a gas while other members are solids.
(ii) Nitrogen is diatomic while other elements like phosphorus and CaCN 2  3 H 2O  CaCO 3  2 NH 3
arsenic form tetra-atomic molecules (P4 , As 4 ) . AlN  3 H 2O  Al (OH )3  NH 3
(iii) Nitrogen form five oxides (N 2 O, NO, N 2 O 3 , N 2 O 4 and Therefore, calcium cyanamide is used as a fertilizer under the name
N 2 O 5 ) while other members of the family form two oxides (tri and nitrolim (CaCN 2  C)
pentaoxides). Uses of nitrogen : N 2 is mainly used in the manufacture of
(iv) Hydrides of nitrogen show H-bonding while those of other compounds like NH 3 , HNO 3 , CaCN 2 etc.
elements do not.
Compounds of nitrogen
(v) Nitrogen does not show pentacovalency because of absence of d-
(1) Hydrides of nitrogen – Ammonia
orbitals while all other elements show pentacovalency.
Preparation of ammonia : Ammonia is prepared in the laboratory by
(vi) Nitrogen dos not form complexes because of absence of d-
heating a mixture of NH 4 Cl and slaked lime, Ca(OH )2
orbitals while other elements show complex formation e.g.,

[PCl6 ] , [ AsCl6 ] etc. 2 NH 4 Cl  Ca(OH )2  CaCl 2  2 NH 3  2 H 2 O

(vii) The hydride of nitrogen ( NH 3 ) is highly basic in nature while the Moist NH 3 gas is dried over quick lime, CaO . However, it
hydrides of other elements are slightly basic. cannot be dried over conc. H 2 SO 4 , P2 O5 because being basic it forms
(viii) Except for NF3 , other halides of nitrogen e.g., NCl 3 , NBr3 salts with them. Anhydrous CaCl 2 also cannot be used because it forms a
and NI 3 are unstable. complex CaCl 2 .8 NH 3 with it.
Nitrogen and its compounds Manufacture : (i) Ammonia is manufacture by Haber’s process. A
N 2 was discovered by Daniel Rutherford. It is the first member of mixture of pure N 2 and H 2 (in the ratio 1 : 3 by volume) is compressed
group 15 in the periodic table. to 200 – 1000 atmospheres and passed over finely divided Fe (as catalyst)
Occurrence : N 2 , occurs both in the free state as well as in the and Mo (as promoter) at 750 K
Fe +Mo, 750K, 200–1000 atm
combined state. N 2 occurs in atmosphere to the extent of 78% by volume N 2  3H 2 2 NH 3  93.6 KJ mol 1
in free state. N 2 is present in many compounds such as potassium nitrate Favourable conditions for maximum yield of NH 3 are :
(nitre). Sodium nitrate (Chile salt peter) and many ammonium compounds.
(a) excess of reactants ( N 2 and H 2 ) (b) high pressure (c) low
N 2 is an important constituent of proteins in plants and animals in
temperature and (d) use of catalyst and a promoter.
combined state.
Preparation : It is prepared by the following methods, (ii) By the hydrolysis of calcium cyanamide (CaCN 2 ) with super-
(1) Laboratory method : In the laboratory N 2 is prepared by heated steam at 450 K . CaCN 2 itself is obtained by heating CaC 2 and
heating an aqueous solution containing an equivalent amounts of NH 4 Cl N 2 at 1270 K .
and NaNO 2 . 
CaC 2  N 2  CaCN 2  C
NH 4 Cl (aq.)  NaNO 2 (aq.)   N 2 (g)  2 H 2O(l)  NaCl
Heat
 CaCN 2  3 H 2 O   CaCO 3  2 NH 3
450 K
HgI2  2 NH 3  I  Hg  NH 2  NH 4 I
Properties of NH : It is a colourless gas with pungent smell, highly
3
2 NH 2  Hg  I  H 2 O  NH 2  Hg  O  Hg  I  NH 4 I
soluble in H 2 O and basic in nature. It liquefies on cooling under pressure
to give liquid ammonia (bp. 240K). On heating, it causes intense cooling or 2 K 2 HgI4  NH 3  3 KOH  H 2 N  Hg  O  Hg  I  7 KI  2 H 2O
and hence is used as a refrigerant in ice, factories and cold storages.
It is used as a refrigerant and in the manufacture of fertilizers.
It burns in excess of air to give N 2 and H 2 O and is oxidised to
Strcture of NH : The N atom in NH 3 is sp3 -hybridized
NO when passed over heate Pt at 1075 K .
3

containing a lone pair of electrons due to which the H  N  H bond

4 NH 3  3O2  2 N 2  6 H 2 O
angle is 107.5 o . As a result NH 3 molecule is pyramidal.
4 NH 3  5 O2 
 4 NO  6 H 2 O
Pt. 1075 K ..
(ostwald process) N
It reduces heated CuO to Cu and Cl 2 to HCl (which 107.5o
combines with NH 3 to give NH 4 Cl ). H
H H
2 NH 3  3CuO   3Cu  3 H 2 O  N 2
Heat
(2) Oxides of nitrogen : Nitrogen combines with O 2 under
8 NH 3  3Cl 2  6 NH 4 Cl  N 2 different conditions to form a number of binary oxides which differ with
Excess respect to the oxidation state of the nitrogen atom. The important oxides
With excess of Cl 2 , it gives NCl 3 . With Br2 it gives NH 4 Br are N 2 O, NO, N 2 O 3 , NO 2 , N 2 O 4 and N 2 O 5 . N 2 O and NO both
and N 2 is set free. are neutral. Nitrous oxide ( N 2 O ) has a sweet taste and its main use is as
anaesthetic. When inhaled in mild quantities it causes hysterical laughter so
NH 3  3Cl 2  NCl 3  3 HCl
Excess
it is also called Laughing gas. Nitric oxide (NO) can be obtained by treating
a mixture of sodium nitrite and ferrous sulphate with dil. H 2 SO 4 . N 2 O5
8 NH 3  3 Br2  6 NH 4 Br  N 2
is the strongest oxidising agent.
With I2 , it gives nitrogen triiodide ammonia (brown ppt) which is
explosive in dry state and decomposes when struck

2 NH 3  3 I2  NH 3 . NI 3  3 HI

8 NH 3 . NI 3  5 N 2  9 I2  6 NH 4 I

It forms amides with active metals like Na, K etc.

2 Na  2 NH 3   2 NaNH 2  H 2
575 K

It forms complexes with many substances, e.g.,

[Ca(NH 3 )6 ] Cl 2 [Co (NH 3 )6 ]Cl 2 ,[Cu(NH 3 )4 ] SO 4
, ,
[ Ag(NH 3 )2 ]Cl , [Cd (NH 3 )4 Cl 2 etc.

Its aqueous solution is weakly basic due to the formation of OH 

ions, NH 3  H 2 O  NH 4  OH 

With sodium hypochlorite in presence of glue or gelatine, excess of

ammonia gives hydrazine

2 NH 3  NaOCl  NH 2 . NH 2  NaCl  H 2 O

It undergoes self ionization in liquid state and acts as a solvent.

2 NH 3  NH 4  NH 2
Many polar compounds are soluble in liquid ammonia.
With Nessler’s reagent (an alkaline solution of K2 Hgl4 ) , ammonia
and ammonium salts give a brown precipitate due to the formation of
Millon’s base.
K 2 HgI4 2 KI  HgI2
 Table : 18.4 Oxides of Nitrogen
Physical
Oxide Structure appearance
Preparation

Nitrous oxide ( N 2 O ) By heating ammonium nitrate upto 240 C 0

Colourless
N  N O gas 
+1 NH NO 
4 3
N O + 2H O, It is Collected over hot water
2 2

(a) By the action of cold dil. HNO on copper turnings (Laboratory 3

method)
3Cu + 8 dil. HNO  3Cu(NO ) + 4H O + 2NO 3 3 2 2

Nitric oxide (NO) (b) By the action of H SO on a mixture of FeSO and KNO (4:1)2 4 4 3

N=O Colourless 2KNO + 5H SO + 6FeSO  2KHSO + 3Fe (SO ) + 4H O + 2NO

+2 3 2 4 4 4 2 4 3 2

(c) By catalytic oxidation of ammonia.

4NH + 5O 
3
Pt
 4NO + 6H O 2 2

850 0 C

(a) By the action of 50% HNO on arsenious oxide. 3

Dinitrogen trioxide ( N 2 O 3 ) O 2HNO + As O + 2H O  NO + NO + 2H AsO

3 2 3 2 2 3 4

O NN Blue solid

+3 O  250 K
NO 2 3

Dinitrogen tetraoxide ( N 2 O 4 ) O O (a) By heating nitrates of heavy metals, e.g., lead nitrate.
Colourless
N N liquid
+4 O O 2Pb(NO )   4NO + 2PbO + 2O
673 K
3 2 2

Nitrogen dioxide ( NO 2 ) (b) By heating copper turnings with conc. HNO 3.

N Brown gas Cu + 4 HNO (conc.)  Cu(NO ) + 2H O + 2NO

+4 O O 3 3 2 2 2

Dinitrogen pentoxide ( N 2 O5 ) O O O (a) By dehydrating HNO with phosphorus pentoxide

Colourless 3

N N gas 4HNO +P O  2N O + 4HPO

+5 O O 3 4 10 2 5 3

(3) Oxyacids of nitrogen : Oxyacids of nitrogen are 4 NH 3  5 O2    4 NO  6 H 2 O

Pt. 1975 K

HNO 2 , HNO 3 , H 4 N 2 O 4 and HNO 4 , which are explosive.

(Nitroxylic acid) (Pernitric acid)
2 NO  O2 ⇌ 2NO 2 ; 4 NO 2  2 H 2 O  O2  4 HNO 3
(i) Nitrous acid (HNO ) : It is prepared by adding ice cold dil, HCl
2
From air (Birkeland Eyde electric arc process)
or dil, H 2 SO 4 to a well cooled solution of any nitrite
N 2  O 2 ⇌ 2 NO ; H of  135 kJ mol 1
(NaNO 2 , Ba(NO 2 )2 etc.).
o

NaNO 2  HCl  NaCl  HNO 2 2 NO  O 2   2 NO 2

50 C

2 KNO 2  H 2 SO 4  K 2 SO 4  2 HNO 2 2 NO 2  H 2 O  HNO 2  HNO 3

It oxidises H 2 S to S, Kl to I 2 and acts as a reducing agent in 3 HNO 2  HNO 3  H 2 O  2 NO

presence of strong oxidising agent, i.e., it reduces acidified
Properties : It is a very strong acid and decomposes on boiling or in
KMnO4 , K 2 Cr2 O7 ,H 2 O2 etc. to Mn 2  , Cr 3  and H 2 O respectively. presence of sunlight. It acts as a strong oxidising agent. It oxidises
(ii) Nitric acid (HNO ) : HNO 3 is called aqua fortis. It is prepared nonmetals and metalloids to their respective oxy-acids, i.e., C to
3

H 2 CO 3 , S to H 2 SO 4 , P to H 3 PO4 , l2 to HlO3 , As to
in the laboratory by distillation of nitre with conc. H 2 SO 4 .
H 3 AsO4 (arsenic acid) and Sb to H 3 SbO 4 (antimonic acid), while
2 NaNO 3  H 2 SO 4  2 HNO 3  Na 2 SO 4 .
nitric acid itself is reduced to NO 2 .
Commercially, it is obtained by Ostwald’s process. In this process,
NH 3 is first catalytically oxidised to NO which is cooled to about I2  10 HNO 3  2 HIO3  10 NO 2  4 H 2 O
300 K and then oxidised by air to NO 2 . Absorption of NO 2 in water in Nitric acid reacts with metals to form nitrates and is itself reduced
presence of oxygen gives HNO 3 to NO , N 2 O, NO 2 or NH 3 (which further reacts with HNO 3 to give
 NH 4 NO 3 ) depending upon the concentration of the acid, activity of the Nitric acid has no action on noble metals ( Au, Pt) but these metals
metal and the temperature of the reaction. dissolve in aqua regia (3 vol. HCl  1 vol. HNO 3 ) forming their respective
(i) Very active metals such as Mn, Mg, Ca , etc. give H 2 on chlorides.
treatment with very dilute HNO 3 (2%). HNO 3  3 HCl  2 H 2 O  NOCl  2[Cl]
(ii) Less active metals like Cu, Hg, Ag, Pb etc. give NO with dil.
Au  3[Cl]  AuCl3 ; Pt  4[Cl]  PtCl4
HNO 3 . Zinc, however, gives N 2 O with dil HNO 3 and NH 4 NO 3
with very dilute HNO 3 . These chlorides subsequently dissolve in excess of HCl forming
their corresponding soluble complexes. Thus,
Zn  10 HNO 3 (dilute) 4 Zn(NO 3 )2  N 2 O  5 H 2 O
AuCl 3  HCl  HAuCl4
Zn  10 HNO 3 (very dilute) 4 Zn(NO 3 )2  NH 4 NO 3  3 H 2 O Auric chloride Aurochloric acid

Similarly, Fe and Sn react with dilute nitric acid to give PtCl4  2 HCl  H 2 PtCl6
Platinic chloride Chloro platinicacid
NH 4 NO 3 .
Sugar on oxidation with nitric acid gives oxalic acid. Nitric acid
(iii) Conc. HNO 3 gives NO 2 both with active metals (Zn, Pb reacts with glycerine to give glycerol trinitrate or nitro glycerine, with
etc.) and less active metals ( Cu , Hg, Ag etc.) toluene it gives 2, 4, 6-trinitrotoluene (T.N.T.) and with cellulose (cotton) it
gives cellulose trinitrate (gun cotton). All these are used as explosives.
Cu  4 HNO 3 (Conc.)  Cu(NO 3 )2  2 NO 2  2 H 2 O
COOH
Tin is, however, oxidized by conc. HNO 3 to metastannic acid C12 H 22 O11  18[O]  6 |  5 H 2O
Cane sugar From HNO 3
(H 2 SnO 3 ) . COOH
Oxalic acid
Sn  4 HNO 3  H 2 SnO 3  4 NO 2  H 2 O

Passivity : Fe, Cr, Ni and Al become passive in conc. HNO 3

(i.e., lose their normal reactivity) due to the formation of a thin protective
layer of the oxide on the surface of the metal which prevents further action.
Table : 18.5 Oxyacids of nitrogen

Name
M. ofF. oxoacid
Formula M. F. Structure Oxidation State of N Basicity pK a
Nature

Hyponitrous acid HNO

2 2 2
.. +1 2(dibasic) Very weak Highly explosive
N  OH
||
HO  N
..

Nitrous acid HNO 2 HN O +3 1 (monobasic) 3.3 Unstable, Weak acid




Nitric acid HNO 3 H O  N  O +5 1 (monobasic) -3.0 Stable, Strong acid




Pernitric acid HNO 4 O  NO O  H +5 1 (monobasic) Unstable and


 explosive

Phosphorus and its compounds Ca5 (PO4 )3 OH . Phosphates are essential constituents of plants and
It is the second member of group 15 (VA) of the Periodic table. animals. It is mainly present in bones, which contains about 58% calcium
Due to larger size of P, it can not form stable P  - P  bonds with phosphate.
other phosphorous atoms where as nitrogen can form P  – P  bonds . (2) Isolation : Elemental phosphorus is isolated by heating the
(1) Occurrence : Phosphorous occurs mainly in the form of phosphorite rock with coke and sand in an electric furnace at about 1770K,
phosphate minerals in the crust of earth. Some of these are : 2Ca 3 (PO4 )2  6 SiO2  6 CaSiO3  P4 O10 ;
(i) Phosphorite Ca 3 (PO4 )2 , (ii) Fluorapatite Ca5 (PO4 )3 F , Calicum silicate

(iii) Chlorapatite 3 Ca3 (PO4 )2 .CaCl 2 , (iv) Hydroxyapatite; P4 O10  10C  P4  10CO
 (3) Allotropic forms of phosphorus : Phosphorus exists in three Due to its polymeric structure, red phosphorus is much less reactive
main allotropic forms, and has m.p. much higher than that of white phosphorus.
(i) White phosphorus, (ii) Red phosphorus, (iii) Black phosphorus Properties : Red phosphorus is a hard, odourless, non poisonous
(i) White or yellow phosphorus : It is obtained from phosphate rock solid, insoluble in organic solvents such as CS 2 , alcohol and ether. Its
or phosphorite as explained above. It exists as P4 units where four P ignition temperature is much higher than that of white phosphorus and
thus does not catch fire easily. It does not show phosphorescence.
atoms lie at the corners of a regular tetrahedron with PPP  60 o . Each
It sublimes on heating giving vapours which condense to give white
P atom is linked to three other P atoms by covalent bonds. there are
phosphorus. It is denser than white phosphorus and is a bad conductor of
total six bonds and four lone pairs of electrons present in a P4 molecule of electricity.
white phosphorus. ··
P It burns in oxygen at 565 K to give phosphorus pentoxide, reacts
with halogens, sulphur and alkali metals only when heated forming their
corresponding salts.
60°
It does not react with caustic alkalies and this property is made use
·· in separating red phosphorus from white phosphorus.
:P P
(iii) Black phosphorus : It is obtained by heating white phosphorus
P at 470 K under high pressure (4000–12000atm) in an inert atmosphere.
··
Properties : White phosphorus is extremely reactive due to strain in
the P4 molecule, poisonous, soft, low melting (317 K) solid, soluble in White phosphorus 470
K Black phosphorus
4000 12000 atm. pressue
CS 2 , alcohols and ether. It has a garlic odour. Persons working with white It has a double layered structure. Each layer is made up of zig-zag
P develop a disease known as Phossy jaw in which jaw bones decay. It chains with P  P  P bond angle of 99 o . Since it is highly polymeric, it
turns yellow on exposure to light. Hence, it is also called yellow phosphorus. has high density. It is the most stable (inactive) form of phosphorus and has
It spontaneously catches fire in air with a greenish glow which is a black metallic luster. It is a good conductor of heat and electricity.
visible in the dark (P4  3O2  P4 O6 ) . This phenomenon is called (4) Compounds of phosphorus
phosphorescence. Because of its very low ignition temperature (303 K) , it (i) Oxides and oxyacids of phosphorus : Phosphorus is quite
is always kept under water. reactive and forms number of compounds in oxidation states of –3 , +3 and
With sulphur it gives tetraphoshorus trisulphide with explosive +5. Phosphorus forms two common oxides namely, (a) phosphorus trioxide
violence which is used in “strike anywhere matches”. ( P4 O6 ) and (b) phosphorus penta oxide (P4 O10 ) .
8 P4  3 S 8  8 P4 S 3 (a) Phosphorus (III) oxide ( P4 O6 ) :
With metals phosphorus forms phosphides. For example, .P.
P4  6 Mg  2 Mg3 P2 .. ..
O O
..
.. ..
127
o

With aqueous alkalies, on heating, white phosphorus gives phosphine

O
..
0 3 1
P4  3 NaOH  3 H 2 O  PH3  3 NaH 2 PO2 ..
(Phosphine ) Sod. hypophosph ite .P. O .P.
..
It is an example of a disproportionation reaction where the oxidation
state of P decreases from 0 to –3 (in PH 3 ) and increases to +1 (in .. .P. ..
O
.. 166 pm O
..
NaH 2 PO2 )
White phosphorus acts as a strong reducing agent. It reduces It is formed when P Phosphorus
is burnttrioxide
in a limited supply of air,
HNO 3 to NO 2 and H 2 SO 4 to SO 2 . It also reduces solutions of P4  3O2  P4 O6 .
(limited)
Cu, Ag and Au salts to their corresponding metals. For examples,
It is a crystalline solid with garlic odour. It dissolves in cold water
P4  8 CuSO 4  14 H 2 O  8 Cu  8 H 2 SO 4  4 H 3 PO4 to give phosphorous acid,

P4  20 AgNO3  16 H 2 O  20 Ag  4 H 3 PO4  20 HNO 3 P4 O6 + 6 H 2 O  4 H 3 PO3 , It is therefore, considered as

cold Phosphorou s acid
(ii) Red phosphorus : It is obtained by heating white phosphorus at anhydride of phosphorus acid.
540  570 K out of contact with air in an inert atmosphere ( CO 2 or
With hot water, it gives phosphoric acid and inflammable phosphine,
coal gas) for several hours.
P4 O6  6 H 2 O (hot)  3 H 3 PO4  PH3
540  570 K
White phosphorus   Red phosphorus Phosphoric acid
CO 2 or coal gas
It reacts vigorously with Cl 2 to form a mixture of phosphoryl
Red phosphorus exists as chains of P4 tetrahedra linked together
chloride and meta phosphoryl chloride.
through covalent bonds to give a polymeric structure as shown.
P4 O6  4 Cl 2  2 POCl3  2 PO2 Cl
P P P Phosphoryl chloride Metaphosph oryl chloride

P P P P P P (b) Phosphorus (V) oxide P4 O10  :

P P P
 ..
: O:

143 pm
P O
.. 102 o .. Metaphosphoric acid +5
.O. 123o
.O. (HPO3 )n Monobasic P
..

160 pm
.O. O
HO
.. P .. P .. Pyrophospric acid O O
: .O. O
.. . .:
O
(Diphosphoric acid).
+5

.. P Tetrabasic P P
.. H 4 P2 O7 OH
.O. .O. HO OH
O
OH
:O
. .: (5) Chemical Fertilizers : The chemical substances which are added
It is prepared by heating white phosphorus in excess of air, to the soil to keep up the fertility of soil are called fertilizers.
Phosphorus pentoxide
P4  5 O2 (excess )  P4 O10 . It is snowy white solid. It readily dissolves in Types of fertilizers : Chemical fertilizers are mainly of four types,
cold water forming metaphosphoric acid. (i) Nitrogenous fertilizers : e.g. Ammonium sulphate (NH 4 )2 SO 4 ,
P4 O10  2 H 2 O  4 HPO3 . With hot water, it gives Calcium cyanamide CaCN 2 , Urea NH 2 CONH 2 etc.
(Cold) Metaphosph oric acid
(ii) Phosphatic fertilizers : e.g. Ca(H 2 PO4 )2 .H 2 O (Triple super
phosphoric acid, P4 O10  6 H 2 O  4 H 3 PO4 .
Hot Phosphoric acid phosphate), Phosphatic slag etc.
(iii) Potash fertilizers : e.g. Potassium nitrate (KNO 3 ), Potassium
P4 O10 is a very strong dehydrating agent. It extracts water from many
sulphate (K 2 SO 4 ) etc.
compounds including H 2 SO 4 and HNO 3 ,
(iv) Mixed fertilizers : These are made by mixing two or more
H 2 SO 4  SO 3 ; 2 HNO 3 4 
 N 2 O5
P O P O
4 10 10 fertilizers in suitable proportion. e.g. NPK (contains nitrogen, phosphorus
 H 2O  H 2O
and potassium).
CH 3 CONH 2 
 CH 3 CN
P4 O10 NPK is formed by mixing ammonium phosphate, super phosphate
Acetamide H 2O Methyl cyanide and some potassium salts.
(ii) Oxyacids of phosphorus : Phosphorus forms a number of oxyacids Oxygen Family
which differs in their structure and oxidation state of phosphorus. These are
H 3 PO2 , H 3 PO3 , H 4 P2 O6 , H 3 PO4 , Oxygen is the first member of group 16 or VIA of the periodic table.
It consists of five elements Oxygen (O), sulphur (S), selenium (Se),
(HPO3 )n , H 4 P2 O5 , H 4 P2 O7 . From these H 3 PO2 , H 3 PO3 are tellurium (Te) and polonium (Po). These (except polonium) are the ore
reducing agents. H 4 P2 O 5 (pyrophosphoric acid) is dibasic acid. forming elements and thus called chalcogens.
(1) Electronic configuration
(HPO3 )n is formed by dehydration of H 3 PO4 at 316 o C .
Elements Electronic configuration ( ns 2 np 4 )
Table : 18.6 Oxyacids of phosphorus
Oxidation 8 O [He] 2 s 2 2 p 4
Name state of P Structure
and Basicity 16 S [ Ne ] 3 s 2 3 p 4
O 34 Se [ Ar] 3d 10 4 s 2 4 p 4
Hypophosphorous +1
P 52 Te [Kr] 4 d 10 5 s 2 5 p 4
acid H 3 PO2 Monobasic H
84 Po [ Xe] 4 f 14 5 d 10 6 s 2 6 p 4
H OH
O
Physical properties
Phosphorous acid +3 (1) Physical state : Oxygen is gas while all other are solids.
P
H 3 PO3 Dibasic (2) Atomic radii : Down the group atomic radii increases because
OH
H the increases in the number of inner shells overweighs the increase in
OH nuclear charge.
O O
(3) Ionisaion energy : Down the group the ionisation energy
Hypophosphoric acid +4 decrease due to increase in their atomic radii and shielding effect.
H 4 P2 O 6 Tetrabasic
P P
(4) Electronegativity : Down the group electronegativity decreases
OH
due to increase in atomic size.
HO OH OH (5) Electron affinity : Element of this group have high electron
Orthophosphoric acid +5 O affinity, electron affinity decreases down the group.
H 3 PO4 Tribasic (6) Non – metallic and metallic character : These have very little
P metallic character because of their higher ionisation energies.
OH
HO OH
 (7) Nature of bonding : Compound of oxygen with non metals are H 2 O  H 2 S  H 2 Se  H 2 Te
predominantly covalent. S, Se, and Te because of low electronegativities
show more covalent character. (2) Oxides : These elements form monoxides (MO), dioxides
(8) Melting and boiling points : The melting point and boiling points ( MO2 ) and trioxides (MO3 ) .
increases on moving down the group. (i) Dioxides : Sulphur, selenium and tellurium burn in air to form
(9) Catenation : Oxygen has some but sulphur has greater tendency SO 2 , SeO 2 and TeO 2 . The dioxide molecules contain p  p bonds
for catenation. which become weaker with increase in atomic number because of the
H  O  O  H, H  S  S  H, increase in the bond length.
(H 2 O 2 ) (H 2 S 2 ) (a) Sulphur dioxide, SO 2 is a gas at room temperature and exists as
H  S  S  S  H, H S S S S H individual molecules even in the solid state. Its molecule has bent structure and is a
(H 2 S 3 ) (H 2 S 4 ) resonance hybrid of the following canonical structures.
(10) Allotropy
S S S
Oxygen – O 2 and O 3
Sulphur – Rhombic , monoclinic, plastic sulphur O O O O O O
Selenium – Red (non-metallic) grey (metallic) SO 2 is acidic in nature and also called the anhydride of
Tellurium – Non-metallic and metallic (more stable)
sulphurous acid. It can act as reducing and oxidising agent. SO 2 also acts
Polonium –  and  (both metallic)
as a beleaching agent in the presence of moisture, but in contrast to Cl 2 ,
(11) Oxidation states : Oxygen shows – 2, + 2 and –1 oxidation
states. Other elements show +2 ,+4 and +6 oxidation states. its bleaching action is temporary.
Chemical properties SO 2  2 H 2 O  H 2 SO 4  2[H ]
(1) Hydrides : The elements of this group form hydrides such as
Colouring matter 2[H ] ⇌ Colourless compound
H 2 O, H 2 S , H 2 Se , H 2 Te an H 2 Po . Following are their characteristics.
(i) Physical states : Water is colourless and odourless while hydrides Hence, SO 2 bleaches due to reduction and the bleaching action is
of the rest of the elements of this group are colourless, unpleasant smelling temporary.
poisonous gases. (b) Selenium dioxide, SeO 2 is a solid with polymeric zig-zag
(ii) Volatile nature : Volatility increases from H 2 O to H 2 S and structure at room temperature however it exist as discrete molecules in the
then decreases. The low volatility and abnormally high boiling point of gaseous phase.
water is due to the association of water molecules on account of hydrogen O O O
bonding because of strongly electronegative oxygen atom linked to hydrogen
=

=
Se Se Se
atom. thus, water is liquid while H 2 S and other hydrides are gases under
normal condition of temperature and pressure. O O O O
(iii) Acidic character : The hydrides of this group behave as weak (c) Tellurium dioxide, TeO 2 is also a solid with polymeric zig-zag
diprotic acids in aqueous solution, the acidic character increasing from structure at room temperature very similar to that of selenium dioxide.
H 2 S to H 2 Te when H 2 O is neutral. (ii) Trioxides : Sulphur, selenium and tellurium can form trioxides
(iv) Thermal stability : The thermal stability decreases from H 2 O also.
(a) Sulphur trioxide, SO 3 : In the gaseous state monomeric SO 3
to H 2 Po because the size of the central atom (from O to Po )
has a planar structure with S  O bond distance of 143 pm and
increases resulting in longer and weaker M  H bond consequently the
bond strength decreases. This results in the decrease of the thermal O  S  O bond angle of 120 o . SO 3 molecule is a resonance hybrid of
stability. following structures.
(v) Reducing character : The reducing power of the hydrides
increases from H 2 O to H 2 Po due to the decreasing bond strength from O O O O

H 2 O to H 2 Po . S S S S
143 pm
(vi) Bond angle : All these hydrides are angular molecules and the 120°
bond angle H  X  H ( X is O, S , Se , Te ) decreases from H 2 O to O O O O O O O O

H 2 Te . Canonical structures Resonance hybrid

In the solid phase sulphur trioxide polymerises to cyclic trimer or to
Increasing order of reducing power of hydrides : a stable linear chain structure. SO 3 is the anhydride of H 2 SO 4 . It is
H 2 O  H 2 S  H 2 Se  H 2 Te acidic in nature and acts as oxidising agent.
Increasing order of bond angles in hydrides : (b) Selenium trioxide, SeO 3 : it is a solid substance which exists
H 2 Te  H 2 Se  H 2 S  H 2 O as a cyclic tetramer, however in the vapour phase it exists as a monomer
The order of stability of hydrides : (c) Tellurium trioxide, TeO 3 : It is a solid at room temperature
H 2 O  H 2 S  H 2 Se  H 2 Te existing as a polymer.
The order of increasing acidic nature of hydrides : The increasing order of acidic nature of oxides is
TeO 3  SeO 3  SO 3 .
 (3) Oxyacids : (3) Laboratory Method : In the laboratory, O 2 is prepared by thermal
H 2 SO 3 , H 2 SO 4 , H 2 S 2 O3 , H 2 SO 5 , H 2 S 2 O8 , H 2 S 2 O7 , H 2 S 2 O6 decomposition of potassium chlorate.
2 KClO3   2 KCl  3O2
420 K
(4) Halides : Oxygen : OF2 , Cl 2 O, Br2 O MnO 2

Sulphur : S 2 F2 , S 2 Cl 2 , SF2 , SCl 2 , SBr2 , SF4 , SCl 4 and SF6 In the absence of MnO2 catalyst, the decomposition takes place at
670-720 K. Therefore, MnO2 acts as a catalyst and also lowers the
Selenium and tellurium : SeF6 and TeF6
temperature for the decomposition of KClO3 .
Anamolous Behaviour of Oxygen
(4) O 2 can also be prepared by the action of water on sodium peroxide
Oxygen is the first member of the group 16 family and differs from
the other members of the family because of as, 2 Na 2 O2  2 H 2 O  4 NaOH  O2 .
(1) Its small size (5) Industrial preparation : The main sources for the industrial
preparation of dioxygen are air and water.
(2) Its high electronegativity
(i) From air : O 2 is prepared by fractional distillation of air. During
(3) Its high ionisation energy
this process, N 2 with less boiling point (78 K) distills as vapour while O 2
(4) Absence of d -orbitals in the valence shell with higher boiling point (90 K) remains in the liquid state and can be
It differs from the other members of the family as follows separated.
(1) Elemental state : Oxygen is a diatomic gas while others are octa- (ii) From water : O 2 can also be obtained by the electrolysis of
atomic solids with eight membered puckered ring structure. water containing a small amount of acid or alkali,
Electrolysis
(2) Oxidation states : Oxygen shows O.S. of –2 in most of its
2H 2O 2 H 2 (g)  O2 (g) .
compounds. It also shows an O. S. of +2 in F2 O and –1 in H 2 O 2 or
Physical properties of O : It is a colourless, tasteless and odourless
other peroxides. It cannot show O.S. beyond 2. Other elements show 2

gas. It is slightly soluble in water and its solubility is about

oxidation states of +2, +4 and +6 because these elements have vacant d -
orbitals so that their valence shell can expand. 30 cm 3 per litre of water at 298 K.

(3) Hydrogen-bonding : Oxygen atom is very small and has quite Table : 18.7 Physical properties of atomic and molecular oxygen
high nuclear charge. therefore, it has high value of electronegativity and is Atomic properties Molecular properties
able to form H -bonds. the other elements, because of their large size, Atomic radius (pm) – 73 Bond length (pm) – 120.7
cannot form H -bonds. As a result, H 2 O is liquid while H 2 S is a gas Ionic radius O (pm) – 140
2–
Bond energy (kJ mol ) – 493
–1

and H 2 Se etc., are solids. Electronegativity – 3.5 Density at S.T.P. (gcm )– 1.429
–3

Ionisation energy (kJ mol ) – 1310

–1
Melting point (K) – 54.4
(4) Maximum covalency : Oxygen has a maxium covalency of two
Electron affinity (kJ mol ) – 140
–1
Boiling point (K) – 90.2
while other elements can show a maximum covalency of six. This is because
these elements have vacant d -orbitals while oxygen has not. Chemical properties of O : It does not burn itself but helps in
2

burning. It is quite stable in nature and its bond dissociation energy is very
(5) Types of compounds : The compounds of oxygen are mainly
ionic and polar covalent due to high electronegativity of oxygen while those high. Therefore, it is not very reactive as such, O2  O  O .
of others are not. Therefore, dioxygen reacts at higher temperatures. However, once
(6) Magnetic character : Oxygen is paramagnetic while others are the reaction starts, it proceeds of its own. This is because the chemical
not. reactions of dioxygen are exothermic and the heat produced during the
reaction is sufficient to sustain the reactions.
Oxygen and its compounds
(1) Action with litmus : Like dihydrogen, it is also neutral and has
Oxygen is the most abundant element in the earth crust (46.5%). It no action on blue or red litmus.
was discovered by Karl Scheele and Joseph Priestley. It occurs in three (2) Reaction with metals : Active metals like Na, Ca react at room
isotopic forms : temp. to form their respective oxides.
16 17 18
8O 8O 8O 4 Na  O2  2 Na 2 O ; 2Ca  O2  2CaO
( Abundance : 99 .76 %) ( Abundance : 0 .037 %) ( Abundance : 0 .204 %)
It reacts with Fe, Al, Cu etc. metals at high temperature
18
Out of the three isotopes, 8O is radioactive. 4 Al  3O2  2 Al2 O3 ; 4 Fe  3O2  2 Fe2 O3
Occurrence : In free state, it occurs in air and constitutes 21% by (3) Action with Non-metals : It form oxides.
volume of air. 1073 K
Preparation of Dioxygen : Oxygen is prepared by the following 2 H 2  O 2     2 H 2 O ;
Electricdischarge
methods.
(1) By the decomposition of oxygen rich compounds : e.g. N 2  O 2   2 NO
3273 K
Nitricoxide
2 KNO 3   2 KNO 2  O2 ; 2 KClO3 
Heat
 2 KCl  3 O 2
Heat

Pot. Nitrate Pot. Chlorate MnO 2 S  O2  SO 2 ; Heat

C  O2   CO 2
Heat

(2) By heating dioxides, Peroxides and higher oxides : e.g. (4) Reaction with compounds : Dioxygen is an oxidising agent and
2 Ag 2 O   4 Ag  O 2 ;
Heat
3 MnO2   Mn3 O4  O 2
Heat it oxidises many compounds under specific conditions. e.g.
Silver oxide Manganese dioxide 700 K
4 HCl  O2   2 H 2 O  2Cl 2 ;
 2 BaO  O 2
Heat CuCl 2
2 BaO2
Barium peroxide Barium oxide
 4 NH 3  5 O2   4 NO  6 H 2 O
1073 K Suboxides : These oxides contain less oxygen than expected from
Pt the normal valency. For example, N 2 O.
CS 2  3O2   CO 2  2SO 2 ;
Heat
Mixed oxides : These oxides are made up of two simple oxides. For
example, red lead Pb3 O4 (2 PbO2  PbO2 ), magnetic oxide of iron,
CH 4  2O2  CO 2  2 H 2 O
Fe3 O4 (FeO  Fe2 O3 ) and mixed oxide of manganese,
Uses of dioxygen
Mn3 O4 (MnO2  2 MnO).
(1) It is used in the oxy-hydrogen or oxy-acetylene torches which are
used for welding and cutting of metals. Ozone or trioxygen
Ozone is an allotrope of oxygen. It is present in the upper
(2) It is used as an oxidising and bleaching agent,
atmosphere, where it is formed by the action of U. V. radiations on O 2 ,
(3) Liquid O 2 is used as rocket fuel.
3 O 2    2O 3 .
U. V . radiation
(4) It is used in metallurgical processes to remove the impurities of Ozone
metals by oxidation. O 3 protects us from the harmful U. V. radiations which causes
Compounds of Oxygen skin cancer. Now a days, ozone layer in the atmosphere is depleting due to
(1) Oxides : A binary compound of oxygen with another element is NO released by supersonic aircrafts and chlorofluoro carbons (CFC’S) i.e.
called oxide. On the basis of acid-base characteristics, the oxides may be freon which is increasingly being used in aerosols and as a refrigerant.
classified into the following four types, Preparation : Ozone is prepared by passing silent electric discharge
(i) Basic oxides : Alkali, alkaline earth and transition metals form through pure, cold and dry oxygen in a specially designed apparatus called
ozoniser. The formation of ozone from oxygen is an endothermic reaction.
basic oxides - Na 2 O, MgO, Fe2 O3 etc. their relative basic character
Silent electric
decreases in the order : alkali metal oxides>alkaline earth metal 3O2 2O 3 H  285.4 kJ
oxides>transition metal oxides. discharge

(ii) Acidic oxides : Non-metal oxides are generally acidic - Ozone is prepared in the laboratory by the following two types of
CO 2 , SO 2 , SO 3 , NO 2 , N 2 O5 , P4 O10 , Cl 2 O7 etc. ozonisers,
(a) Siemen’s ozoniser, (b) Brodie’s ozoniser
(iii) Amphoteric oxides : Al2 O3 , SnO 2 etc. For the better yield of ozone : (a) Only pure and dry oxygen should
be used. (b) The ozoniser must be perfectly dry. (c) A fairly low
(iv) Neutral oxides : H 2 O, CO, N 2 O, NO etc.
temperature ( 273 K) must be maintained. (d) The electric discharge
Trends of oxides in the periodic Table : On moving from left to the must be sparkless.
right in periodic table, the nature of the oxides change from basic to Physical properties : Ozone is a light blue coloured gas, having
amphoteric and then to acidic. For example, the oxides of third period has pungent odour. It is heavier than air. Its vapour density is 24. It is slightly
the following behaviour, soluble in water.
Cl 2 O7 Chemical properties : The important chemical properties of ozone
Na 2 O Al2 O 3 SiO2 P4 O10 SO 2 are discussed below,
MgO very
strongly amphoter weakly strongly (1) Decomposition : Pure ozone decomposes on heating above 475
basic acidic strongly
basic ic acidic acidic
acidic K to form O 2 gas.
Basic to acidic character increases 2O 3   3O2 H  285.4 kJ
475 K

However, on moving down a group, acidic character of the oxides (2) Oxidising agent : Ozone is one of the most powerful oxidising
decreases. For example in the third group, the acidic character of oxides agent with the liberation of dioxygen. In fact, ozone is a stronger oxidising
decreases as: agent than molecular oxygen because ozone has higher energy content and
decomposes to give atomic oxygen as:
B 2 O 3 acidic Al2 O 3 Ga 2 O 3 (weakly In2 O 3 , Tl 2 O 3
O3  O2  O
amphoteric basic) basic Atomic oxygen
Therefore, ozone oxidises a number of non-metals and other
Acidic to basic character increases reducing agents. e.g.
On the basis of oxygen content the oxides may be classified into the 2 Ag  O3  Ag 2 O  O 2 ; S  3O 3  SO 3  3O 2
Metal Silver oxide Non metal
following types,
Normal oxides : These contain oxygen atoms according to the PbS  4 O 3  PbSO 4  4 O 2
Compound
normal oxidation number i.e. – 2. For example, MgO, H 2 O,
Mercury is oxidised to mercurous oxide,
CaO, Li 2 O, Al2 O3 etc. 2 Hg  O3  Hg 2 O  O 2
Polyoxides : These contain oxygens atoms more than permitted by Mercurous oxide

the normal valency. Therefore, these contain oxygen atoms in oxidation state During this reaction mercury loses its meniscus and starts sticking
different than –2. to the sides of the glass. This is known as tailing of mercury. Mercurous
oxide formed in this reaction dissolves in mercury and starts sticking to the
Peroxides : These contains O 22  ion having oxidation number of
glass surface.
oxygen as –1. For example, (3) Bleaching agent : Due to the oxidising action of ozone, it acts as
H 2 O2 , Na 2 O2 , BaO2 , PbO2 etc. a mild bleaching agent as well as a sterilizing agent. It acts as a bleaching
agent for vegetable colouring matter.
Superoxides : These contains O 2 ion having oxidation number of
Vegetable colouring matter  O3  Oxidised coloured matter O2
oxygen as –1/2. For example, KO 2 , PbO2 , etc. (Colourless )
 For example, ozone bleaches indigo, ivory, litmus, delicate fabrics
etc.
(4) Formation of ozonides : Ozone reacts with alkenes in the
presence of CCl 4 to form an ozonide. e.g.
O

CH 2  CH 2  O 3   H 2 C
CCl 4
CH 2
Ethylene
(4) Colloidal or  -sulphur : It is prepared by passing H 2 S
O O through a solution of an oxidizing agent or water or by treating sodium
Ethylene ozonide
thiosulphate with dil. HCl.
Structure of O : The structure of O 3 molecule is angular as shown
3 Properties of sulphur : It burns in air with, a blue flame forming
in fig. The O  O  O bond angle is 116.8° and O  O bond length is 128 SO 2 , gives sulphur hexafluoride with F2 and sulphur mono chloride
pm. with Cl 2 , sulphides with metals like Na, Ca, Zn, Hg, Fe, Cu etc., reduces
O HNO 3 to NO 2 and H 2 SO 4 to SO 2 . With NaOH solution on heating,
12816.8°pm 12816.8°pm
116.8° S 8  12 NaOH  4 Na 2 S  2 Na 2 S 2 O3  6 H 2 O .
O O It gives sodium sulphide and sodium thiosulphate, with excess of
Uses of ozone
sulphur, 2 Na 2 S  S 8  2 Na 2 S 5 .
(1) O 3 is used for disinfecting water for drinking purposes because
Uses of sulphur : It is used in the manufacture of matches, gun
ozone has germicidal properties. powder (mixture of charcoal, sulphur and potassium nitrate), explosives and
(2) It is used for purifying air of crowded places such as cinemas,
fire works SO 2 , H 2 SO 4 , CS 2 and dyes, sulpha drugs and ointment for
under ground railway, auditoriums, tunnels, mines etc.
curing skin diseases and in the vulcanization of rubber.
(3) It is used in industry for the manufacture of KMnO4 , artificial Compounds of Sulphur
silk, synthetic camphor etc. (1) Hydrogen Sulphide : It is prepared in the laboratory by the
Sulphur and its compounds action of dil. H 2 SO 4 on ferrous sulphide in kipp’s apparatus,
Sulphur is the second member of oxygen family and belongs to
group-16 (VI A) of the periodic table. FeS  H 2 SO 4  FeSO 4  H 2 S . It is colourless gas having foul smell
Occurrence : Sulphur occurs in the earth’s crust to the extent of resembling that of rotten eggs. It reacts with many cations (of group II and
0.05%. It occurs in the free state as well as in combined state. Sulphur IV) to give coloured sulphides,
occurs mainly as sulphides and sulphates. eg. Cu 2  S 2  CuS ; Cd 2  S 2  CdS ;
Black ( Yellow)
Table 18.8
2 2 2 2
Sulphide Ores Sulphate Ores Ni S  NiS ; Co S  CoS
(Black) (Black)

Iron pyrites (fool’s gold) – FeS 2 Gypsum – CaSO 4 .2 H 2 O The solubility of sulphides can be controlled by the H  ions
Galena – PbS Epsom salt – MgSO4 .7 H 2 O concentration and therefore, H 2 S finds extensive use in qualitative
analysis of cation radicals.
Copper pyrites – CuFeS 2 Barytes – BaSO 4
: :
Cinnabar – HgS Zinc blende – ZnS S
Extraction of sulphur (Frasch process) : Sulphur is generally 93.3O
extracted from underground deposits by drilling three concentric pipes upto
the beds of sulphur (700 – 1200 feet deep). H H
(2) Halides of sulphur : Two important halides of sulphur are SF4
Allotropy in sulphur : Sulphur exists in four allotropic forms,
(1) Rhombic or octahedral or -sulphur : It is a bright yellow solid, and SF6 .
soluble in CS 2 and stable at room temp. All other varieties of sulphur (i) Sulphur tetrafluoride : SF4 is formed by the reaction of
gradually change into this form on standing. sulphur with CoF3 .
(2) Monoclinic sulphur or prismatic or -sulphur: It is prepared by S  4 CoF3  SF4  4 CoF2
melting the sulphur and then cooling it till a crust is formed. On removing
the crust, needle shaped crystals of monoclinic sulphur separate out. It is It is a colour gas which is quite reactive. It is hydrolysed with water.
dull yellow in colour, soluble in CS 2 and stable only above 369K. Below SF4  2 H 2 O  SO 2  4 HF
this temperature it changes into rhombic form. It is used for fluorinating inorganic and organic compounds.
Thus, at 369K both these varities co-exist. This temperature is Structure : It has see-saw structure with sp 3 d -hybrdization and is
called transition temperature and the two sulphurs are called enantiotropic derived from triogonal bipyramid geometry in which an equatorial position
substances. It also exist as molecules similar to that of rhombic sulphur but is occupied by a lone pair of electrons.
the symmetry of the crystals is different. F
(3) Plastic or amorphous or  -sulphur : It is a super cooled liquid F
insoluble in CS 2 , soft and amorphous. It consists of long zig-zag chains of : S
S-atoms.
F
F
.. .. ..
:S ..S S:
.. O
105 C ..
..S .. ..S
..S
.. ..
S S
 (ii) Sulphur hexafluoride : SF6 is prepared by burning sulphur in a SO 2 molecule has a bent structure with a O – S – O bond angle
stream of fluorine. OF is not known though sulphur forms SF . This is because
6 6
of 119 . Sulphur is sp 2 hybridized.
o

oxygen has no d -orbitals in its valence shell. ..

SF6 is a colourless gas. It is extremely inert substance even at red
heat. It does not react with water. on account of its chemical inertness and
S
p – d
dielectric strength, it is used as an insulator in high voltage generators and p – d
119O
switch-gears.  

Structure : It has an octahedral structure with sp 3 d 2 - O O

(ii) Sulphur trioxide (SO ): It is formed by the oxidation of SO 2 .
3

hybridisation around the central sulphur atom.

Therefore, all S  F bond distances are equal in its structure. 2SO 2  O2  2SO 3
700 K , 2 atm.
V2O5
F F
F In the gaseous phase, it exists as planar triangular molecular species
S involving hybridization of the S-atom. It has three S–O  bonds and three
F F S–O  bonds. The O–S–O bond angle is of 120 .
F o

(3) Oxides of sulphur : Sulphur forms several oxides of which O

sulphur dioxide (SO 2 ) and sulphur trioxide (SO 3 ) are most important.
p – 
(i) Sulphur dioxide (SO ) : It is prepared by burning sulphur or iron d
S
2

pyrites in air. p – p –
S 8  8 O2  8 SO 2 ; 4 FeS 2  11O2  2 Fe2 O3  8 SO 2 d

120O

d

In laboratory, it is prepared by heating copper turnings with conc. O O

(4) Oxyacids of sulphur : Sulphur forms many oxyacids. Some of
H 2 SO 4 these are,
Cu  2 H 2 SO 4  CuSO 4  SO 2  2 H 2 O
It is a colourless gas with irritating and suffocating smell.
Table : 18.9 Oxyacids of sulphur
Formula Name Important properties Structural formula
H 2 SO 3 (+4) Sulphurous acid Free acid does not exist diprotic, ..
strong reducing agent O  S  OH
|
OH
H 2 SO 4 (+6) Sulphuric acid Stable diprotic, dehydrating agent O
||
(Oil of vitriol) O  S  OH
|
OH
H 2 S 2 O 3 (–2 and +6) Thiosulphuric acid Free acid does not exist but its salts S
e.g. Na 2 S 2 O 3 All quite stable ||

reducing agent O  S  OH
|
OH
H 2 S 2O4 (+3) Dithionous acid O O
|| ||
HO  S  S  OH
H 2 S 2 O 6 (+5) Dithionic acid Free acid is moderately stable but its O O
salts are quite stable. || ||
OS— S O
| |
OH OH
H 2 S 2 O7 (+6) Disulphuric acid Strong oxidising agent O O
(Pyrosulphuric acid) || ||
(Oleum) O  S O S  O
| |
OH OH
H 2 SO 5 (+6) Peroxomonosulphuric acid Stable crystalline solid, powerfull O
(Its salts known as persulphates) oxidising agent ||
(Caro's acid) HO  S — OOH
||
O
H 2 S 2 O 8 (+6) Peroxodisulphuric acid Strong oxidising agent. O O
(its salts are known as disulphates) || ||
(Marshals acid) O  S  OO S  O
| |

OH OH
 O O O O O
Sulphuric acid (H SO ) : H SO is a very stable oxyacid of sulphur. It
2 4 2 4

is often called king of chemicals, since it is one of the most useful chemicals S S S
in industry. OH
O H O O H O O
Manufacture of sulphuric acid : H SO can be manufactured by OH
2 4

following process, H H
Lead chamber process : In this process, SO is oxidized to SO by Structure of H2SO4 H-bonding in conc. H2SO4
2 3

Properties : H SO has high b.p. (611K) and is also highly viscous due
the oxides of nitrogen and the SO thus formed is dissolved in steam to 2 4

3
to H-bonding. It has strong affinity for H O and a large amount of heat is
form H SO .
2 4
evolved when it is mixed with water.
2

SO + NO  SO + NO ; 2NO + O  2NO
2 2 3 2 2
(i) H SO is a strong dibasic acid. It neutralizes alkalies, liberates CO
2 4 2

SO + H O  H SO 3 2 2 4 from carbonates and bicarbonates.

Contact process : In the contact process, SO obtained by burning of 2
(ii) It reacts with more electropositive (than hydrogen) metals to
S or iron pyrities is catalytically oxidized to SO in presence of finely divided 3
evolve H and produces SO on heating with less electropositive metals than
2 2

Pt or V O as catalyst.
2 5
hydrogen .eg.,
S + O  SO or 4FeS + 11O  2Fe O + 8SO
2 2 2 2 2 3 2
H 2 SO 4  2 KOH  K 2 SO 4  2 H 2 O ;
V O or Pt, 673-732 K
2SO 2  O2 2 5

2SO 3 . Cu  2 H 2 SO 4  CuSO 4  SO 2  2 H 2 O
V O is, however, preferred since is much cheaper than Pt and is also (iii) It is a strong oxidizing agent and oxidises as follows,
H 2 SO 4  H 2 O  SO 2  O
2 5

not poisoned by arsenic impurities.

The favorable conditions for maximum yield of SO are, 3
C  2 H 2 SO 4  2SO  CO  2 H 2 O
(a) High concentration of SO and O (b) Low temperature of 673 to 2 2.
S  2 H 2 SO 4  3 SO 2  2 H 2 O
723 K, (c) High pressure about 2 atmospheres.
P4  10 H 2 SO 4  4 H 2 PO4  10 SO 2  4 H 2 O
SO thus obtained is absorbed in 98% H SO to form oleum which
3

on dilution with water gives H SO of desired concentration.

2 4

2 HBr  H 2 SO 4  Br2  2 H 2 O  SO 2
2 4

SO 3 + H 2 SO 4  H 2 S 2 O7 ; H 2 S 2O7  H 2O  2 H 2 SO 4 2 HI  H 2 SO 4  2 H 2 O  I2  2SO 2
oleum (iv) It reacts with number of salts. It liberates HCl from
Contact process is preferred over lead chamber process (gives 98% chlorides, H 2 S from sulphides, HNO from nitrates. 3

pure H 2 SO 4 ) since it gives H SO of greater purity (100%). 2 4 (v) It acts as a strong dehydrating agent, as it dehydrates, sugar to
sugar charcoal (carbon), formic acid to CO, oxalic acid to CO+ CO 2 and
Structure : H SO is a covalent molecule with sulphur in a +6
2 4

oxidation state. The two oxygen atoms are linked to sulphur by double ethyl alcohol to ethylene.
bonds while the other two oxygen atoms. (vi) It is also a good sulphonating agent and used for sulphonation
Are linked by single covalent bonds. Thus it has tetrahedral of aromatic compounds. eg.,
structure. Infact, sulphuric acid has an associated structure due to the
presence of hydrogen bonds. As a result, it is a dense and viscous liquid and
has a high boiling point of 590 K
Flow sheet diagram of it’s preparation is as follows
Impure SO2 Pyrite burners

(If impurities are present, passed through

purifying unit again) Impure SO2

Dust Chamber Cooler Scrubber Drier Arsenic purifier Testing Box

Purifying unit
Pure
SO2
Conc. H2SO4

H2SO4 Dilution Oleum Absorption Tower SO3 Catalyst Chamber Pre heater

BaCl2  H 2 SO 4  BaSO4  2 HCl C12 H 22 O11    12C  11H 2 O

Conc. H 2 SO 4
(white ppt) Sugar Carbon

Pb(NO 3 )2  H 2 SO 4  PbSO4  2 HNO 3 HCOOH    CO + H O

Conc . H 2 SO 4
2

(white ppt.)
 Uses : H SO is used (i) in the preparation of fertilizers like
2 4
Fluorine is the first member of group 17 or VIIA of the periodic
(NH ) SO 4 and super phosphate of lime, (ii) in lead storage batteries (iii) in table. It consists of five elements Fluorine (F), Chlorine (Cl), bromine (Br),
iodine (I) and astatine (At). These are known as halogen because their salts
4 2

preparation of dyes, paints and explosives (iv) in textile and paper industry are found in sea water. Halogen is a greek word meaning a sea salt.
(v) for training of tanning (vi) as a dehydrating agent.
(1) Electronic configuration
(5) Sodium thiosulphate Na 2 S 2O3 .5 H 2O : It is manufactured by
saturating a solution of sodium carbonate with SO which gives a solution of Elements Electronic configuration ( ns 2 np 5 )
2

sodium sulphite,
9F [He] 2 s 2 2 p 5
Na 2CO3  SO 2  H 2O  Na 2 SO 3  CO 2  H 2O
17 Cl [ Ne ] 3 s 2 3 p 5
The resulting solution is boiled with powdered sulphur as,
Na 2 SO 3  S   Na 2 S 2 O3
373 K 35 Br [ Ar] 3d 10 4 s 2 4 p 5
The solution is then cooled to get crystals of sodium thiosulphate. 53 I [Kr] 4 d 10 5 s 2 5 p 5
Physical properties : (i) Sodium thiosulphate is a colourless
85 At [ Xe] 4 f 14 5 d 10 6 s 2 6 p 5
crystalline solid. In the hydrated form, it is called hypo. (ii) It melts at 320 K
and loses its water molecules of crystallization on heating to 490K.
Chemical properties Physical properties
(i) Action with halogens : It reacts with halogens as, (1) Atomic and ionic radii : A halogen atom has the smallest radius
(a) Chlorine water oxidizes sodium thiosulphate to sodium as compared to any other element in its period. This is due to the increased
sulphate and sulphur is precipitated, effective nuclear charge which results in greater attraction of the electrons
Na S O + Cl + H O  2HCl + Na SO +S
2 2 3 2 2 2 4
by the nucleus. The atomic radii. Increase from fluorine to iodine down the
This property enables it to act as an antichlor in bleaching i.e. it group due to increase in number of shells.
destroys the unreacted chlorine in the process of bleaching. Element F Cl Br I
(b) Bromine water also oxidizes sodium thiosulphate to sodium Covalent radius (pm) 72 99 114 133
sulphate and sulphur,
Na S O + Br + H O  Na SO + 2HBr + S Ionic radius (pm) 133 184 196 220
2 2 3 2 2 2 4

(c) With iodine it forms a soluble compound called sodium (2) Ionization energy : Ionization energy of these elements are
tetrathionate, higher than those of the corresponding elements of group 16 due to
increased nuclear charge. these values decrease systematically as we move
2 Na 2 S 2O3  I2  Na 2 S 4 O6  2 NaI
Sod. tetrathionate down the group from F to 1
Therefore, hypo is commonly used to remove iodine stains from the Element F Cl Br I
clothes.
I.E (kJ mol ) –1
1680 1256 1142 1008
(ii) Action of heat : Upon heating, sodium thiosulphate
1

decomposes to form sodium sulphate and sodium pentasulphide, Thus iodine which has a comparatively low value of I.E., has a
tendency to lose an electon to form positive iodinium ion, I and thus shown
+

4 Na 2 S 2 O3   3 Na 2 SO 4 
Heat
Na 2 S 5 electropositive or metallic character.
Sodium pentasulphide

(iii) Action with acids : Sodium thiosulphate reacts with dilute (3) Electronegativity : Fluorine is the most electronegative element
hydrochloric acid or Sulphuric acid forming sulphur dioxide and sulphur. in the periodic table. With increase in atomic number down the group, the
The solution turns milky yellow due to sulphur. electronegativity decreases.
Na S O + 2HCl  2NaCl + SO + H O + S Element F Cl Br I At
2 2 3 2 2

Electronegativity 4.0 3.2 3.0 2.7 2.2

(iv) Action with silver halides : Sodium thiosulphate forms soluble
complex when treated with silver chloride or silver bromide, The decreasing order of electronegativity is F  Cl  Br  I
2 Na 2 S 2 O3  2 AgBr  Na 3 Ag(S 2 O3 )2  NaBr . (4) Electron affinity : Electron affinity of chlorine, bromine and
Sodium dithiosulphate
argentate (I) compex iodine decrease as the size of the atom increases. The electron affinity of
This property of hypo is made use in photography. fluorine is, however, lower than that of Cl and Br , because of its small
Uses of sodium thiosulphate size as a result of which inter-electronic repulsions present in its 2 p
subshell are comparatively large. Thus chlorine has the highest electron
(i) It is largely used in photography as a fixing agent.
affinity.
(ii) It is used as a preservative for fruit products such as jams and
squashes.
Element F Cl Br I
Electron affinity (kJ mol )
–1
333 348 325 296
(iii) It is used as an antichlor in bleaching.
The decreasing order of electron affinity is Cl  F  Br  I
(iv) It is used as a volumetric agent for the estimation of iodine.
(5) Oxidation states : All the halogens show an oxidation state of –1.
(v) It is used in medicine.
Fluorine being the most electronegative element always shows an oxidation
Halogen Family state of –1 while other halogens also show positive oxidation states up to a
maximum of +7 (i.e. +1, +3, +5 and +7) due to the availability of vacant d -
orbitals in the valence shell of these atoms. Some halogens also show +4 and I due to an increase in the vander Waals forces of attraction which
+6 oxidation states in oxides and oxy acids. increase down the group as the size of the atom increases.
(6) Nature of bonds : All the halogens have seven electrons in the
Element F Cl Br I
valence shell and hence require one more electron to acquire the nearest
inert gas configuration either by gaining an electron from the metallic atom Melting point (K) 54 172 266 386
to form halide, X  ion, or by sharing an electron with an electronegative Boiling point (K) 85 239 332 458
element. Thus, halogens form both ionic and covalent compounds. The
Hence, the melting points and boiling points show the order as
halides of highly electropositive metals are ionic while those of weakly
F  Cl  Br  I .
electropositive metals and non-metals are covalent. The tendency to form
ionic compounds decreases from F to I. Thus, F because of its high (13) Solubility : Halogens, being non polar in nature do not readily
electronegativity forms ionic compounds even with less electropositive dissolve in a polar solvent like water. however, fluorine reacts with water
metals like Hg, Bi, Sn etc. while other halogens form only covalent vigorously even at low temperature (exothermally) forming a mixture of
ozone and oxygen
compounds.
(7) Non-metallic character : All the halogens are non-metallic in 2 F2  2 H 2 O  4 HF  O 2
nature due to their high ionization energies. The non-metallic character
gradually decreases down the group. However, iodine is, solid and has 3 F2  3 H 2 O  6 HF  O3
metallic lustre.
Chlorine and bromine are fairly soluble but iodine is very little
(8) Atomicity and physical state : All the halogens exist as diatomic
soluble in water. chlorine, bromine and iodine are more soluble in organic
covalent molecules (F2 , Cl 2 , Br2 and I 2 ) . F2 and Cl 2 are gases at room
solvents like CCl 4 , CS 2 or CHCl 3 and produce coloured solutions.
temperature, Br2 is corrosive liquid and I 2 is volatile solid.
Thus Cl 2 , Br2 and I 2 give yellow, brown and violet colour respectively. It
(9) Colour : All the halogens have characteristic colours. F2 is light is believed that in non-polar solvents, halogens exist as free molecules just
yellow, Cl 2 is greenish yellow, Br2 is reddish brown and I 2 is deep violet. as in the gas phase.
The colour of halogens is due to the reason that their molecules absorb In nucleophilic (electron donating) polar solvents like alcohols,
light in the visible region as a result of which electron are excited to higher ketones or liquid SO 2 , halogens produce brown solution. This colour is
energy levels. The amount of energy needed for excitation decreases due to the complex formation (solvent  halogen) which are charge
progressively from F2 to I 2 and consequently there is a progressive transfer compounds.
deepening of colour of the halogens from F2 to I 2 . Since, fluorine atom
The solubility of iodine (I 2 ) in water increases with addition of
requires large amount of energy for excitation of electrons and therefore
absorbs violet light and apears yellow. On the other hand, iodine requires KI or NaI due to the formation of polyhalide (triiodide, I 3 ) ion,
low energy for excitation of electrons (absorbs yellow light) and appears KI  I 2 ⇌ KI 3
deep violet.
(10) Bond dissociation energy : Bond dissociation energies of However, this solution behaves as a simple mixture of KI and free
chlorine, bromine and iodine decrease down the group as the size of the I 2 and contains K  and I  ions and free I 2 molecules. It has a brown
atom increases. The bond dissociation energy of fluorine, is however, lower colour. The solution of iodine in water (due to its very little solubility) is
than those of chlorine and bromine because of inter electronic repulsions also brown.
present in the small atom of fluorine
(14) Oxidising power : All the halogens acts as strong oxidising
X2
F2
Cl2
Br 2
I 2 agents since they have a strong tendency to attract electrons and have
Bond dissociation energy (kJ 158 243 192 151 positive values of electrode potentials (E o ) . The oxidising power, however,
mol )
–1

decreases as we move down the group from F to I . i.e.,

Hence bond energy decreases in the order Cl 2  Br2  F2  I2 F2  Cl 2  Br2  I2

(11) Bond length in X molecule : As the size of the halogen atom

2
Since F2 is the strongest oxidising agent, it will oxidise all other
increase, the bond length of X  X bond in X 2 molecule increases from halide ions to halogens.
F2 to I 2
F2  2 X   2 F   X 2 (X  Cl, Br, I)
X–X bond F–F Cl–Cl Br–Br I–I
Similarly, Cl 2 will displace Br  and I  ions from their solutions
Bond length (pm) 143 199 228 266
while Br2 will displace I  ions only.
Thus, the bond length increases in the order
F2  Cl 2  Br2  I2 . Cl 2  2 X   2Cl   X 2 (X  Br, I)
(12) Melting points and boiling points : Melting points and boiling
Br2  2 I   2 Br   I 2
points of these elements increase as we move down the group from F to
 Hence F2 is the strongest and I 2 is the weakest oxidising agent.  Acidic strength in aqueous solution is in the order,

This is also indicated by the decrease in the electrode potential (E o ) for HI > HBr > HCl < HF.

the reaction X 2 (aq)  2e   2 X  (aq) on moving down the group.  Reducing character of hydrides follow the order,
HI > HBr > HCl > HF.
X 2
F2
Cl2
Br 2
I 2
At 2

 Boiling point HF > HI > HBr > HCl. Thermal stability,

E (volts)
o
2.87 1.36 1.09 0.53 0.3
H – F > H – Cl > H – Br > H – I.
The electron affinity of fluorine is less than that of chlorine but still
it is the strongest oxidising agent. This is because of its low bond HCl is also called Muriatic acid.
(4) Hydrides : All the halogens combine directly with hydrogen to
dissociation energy (158 kJ mol 1 ) and high heat hydration
form halogen acids but their reactivity progressively decreases from fluorine
(510 kJ mol 1 ) as compared to chlorine (for which the values are 243 to iodine, H + X  2HX (X = F, Cl, Br or I).
2 2

1 (i) Boiling points or volatility : In other words volatility decreases in

and 372 kJ mol , respectively).
the order : HCl > HBr > HI > HF as the boiling points increase in the order :
(15) Heat of hydration : The heat of hydration of the halide ion HCl (189K) < HBr (206K) < HI (238K) < HF (292.5K).

( X ) decreases as the size of the halogen decreases down the group from (ii) Thermal stability : Thermal stability of the hydrides decrease from
F to I . HF to HI i.e., HF > HCl > HBr > HI.
X ion
–

F Cl  Br  I (iii) Acidic strength : The acidic strength of halogen acids decreases

Heat of hydration (kJ 510 372 339 301 from HI to HF i.e, HI > HBr > HCl > HF.
mol ) –1
(iv) Reducing properties : Since the stability of hydrides decreases
Thus, the decreasing order of heat of hydration of halides is as from HF to Hl, their reducing properties increase in the order HF < HCl <
follows : HBr < HI.
(v) Dipole moments : The dipole moments of hydrogen halides decrease
F   Cl   Br   I 
in the order : HF > HCI > HBr > HI as the electro negativity of the halogen
Chemical properties
atom decreases form F to I.
(1) Reactivity : The halogen are most reactive elements due to their
HX HF HCl HBr Hl
low bond dissociation energy, high electron affinity and high enthalpy of
hydration of halide ion. F > Cl > Br > I Dipole moment (D) 1.74 1.07 0.78 0.38
(2) Reaction with H O : Halogens readily decomposes water. This
2
(5) Oxides : Halogens (except F ) do not combine readily with 2

tendency decreases on moving down the group. Fluorine decomposes water oxygen. However, a number of compounds of halogens with oxygen have
very energetically to give oxygen and ozone, been prepared by indirect methods. Only two compounds of fluorine with
oxygen, i.e. oxygen difluorine (OF ) and oxygen fluoride (O F ) are known.
2 H 2 O  2 F2  4 HF  O2 ; 3 H 2 O  3 F2  6 HF  O3 2

Chlorine forms largest number of oxides i.e. Cl O, ClO , Cl O and Cl O while

2 2

Oxygen Ozone 2 2 2 6 2 7

iodine forms the least, i.e. I O . Bromine, however, forms three oxides (Br O,
2 5 2

Fluorine gives fumes in moist air. This is due to the formation of BrO C BrO ). In all these compounds, bonds are largely covalent. All the
2 3

HF, which is a liquid and can absorb moisture to form liquid droplets and oxides of halogens are powerful oxidizing agents. These compounds are very
therefore, gives fumes with moist air. Chlorine and bromine react less reactive and are unstable towards heat. The stability of oxides is greatest for
vigorously, iodine while bromine oxides are the least stable. For a particular halogen,
higher oxides are more stable than the lower ones.
Cl 2  H 2 O  HCl  HClO Iodine-oxygen bond is stable due to greater polarity of the bond
Hypochloro us acid
(due to larger electro negativity difference between I and O) while in
Br2  H 2 O  HBr  HBrO chlorine-oxygen bond, the stability is gained through multiple bond
Hypobromou s acid
formation involving the d-orbital of chlorine atom. Bromine lacks both these
In the presence of sunlight, HClO (hypochlorous acid) HBrO
characteristics and hence forms least stable oxides.
(hypobromous acid) liberate oxygen.
Oxides of chlorine, bromine and iodine are acidic and the acidic
2 HClO  2 HCl  O2 ; 2 HBrO  2 HBr  O 2
character increases as the percentage of oxygen increases in them.
Iodine is only slightly soluble in water. However, it dissolves in 10% Iodine also forms I O and I O compounds which are believed not to
2 4 4 9

aqueous solution of Kl due to the formation of I 3 ions. be true oxides but are basic iodyliodate, IO(IO ) and normal iodine triodate, 3

I(IO ) having tripositive iodine as the cation.

I2  KI ⇌ KI 2  I 
⇌ I 3 3 3

Complex ion OF is V-shaped having bond angle 103 , Cl O is also V-shaped with
2
o

(3) Reaction with hydrogen : Form covalent halides. bond angle 111 while ClO is angular with-bond angle 118 . It is paramagnetic
o

2
o

due to odd number of electrons having three-electron bond. It is regarded

as a mixed anhydride of chloric and chlorous acids. 2ClO + H O  HClO +
o
200 C
H 2  F2   2 HF (very violent) 2 2 2

HClO
H 2  Cl 2  2 HCl Sunlight 3

(6) Oxoacids of halogens : Fluorine does not form any oxoacid since
H 2  Br2   2 HBr
Heat
it is the strongest oxidizing agent. Chlorine, bromine and iodine mainly
pt. catalyst
form four series of oxoacids namely hypohalous acid (HXO), halous acid
H 2  I2 Heat 2 HI (poor yield) (HXO ) halic acid (HXO ) and perhalic acid (HXO ) as given below :
2 3 4
 Table 18.10 (10) Inter halogen compounds : The compounds of one halogen with
the other are called inter halogens or inter halogen compounds. The main
Oxidation Chlorine Bromine Iodine Thermal stability Oxidising
reason for their formation is the large electronegativity and the size
state and acid strength power
differences between the different halogens. Taking A as the less
+1 HClO HBrO HIO electronegative and B as the more electronegative halogen, they are divided

Decreases
into the following four types the less electronegative halogen (A) is always

Increases
+3 HClO – –
2

written first.
+5 HClO HBrO HIO
3 3 3
AB AB 3
AB AB 5 7

+7 HClO HBrO HIO

4 4 4
ClF ClF3 , BrF3 BrF5 IF5 IF7
Acidity decreases  BrF, BrCl, ICl
IF3 , ICl3
3
(i) Hybridized ion : In all these oxoacids, the halogen atom is sp - IBr, IF
hybridized.
(ii) Acidic character : All these acids are monobasic containing an— These interhalogen compounds are unstable and more reactive
OH group. The acidic character of the oxoacids increases with increase in (i) General properties
oxidation number, i.e., HClO < HClO < HClO < HClO and the strength of
2 3 4
(a) Largest halogen always serves the central atom.
the conjugate bases of these acids follows the order,
(b) The highest interhalogen compound i.e. IF is obtained with
  
7

ClO > ClO 2 > ClO 3 > ClO4 iodine, the largest halogen attached to the smallest one
(iii) Oxidising power and thermal stability : The oxidizing power of (c) The bonds in interhalogen compounds are essentially covalent.
these acids decreases as the oxidation number increases, i.e., HClO < HClO 2
(d) Thermal stability decreases as the size difference decreases and
< HClO < HClO . Stability of oxoacids of chlorine in the increasing order
3 4
increases as the polarity of the bond increases. Thus ClF is thermally more
is, HClO < HClO < HClO < HClO and the increasing stability order of
2 3 4
stable as compared to IBr.
anions of oxoacids of chlorine is, ClO   ClO2  ClO3  ClO4 . (e) They ionize in solution or in the liquid state,
As the number of oxygen atoms in an ion increases there will be a 2 ICl ⇌ I   ICl2 ; 2ICl3 ⇌ ICl2  ICl4
greater dispersal of negative charge and thus greater will be the stability of
(f) Hydrolysis of interhalogen compounds always produces a halide
ion formed. For different halogen having the name oxidation number, the
ion derived from smaller halogen and oxyhalide derived from larger halogen,
thermal stability decreases with increase in atomic number i.e., it is in the
order HClO > HBrO > HIO and ClO > BrO > IO However, in HXO3 is – – – ICl  H 2O  Cl   OI  2 H  ;
most stable. The stability order being HClO < HBrO < HIO . 3 3 3
BrF5 3 H 2O  5 F   BrO3  6 H 
(iv) Perhalates are strong oxidizing agents, the oxidizing power is in
(g) They are strong oxidizing agents.
the order, BrO4  IO4  ClO4 .
(h) Largest number of interhalogens are formed by fluorine due to
Thus BrO is the strongest oxidizing agent (though its reaction is
4
its smaller size and higher electronegativity or oxidizing power.
quite slow) and ClO4 is the weakest. (ii) Structure : Interhalogen compounds are,
(v) The acidity of oxoacids of different halogens having the same (a) AB type i.e. ICl, IBr, IF etc, are linear
oxidation number decreases with increase in the atomic size of the halogen (b) AB type i.e. IF , ClF , BrF have distorted trigonal bipyramidal
3 3 3 3

(dsp -hybridization) structures of T-shape due to two lone pairs in

3

i.e. HClO4  HBrO4  HIO4 .

equatorial positions ICl is dimeric, I Cl and has a planar structure.
3 2 6

(7) Reaction with alkalies : (c) AB types i.e. BrF , IF have distorted octahedral (d sp -
5 5 5
2 3

2 F2  2 NaOH  2 NaF  OF2  H 2O hybridization) shapes or square pyramidal due to a lone pair one of the
(cold dilute) axial positions.
2 F  4 NaOH  4 NaF  O2  2 H 2O (d) AB type i.e. IF , have pentagonal bipyramidal (d sp -hybridization)
7 7
3 3

(hot conc.) structures.

(11) Polyhalide ions : Halogens or interhalogens combine with halide
Halogen other than fluorine (Cl2 , Br2 , I2 ) react with NaOH as
ions to form polyhalide ions. The most common example of polyhalide ion
follows, formation is furnished by the increase in solubility of iodine in water in the
X 2 (g)  2OH    X   OX   H 2 O
15 C o
presence of KI which is due to the formation of tri iodide ion, I3
(cold dilute) (hypohalite ion)
I   I2  I3
o
X 2 (g)  6 OH    5 X   XO3  3 H 2 O
70 C
Many other examples of polyhalides ions are
(hot conc) (halate ion)
(i) Cl 3 , Br3 , ICl2 , IBr2 including I3 . In these ions, one of the
(8) Bleaching action of halogen : Cl 2 acts as bleaching agent, its
halogen atoms (in case of similar atoms) or halogen atom larger in size
bleaching action is permanent. Cl 2 water can also act as ink remover. undergoes sp 3 d -hybridization giving a linear shape with three lone pairs
(9) Reaction with other halides at equatorial positions.
2 KBr(aq.)  Cl 2 (g)  2 KCl (aq.)  Br2 (aq.) (ii) Cl 3 , Br3 , I3 , ICl2 , IBr2 . Here we find central atom sp 3
2 KI(aq.)  Cl2 (g)  2 KCl(aq.)  I2 (aq.) hybridized giving a bent shape with two lone pairs of electrons on the
central atom.
 (iii) ICl4 , BrF4 , I5 . Here central atom involves sp 3 d 2 While other halogen acids ( HCl, HBr and HI ) do not react with
hybridization giving square planar shape with two lone pairs of electrons on silicates and hence can be stored in glass bottles.
axial positions. (7) AgF is soluble in H 2 O while all other silver halides i.e.,
(iv) ICl4 , BrF4 , I5 . In these ions central atom involves sp 3 d AgCl, AgBr and AgI are insoluble in water. In constant, CaF2 is
hybridization giving a distorted tetrahedral structure with one lone pair of insoluble while other calcium halides i.e., CaCl 2 , CaBr2 , CaI2 are soluble
electrons on equatorial position.
in H 2 O .
(v) I7 , IF6 . The central atom I undergoes sp 3 d 3 hybridization
(8) Due to absence of d -orbitals, fluorine, does not form
giving a distorted octahedral structure with one lone pair of electrons. polyhalide ions while other halogens form polyhalides of the type
(vi) I7 . Here central I atom involves sp 3 d 2 hybridization giving I3 , Br3 , I5 etc.
an octahedral structure. Preparation of halogens and its uses
Fluorine due to its highest electronegativity (and only –1 oxidation (1) Fluorine
state) does not form polyhalide ions where it acts as a central atom. (i) Occurrence of fluorine : Fluorine does not occur free in nature
(12) Pseudohalogen and pseudohalides but occurs mostly as fluorspar CaF2 , cryolite, Na 3 AlF6 and fluorapatite,
Pseudohalogen Pseudohalide CaF2 .3Ca 3 (PO4 )2 . Traces of fluoride occur in sea water, bones, teeth,
Cyanogen – (CN )2 Cyanide – CN  blood, milk etc.
(ii) Difficulties encountered during its isolation : (a) F2 attacks all
Oxocyanogen – (OCN )2 Cyanate – OCN 
the materials of the apparatus such as glass, platinum, carbon and other
Thiocyanogen – (SCN ) 2 
Thiocyanate – SCN metals, (b) F2 is the strongest oxidising agent and hence no oxidising

Selenocyanogen – (SeCN ) 2 Selenocyanate – SeCN agent can oxidise F  ions to F2 . (c) F2 cannot be prepared even by
electrolysis of an aqueous solution of HF because F2 formed reacts
(13) Anomalous behaviour of fluorine : Fluorine differs from rest
of the elements of its family due to (i) its small size (ii) highest violently with water. If also cannot be prepared by electrolysis of anhydrous
electronegativity, (iii) low bond dissociation energy and (iv) absence of d- HF because it is not only poisonous, corrosive and volatile but also is a
orbitals in the valence shell. The main points of difference are : bad conductor of electricity.
(1) Fluorine is most reactive of all the halogens due to lower value
(iii) Preparation : F2 is now prepared by electrolysis of a solution
of F  F bond dissociation energy ( F2  158, Cl 2  243 , bromine = 192
and iodine = 151 kJ mol ) .
–1
of KHF2 (1 part) in anyhydrous HF (5 parts) in a vessel (modern
(2) Being the most electronegative element, it shows only an method) made of Ni  Cu alloy or Ni  Cu  Fe alloy called the monel
oxidation state of –1 and does not show positive oxidation states due to metal using carbon electrodes. During the electrolysis following reactions
absence of d -orbitals in its valence shell. Other halogens show positive occur.
oxidation states of +1, +3, +5 and +7.
KHF2  KF  HF ; KF  K   F 
(3) Due to small atomic size and high electronegativity of F, HF
undergoes strong H -bonding while other halogen acids do not. As a result, At cathode : K   e   K ; 2 K  2 HF  2 KF  H 2 
(i) HF is a liquid (boiling point 292.5K), while other halogen acids
At anode : F   F  e  ; F  F  F2
are gases at room temperature (boiling point of HCl  189 K ,
HBr  206 K , HI  238 K ). (iv) Properties : It is the most reactive of all the halogens. It
Combines with metals as well as non-metals to form fluorides. It
(ii) HF is weakest of all the halogen acids due to high strength of
decomposes water forming O 2 and O 3 and reacts vigorously with
H  F bond.
(iii) Due to H -bonding, HF can form acid salts of the type hydrogen of hydrocarbons leaving behind fluorinated hydrocarbons.

KHF2 , i.e., K  [H  F....... F  ] while HCl, HBr and HI do not form 2 H 2 O  2 F2   4 HF  O 2

Cold
Oxidation
such salts (i.e., no KHCl 2 , KHBr2 and KHI2 are known).
3 H 2 O  3 F2  6 HF  O 3
Hot
(4) Fluorides have the maximum ionic character. For example Oxidation
AlF3 is ionic while other halides of Al are covalent. ( HF being a volatile liquid fumes in air)
(5) Of all the halogens, fluorine has the highest positive electrode
CH 4 
F2
 CH 3 F 
F2
 CH 2 F2 
F2
 CHF3 
F2
 CF4
potential ( F2  2.87, Cl 2  1.36, Br2  1.09 and I2  0.53 volt) i.e., it
is most easily reduced and hence acts as the strongest oxidising agent. It It is a strong oxidising agent and oxidises KClO3 to
brings about the highest oxidation of other elements with which it
KClO4 , KlO3 to KlO4 and bisulphates to peroxy sulphates.
combines. For example with S , it gives SF6 , with I 2 it gives IF7 . Other
halogens do not always bring about the highest oxidation state. For example, KClO3  F2  H 2 O  KClO4  H 2 F2
with sulphur Cl 2 gives SCl 4 , Br2 gives SBr2 while I 2 does not react at
2 NaHSO 4  F2  Na 2 S 2 O8  2 HF
all. F2 is so powerful oxidising agent that it can even oxidise inert-gases.
It reacts with NH 3 to form nitrogen and with H 2 S forming
(6) HF cannot be stored in glass bottles sicne it reacts with
silicates to form fluorosilicates. SF6 .
Na 2 SiO3  6 HF  Na 2 SiF6  3 H 2 O
 2 NH 3  3 F2  N 2  6 HF (oxidation reaction) Other oxidising agents such as PbO2 , Pb3 O4 , CaOCl 2 , O3 etc.
also react with HCl to liberate Cl 2 .
H 2 S  4 F2  SF6  2 HF
(iii) Properties : It combines with metals and non metals to form
Fluorine reacts with cold and dilute sodium hydroxide solution to chlorides. it decomposes water forming HCl and HClO (hypochlorous
give oxygen difluoride (OF2 ) acid) which is unstable and decomposes giving nascent oxygen which is
responsible for oxidising and bleaching action of chlorine.
2 F2  2 NaOH (cold, dil)  2 NaF  H 2 O  OF2
Cl 2  H 2 O  HCl  HClO ; HClO 
hv
HCl  [O]
However, with hot and concentrated sodium hydroxide solution it
gives oxygen Coloured matter  O  Colourless matter.
2 F2  4 NaOH(Hot, conc.)  4 NaF  2 H 2 O  O 2 The bleaching action is permanent and colour is not restored on
standing. However, it cannot be used for bleaching delicate articles such as
Since F2 is the strongest oxidising agent, it is always reduced and straw, silk, wool etc. which are damaged by it.
hence does not show disproportionation reactions while others halogens do.
Cl 2 oxidises Br  and I  ions to Br2 and I 2 respectively.
F2 oxidises all other halide ions to the corresponding halogens
Cl 2  2 X   2Cl   X 2 (X  Br or I) .
(F2  2 X   2 F   X 2 ) ; (X  Cl, Br or I)
It combines with alkalies forming hypochlorite and chlorate salts in
(v) Uses of fluorine : Fluorine is used in the manufacture of UF6 cold and hot conditions respectively.
(which is used for nuclear power generation), SF6 (which is used as an 2 NaOH(dil.) Cl 2   NaCl  NaClO  H 2 O
Cold

electrical insulator), chlorofluorocarbons, teflon, cryolite and HF .

(vi) Fluorocarbons are the derivatives of hydrocarbons in which 6 NaOH(Conc.)  3Cl 2   5 NaCl  NaClO3  3 H 2 O
Heat

H -atoms are replaced by F -atoms. these are obtained by fluorination of During these reactions, halogen is simultaneously reduced to X 
hydrocarbons with F2 diluted with an inert gas such as N 2 in presence of
ion and is oxidised to either hypohalite ( XO  ) or halate ( XO 3 ) ion. Such
CuF2 as catalyst. Fluorocarbons are widely used in industry because of reactions are called disproportionation reactions.
their extreme inertness (non-in-flammability and extreme stability). Freon
With slaked lime, Cl 2 gives bleaching powder (CaOCl 2 )
(CF2 Cl 2 ) is used as a refrigerant, tetrafluoroethylene (F2 C  CF2 ) is
used for the manufacture of teflon which is highly non-inflammable, has Ca(OH )2  Cl 2  CaOCl 2  H 2 O
high thermal stability and is chemically inert i.e., is not attacked by acids
and corrosive chemicals. It is used for making pipes, surgical tubes, non- With ammonia, Cl 2 reacts as follows :
stick utensils and as an electrical insulator.
8 NH 3 (excess )  3Cl 2  6 NH 4 Cl  N 2 
(2) Chlorine
(i) Occurrence : Chlorine mainly occurs as rock salt (NaCl) NH 3  3Cl 2 (excess )  NCl 3  3 HCl
Carnallite, (KCl, MgCl2 .6 H 2 O) and Calcium chloride. (CaCl 2 ) . With SO 2 and CO , addition compounds are formed
(ii) Preparation : On a commercial scale chlorine is prepared by
electrolysis of an aqueous solution of sodium chloride (brine solution) SO 2 (dry)  Cl 2  SO 2 Cl 2 (Sulphuryl chloride)
(Nelson cell, Castner and Kellner’s cell for the manufacture of NaOH )
CO  Cl 2  COCl 2 (Carbonyl chloride or phosgene)
when Cl 2 is evolved at the anode and H 2 is evolved at the cathode.
Cl 2 is strong oxidising agent. It oxidises FeCl 2 to FeCl 3 , moist
2 NaCl  2 H 2 O    2 NaOH  Cl 2   H 2 
Electrolysis

SO 2 to H 2 SO 4 , SO 32 to SO 42  , thiosulphate to sulphate and sulphur.

It can also be prepared by electrolysis of molten NaCl (Down’s
cell for the manufacture of metallic sodium). When Cl 2 is evolved at the (iv) Uses of chlorine : It is used in the manufacture of
anode and sodium metal at the cathode. HCl, NaOCl , bleaching powder, chlorates, vinyl chloride, insecticides such
2 NaCl    2 Na  Cl 2 
Electrolysis as DDT, chlorinated organic solvents like CHCl 3 ,CCl 4 . It is also used in

In the laboratory, Cl 2 is prepared by the action of MnO2 or sterilisation of drinking water, in the extraction of Au and Pt and as a
bleaching agent for paper, pulp and textiles.
KMnO4 or K 2 Cr2 O7 on conc. HCl or a mixture of NaCl and Conc. (3) Bromine
H 2 SO 4 (i) Occurrence : It mainly occurs in sea water and salt lakes as
MnO2  4 HCl  MnCl2  Cl 2  2 H 2 O NaBr, KBr and MgBr2 .
(ii) Preparation : On a commercial scale, bromine is prepared either
2 KMnO4  16 HCl  2 KCl  2 MnCl2  5 Cl 2  8 H 2 O
from sea water (containing NaBr, KBr and MgBr2 ) or the mother
K 2 Cr2 O7  14 HCl  2 KCl  2CrCl3  7 H 2 O  3Cl 2 liquor (containing MgBr2 ) left after crystallisation of chlorides from
MnO2  2 NaCl  3 H 2 SO 4  2 NaHSO 4  MnSO 4  2 H 2 O  Cl 2 carnallite. On passing Cl 2 gas through these solutions, bromides get
2 KMnO4  10 NaCl  13 H 2 SO 4  oxidised to bromine which is cooled and condensed to Br2 liquid.

10 NaHSO 4  K 2 SO 4  2 MnSO 4  8 H 2 O  5Cl 2 2 Br   Cl 2  2Cl   Br2

 In the laboratory, bromine can be prepared by heating NaBr with With cold, dilute NaOH , iodine gives hypoiodous acid
MnO2 and conc. H 2 SO 4 . NaOH  I2   NaI  HIO
Cold

2 NaBr  MnO2  3 H 2 SO 4  2 NaHSO 4  MnSO 4  2 H 2 O  Br2 However, with hot, conc. solution of NaOH , the reaction is
It is also obtained by adding HCl to a mixture containing similar to that of Cl 2 or Br2 .
potassium bromide and potassium bromate. Iodine does not displace chlorine and bromine from chlorides and
bromides respectively, but it displaces them from their oxy salts
5 KBr  KBrO3  6 HCl  6 KCl  3 Br2  3 H 2 O
(iii) Properties : Bromine is a reddish brown heavy liquid. 2 KClO3  I2  2 KIO3  Cl 2
Its reaction with water, oxidising and bleaching action, reaction with 2 KBrO3  I2  2 KIO3  Br2
alkalies, NH 3 , metals and non metals are similar to that of chlorine. Br2
With Na 2 S 2 O 3 , iodine solution is decolourised due to the
oxidises only iodide ions to I 2 . Bromine water reacts with mercuric oxide formation of colourless iodide and tetrathionate ions.
to form mercury oxy bromide
2 Na 2 S 2 O3  I2  2 NaI  Na 2 S 4 O6
2 HgO  2 Br2  H 2 O  HgBr2 .HgO  2 HBrO
Bromine water Mercury oxy bromide With ammonia it reacts as follows
(iv) Uses of bromine : The main use of bromine is in the 2 NH 3  3 I2  NI 3 . NH 3  3 HI
manufacture of ethylene bromide which is used as an additive to leaded (explosive)

petrol. It is also used to prepare AgBr , bromine water, dyes, drugs and 8 NI 3 . NH 3  5 N 2  9 I2  6 NH 4 I
benzyl bromide (an effective tear gas).
With strong oxidising agents such as HNO 3 ,O3 and Cl 2 , iodine
(4) Iodine
(i) Occurrence : It mainly occurs in sea weeds or alkali metal gives iodic acid (HIO3 )
iodides. Caliche (crude chile salt petre) which is mainly sodium nitrate
I2  10 HNO 3  2 HIO3  10 NO 2  4 H 2 O
contains iodine as sodium iodate (NaIO3 ) .
(ii) Preparation of iodine : On a commercial scale iodine is prepared I2  H 2 O  O3  2 HIO3  5 O 2
from sea weeds and caliche. I2  5 Cl 2  6 H 2 O  2 HIO3  10 HCl
(a) From sea weeds : Sea weeds (Laminaria variety) are dried, burnt
(iv) Uses of iodine : It is used to prepare tincture of iodine (2%
and ash (called kelp constains about 1% I 2 as iodides of alkali metals
solution of I 2 in alcohol), iodex, iodoform, KI , iodised salt (which
besides chlorides and sulphates) is extracted with hot water. sulphates and
chlorides are separated by fractional crystallisation, the mother liquor is contains KI or NaI , 0.5 g per kg of NaCl ) and as a laboratory
treated with Cl 2 gas or heated with MnO2 and conc. H 2 SO 4 to reagent.
liberate I 2 which is cooled and condensed to give violet crystals. (5) Hydrogen halides : All the halogens combine with hydrogen to
form hydrogen halides (HX ) .
2 NaI  Cl 2  2 NaCl  I2
(i) Preparation of HF and HCl : These are prepared by heating
2 NaI  MnO2  3 H 2 SO 4  2 NaHSO 4  MnSO 4  2 H 2 O  I2 fluorides and chlorides respectively with conc. H 2 SO 4 .
(b) From Caliche : The mother liquor left after crystallisation of
CaF2  H 2 SO 4   CaSO 4  2 HF
Heat
NaNO 3 is treated with NaHSO 3 to liberate I 2 from NaIO3 .
2 NaCl  H 2 SO 4   Na 2 SO 4  2 HCl
Heat
2 NaIO3  5 NaHSO 3  3 NaHSO 4  2 Na 2 SO 4  H 2 O  I2
(ii) Preparation of HBr and HI :These are prepared by heating
In the laboratory, I 2 is prepared by heating a mixture of potassium bromides and iodides respectively with phosphoric acid
iodide and MnO2 with conc. H 2 SO 4 .
3 NaBr  H 3 PO4   Na 3 PO4  3 HBr
Heat

2 KI  MnO2  3 H 2 SO 4  2 KHSO 4  MnSO 4  H 2 O  I2

3 NaI  H 3 PO4   Na 3 PO4  3 HI
Heat

(iii) Properties : It is a dark violet shining solid which sublimes on

heating. It is least soluble in water. However, its solubility can be increased Conc. H 2 SO 4 cannot be used for the preparation of HBr and
by adding 10% KI solution due to the formation of I 3 complex ion in HI because these being strong reducing agents reduced H 2 SO 4 to
 SO 2 and are themselves oxidised to Br2 and I 2 respectively.
which I ion acts as a lewis base (ligand) and I 2 molecule behaves as a
lewise acid (central atom) which accommodates lone pair of electrons
2 HBr  H 2 SO 4  SO 2  Br2  2 H 2 O
donated by I  ion in the antibonding sigma p z molecular orbital.
(6) Bleaching powder is obtained by the action of chlorine on dry
I2  I   I3 (complex ion) slaked lime (Hasenclever method).

The aqueous solution containing I 3 complex ion has a brown Ca(OH )2  Cl 2   CaOCl 2  H 2 O
313 K

colour. It is soluble in many organic solvents. Its solution in CS 2 ,CHCl 3 An aqueous solution of bleaching powder gives tests for Cl  and

and CCl 4 is violet while in strong donor solvents like alcohols, ethers and ClO ions. On long standing, it undergoes auto-oxidation to form calcium
amines is brown. chlorate. However, when heated, in presence of CoCl 2 , it gives O 2
 6 CaOCl 2  5 CaCl 2  Ca(ClO3 )2 Properties :
(1) Atomic radii : The atomic radii of noble gases increases on
2CaOCl 2   2CaCl 2  O 2
CoCl 2
moving down the group and their atomic radii correspond to the vander
It is used for bleaching cotton, wood pulp etc., as a disinfectant, as Waal’s radii.
a germicide for sterilization of drinking water, in the manufacture of (2) Boiling points : The m.pt. and b.pt. increases from He to Rn,
chloroform and for making wood unshrinkable. because of increase in magnitude of vander Waal’s forces.
Noble Gases (3) Polarizabiltiy : The polarizability increases down the group, He
< Ne < Ar < Kr < Xe
Helium is the first member of group 18 or zero of the periodic
(4) Ionisation energy and electron affinity : Noble gases have stable
table. It consists of six elements helium (He), Neon (Ne), argon (Ar),
krypton (Kr), xenon (Xe) and radon (Rn). Zero group occupies the ns 2np 6 fully filled electronic configuration, so these have no tendency to
intermediate position between the elements of VIIA (17th) and IA (1st) add or lose electron. Therefore, ionisation energy of noble gases is very high.
groups. These are collectively called as inactive gases or inert gases. On the other hand their electron affinity is zero.
However, these are now called noble gases as some compounds of these (5) Heat of vaporisation : They posses very low values of heat of
gases have been obtained under certain specific conditions. vapourisation, because of presence of very weak vander Waal’s forces of
(1) Electronic configuration attraction between their monoatomic molecules. However the value of heat
of vaporisation increases with atomic number down the group and this
Electronic configuration
Elements Discovery shows that there is an increasing polarizability of the larger electronic
( ns 2 np 6 ) clouds of the elements with higher atomic number.
2 He Lockyer and 1s 2 (6) Solubility in water : They are slightly soluble in water. Their
Janssen (1868) solubility generally increases with the increase in atomic number down the
10 Ne Ramsay 1s 2 , 2 s 2 2 p 6 group.

Rayleigh and (7) Adsorption by charcoal : All of them except helium are adsorbed
18 Ar 1 s 2 , 2 s 2 2 p 6 ,3 s 2 3 p 6
Ramsay (1894) by cocount charcoal at low temperature. The extent of adsorption increases
Ramsay and down the group.
36 Kr 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 ,
Travers (1898) (8) Characteristic spectra : All of them give characteristic spectra,
4 s2 4 p6 by which they can be identified.
Xe Ramsay and (9) Liquification of gases : It is difficult to liquify noble gases as
54 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 ,
Travers (1898) their atoms are held by weak vander Waal’s forces. Ease of liquification
4 s 2 4 p 6 4 d 10 4 f 14 , 5 s 2 5 p 6 increases down the group from He to Rn. Helium has the lowest boiling
Dorn (1900) point (4.18 K) of any known substance. The ease of liquification increases
86 Rn 1s 2 ,2 s 2 2 p 6 ,3 s 2 3 p 6 3d 10 , down the group due to increase in intermolecular forces.
4 s 2 4 p 6 4 d 10 4 f 14 , The elements helium (He), neon (Ne), argon (Ar), krypton (Kr),
2 6 10
5 s 5 p 5 d ,6 s 6 p 2 6 xenon (Xe) and radon (Rn), constitute zero group of the periodic table.
These are gases at ordinary temperature and do not have chemical reactivity
(2) Occurrence : Due to the inert nature of noble gases, they always and therefore, these are called inert gases.
occur in the free state. Except radon, all these gases are present in Compounds of Xenon
atmosphere in the atomic state.
In 1962, N. Bartlett noticed that PtF is a powerful oxidizing agent
Element
6

He Ne Ar Kr Xe which combines with molecular oxygen to form ionic compound, dioxygenyl

Abundance
5.2  10 4 1.8  10 3 9.3  10 1 1.4  10 3 8.7  10 6 hexafluoro platinate (v) O 2 [PtF6 ] , O2(g)  PtF6(g)  O2 [PtF6 ] ,This
(Volume %)
indicates that PtF has oxidized O to O 2 . Now, oxygen and xenon have
6 2

He is also present in natural gas to the extent of 2 to 7%. some similarities,

(3) Isolation (i) The first ionization energy of Xe gas (1170kJ mol -1 ) is fairly
(i) Helium : It is commercially obtained from natural gas. The
close to that of oxygen (1166kJ mol 1 ) .
natural gas contains hydrocarbons (methane etc.), CO , H S and He as the 2 2

main constituents. (ii) The molecular diameter of oxygen and atomic radius of Xe are
The natural gas is compressed to about 100 atm and cooled to 73K. similar (4Å)
He remains unliquefied while other gases get liquefied. About 99% pure He On this assumption, Bartlett reacted Xenon and PtF6 in gas phase
is prepared by this method. and a orange yellow solid of the composition XePtF was obtained,6

(ii) Argon, Neon, Krypton and Xenon : These gases are prepared by Xe (g)  PtF6(g)  Xe  [PtF6 ](s) .
the fractionation distillation of liquid air. Fractional distillation of air gives Orange yellow
O , N and mixture of noble gases. The individual gases may be obtained by
2 2

adsorption of air on coconut charcoal. The charcoal adsorbs different gases at Some important stable compounds of Xe are,
different temperatures and can be collected. +2 +4 +6
(iii) Radon : It can be obtained by radio active disintegration of XeF2 XeF4 , XeOF2 XeF6 , XeOF4 , XeO 3
radium (226), Ra 88
226
 Rn + 2  4 .
86
222
 Fluorides : Xenon forms three compounds with fluorine. These are : Properties : It is colourless, crystalline solid, highly soluble in
Xenon difluoride (XeF ), Xenon tetrafluoride (XeF ) and Xenon hexafluoride
2 4
anhydrous HF giving solution which is a good conductor of electricity,
(XeF ). 6
HF  XeF6  XeF5  HF2 .
(1) Xenon difluoride (XeF ) is formed when a mixture of Xenon and
It is the most powerful fluorinating agent and reacts with H to give
2

fluorine in the ratio 1 : 3 by volume is passed through a nickel tube at 673 2

Xe and HF. Partial hydrolysis of XeF yields XeOF an complete hydrolysis

K, Xe  Fe  XeF2 Ni, 673K 6 4

yields xenon trioxide, XeO . 3

Structure : XeF has trigonal bipyramid geometry due to sp 3 d - XeF6  H 2 O  XeOF4  2 HF

2

hybridization of Xe. Three equatorial positions are occupied by lone pairs of XeF6  3 H 2 O  XeO 3  6 HF
electrons giving a linear shape to the molecule. It forms addition compounds with alkali metal fluorides (except LiF)
Properties : XeF is a colourless crystalline solid, reacts with H 2 to
2
of the formula XeF . MF where M represents the alkali metal.
6

give Xe and HF. It is hydrolysed completely by water, Oxides : Xenon forms two oxides such as xenon trioxide (XeO ) and 3

xenon tetraoxide (XeO ).

2 XeF2  2 H 2 O  2 Xe  O2  4 HF .
4

(1) Xenon trioxide (XeO ) is prepared by complete hydrolysis of XeF

3 4

It also forms addition compounds with reactive pentafluorides like and XeF 6

SbF , TaF etc.

5 5
6 XeF4  12 H 2  2 XeO 3  4 Xe  3O2  24 HF
XeF2  2SbF5  XeF2 . 2SbF5 XeF6  3 H 2 O  XeO 3  6 HF
It is a mild fluorinating agent and hence reacts with benzene to give Structure : XeO has tetrahedral geometry due to sp 3 hybridization
3

fluorobenzene. of Xe. One of the hybrid orbitals contains a lone pair of electrons giving a
(2) Xenon tetrafluoride (XeF ) is prepared by heating a mixture of
4
trigonal pyramidal shape. The molecule has three Xe = O double bonds
xenon and fluorine in the ratio 1 : 5 in a nickel vessel at 673 K and then containing p  d overlapping.
suddenly cooling it in acetone. XeF4 is also formed when an electric Properties : It is a colourless solid, highly explosive and powerful
discharge is passed through a mixture of xenon and excess of fluorine, oxidizing agent.
Xe  2 F2   XeF4
Ni, 673K (2) Xenon tetraoxide (XeO ) is prepared by the action of conc. H SO
4 2 4

on sodium or barium xenate (Na 4 XeO 6 ; Ba2 XeO 6 ) at room

Structure : XeF4 has square planar shape due to sp 3 d 2
temperature,
hybridization of Xe giving octahedral geometry with two trans positions Na 4 XeO 6  2 H 2 SO 4  XeO 4  2 Na 2 SO 4 2 H 2 O
occupied by lone pairs of electrons.
Ba2 XeO 6  2 H 2 SO 4  XeO 4  2 BaSO4  2 H 2 O
F F
. . XeO is purified by vacuum sublimation at 195 K.
4

Xe Structure : XeO has tetrahedral structure due to sp 3 hybridization

  4

F F of Xe. There are four Xe–O double bonds containing p  d

Properties : XeF4 is a colourless, crystalline solid, soluble in overlapping.
anhydrous HF, reacts with H 2 to form Xe and HF and reacts with water Properties : It is quite unstable gas and decomposes to xenon and
to give highly explosive solid, XeO 3 . (complete hydrolysis), oxygen, XeO 4  Xe  2O2 .
6 XeF4  12 H 2 O  4 Xe  2 XeO 3  24 HF  3O2 Oxyfluorides : Xenon forms three types of oxy fluorides such as
Partial hydrolysis yields XeOF , xenon oxydifluoride (XeOF ), xenon oxytetrafluoride XeOF4 and xenon
2
2

dioxydifluoride (XeO F ).
XeF4  H 2 O  XeOF2  2 HF
193K 2 2

(1) Xenon oxydifluoride (XeOF ) is formed by partial hydrolysis of

2

It also forms addition compounds with SbF , 5 XeF at 193 K,

4

XeF4  SbF5  [ XeF3 ] [SbF6 ] .

XeF4  H 2 O   XeOF2  2 HF .
193 K

It also acts as a strong fluorinating agent.

(3) Xenon hexafluoride (XeF ) is prepared by heating a mixture of Structure : XeOF has trigonal bipyramid geometry due to sp 3 d-
2
6

xenon and fluorine in the ratio 1 : 20 at 473—523K under a pressure of 50 hybridization of Xe. Two equatorial positions are occupied by lone pairs of
atmospheres. electrons giving a T-shape to the molecule. There is one Xe–O double bond
473 523 K , 50 atm. containing p  d overlapping.
Xe  3 F2   XeF6
(2) Xenon oxytetrafluoride (XeOF ) is prepared by partial hydrolysis of
Structure : XeF has pentagonal bipyramid geometry due to sp d 3 3
4

hybridization. One trans position is occupied by a lone pair giving a XeF ; XeF6  H 2 O  XeOF4  2 HF . It can also be prepared by the
6

distorted octahedral shape. reaction of SiO with XeF ,

2 6

2 XeF6  SiO2  2 XeOF4  SiF4 .

F
F F
F Structure : XeOF has octahedral geometry due to sp 3 d 2 -
4

Xe
.. hybridization of Xe. One trans position is occupied by a lone pair giving
F F pyramid shape to the molecule. There is one Xe–O double bond containing
p  d overlapping.
 Properties : It is a colourless volatile liquid which melts at 227 K. It by sodium chloride while it is retard by borax or alum. Addition
reacts with water to give XeO F and XeO , 2 2 3 of alum to plaster of paris makes the setting very hard. The
XeOF4  H 2 O  XeO 2  2 HF , mixture is known as keen’s cement.
 B C (boron carbide) is one of the hardest known artificial
XeO 2 F2  H 2 O  XeO 3  2 HF .
4 3

substance and is called norbia.

It is reduced by H to Xe, 2
 Bitter almonds contain HCN in free state. It is produced by the
XeOF4  3 H 2  Xe  H 2 O  4 HF action of water on amygadatin (present in bitter almonds) in the
presence of enzyme emulsion (also present in bitter almonds).
(3) Xenon dioxydifluoride (XeO F ) is formed by partial hydrolysis of

2 2

XeOF or XeF
4 6
Industrial lubricant oildag is a suspension of graphite in oil and
colloidal solution of graphite is called aquadag.
XeOF4  H 2 O  XeO 2 F2  2 HF
 Broken glass pieces added during glass making is known as
XeF6  2 H 2 O  XeO 2 F2  4 HF cullet.
It can also be prepared by mixing XeO and XeOF at low 3 4

temperature (195K). The product is purified by fractional distillation,

XeO 3  XeOF4   2 XeO 2 F2
195 K

Structure : XeO F has trigonal bipyramid geometry due to sp 3 d -

2 2

hybridization of Xe. One equatorial position is occupied by a lone pair of

electrons giving a see-saw structure (shape) to the molecule. There are two
Xe–O double bonds containing p  d overlapping.
Properties : It is a colourless solid which melts at 303K. It is easily
hydrolysed to give XeO 3

XeO 2 F2  H 2 O  XeO 3  2 HF
Uses of noble gases
(1) He is used for filling of balloons and air ships because of its non-
inflammability and high power (which is 92.6% to that of hydrogen).
(2) Oxygen-helium (1 : 4) mixture is used for treatment of asthma
and for artificial respiration in deep sea diving because unlike nitrogen,
helium is not soluble in blood even under high pressure.
(3) Helium is also used for creating inert atmosphere in chemical
reactions.
(4) Liquid helium is used as a cryogenic fluid to produce and
maintain extremely low temperatures for carrying out researches and as a
coolant in atomic reactors and super conducting magnets.
(5) It is also used in low temperature gas thermometry and as a
shield gas for arc welding.
(6) Argon is used for creating inert atmosphere in chemical
reactions, welding and metallurgical operations and for filling in
incandescent and fluorescent lamps. It is also used in filling Geiger-Counter
tubes and thermionic tubes.
(7) Krypton and Xenon are also used in gas filled lamps. A mixture
of Krypton and Xenon is also used in some flash tubes for high speed
photography.
(8) Radon is used in radioactive research and therapeutics and in
the non-surgical treatment of cancer and other malignant growths.

 Among all the alkalimetals Li is the strongest and Na is the

weakest reducing agent.
 Lindlar’s catalyst is Pd poisoned with BaSO in quinoline.
4

 Keen’s cement : The setting of plaster of paris may be catalysed