7
Chapter
THE P-BLOCK ELEMENTS
NCERT CRUX
Introduction
 Group 13 to 18 of the periodic table of elements
constitute the p–block. The p–block contains metals,
metalloids as well as non–metals. Here, in this chapter
we will study only four groups i.e. group 15 to
group 18.
Group 15 Elements:
The Nitrogen Family
Group 15 includes nitrogen phosphorus, arsenic, antimony
and bismuth. As we go down the group, there is a shift
from non-metallic to metallic through metalloidic character.
Nitrogen and phosphorus are non-metal, arsenic and antimony
metalloid and bismuth is a typical metal.
Electronic Configuration
 The general valence shell electronic configuration of
these elements is ns2 np3.
Atomic and physical properties
 Ionisation enthalpy: N > P > As > Sb > Bi
(IA. of 15group >>> 14group → as half filled)
 Electronegativity: N > P > As > Sb = Bi
 Covalent radius: Bi > Sb > As > P > N (Small increase
from Sb to Bi as fully filled d & f orbitals)
 Melting point: As > Sb > Bi > P > N
 Boiling Point: Sb > Bi > As > P > N
 Density: Bi > Sb > As > P > N
 Basicity also decreases in the order:
NH3 > PH3 > AsH3 > SbH3 > BiH3.
 Boiling point: BiH3 > SbH3 > NH3 > AsH3 > PH3
 Exceptionally, B.P. of NH3 >> PH3 is due to H-bonding
in NH3.
Chemical Properties
Oxidation states
 VA group elements exhibit -3, +3 and + 5 oxidation
numbers.
Nitrogen is restricted to a maximum covalency of 4 since
only four (one s and three p) orbitals are available for
bonding. The heavier elements have vacant d orbitals in the
outermost shell which can be used for bonding (covalency)
and hence , expand their covalence as in PF6–.
The stability of -3 oxidation state decrease from N to Bi due to
decrease of non-metallic nature.
 The stability of +5 oxidation state decreases and +3
oxidation state increases down the group from N to Bi
due to inert pair effect.
 In the case of nitrogen, all oxidation states from +1 to +4
tend to disproportionate in acid solution. For example,
3HNO2 → HNO3 + H2O + 2NO
The single N–N bond is weaker than the single P–P bond
because of high interelectronic repulsion of the non–
bonding electrons, owing to the small bond length. As
a result the catenation tendency is weaker in nitrogen.
(i) Reactivity towards hydrogen
● Trends in some properties of hydrides of VA
group elements:
Š M.P’s PH3 < AsH3 < SbH3 < NH3
Š B.P’s PH3 < AsH3 < NH3 < SbH3
Š B.L’s NH3 < PH3 < AsH3 < SbH3
Š B.E’s NH3 > PH3 > SbH3 > AsH3
Š B.A’s NH3 > PH3 > AsH3 > SbH3
 2 CUET 2023-24 PW
Š Reducing power: NH3 < PH3 < AsH3 < SbH3
<BiH3.
Š Basic Nature: NH3 > PH3 > AsH3 > SbH3
>BiH3.
Š Stability: NH3>>PH3>AsH3> SbH3>> BiH3.
(ii) Reactivity toward oxygen
● As oxidation number of the element increases,
acidic nature of its oxides increases.
● As the atomic number increases acidic nature of
oxides decreases.
● Acidic nature decreases or basic nature increases
from N2O5 to Sb4O10
● From top to bottom Oxidising nature of trioxides
decreases.
(iii) Reactivity toward halogen
● Pentahalides use the sp3d hybridised orbitals of the
central atom.
● Bi cannot form stable pentahalides due to inert
pair effect.
● The extent of hydrolysis decreases from NX3 to
BiX3.
● Pentahalides are more covalent than trihalides. All
the trihalides of these elements except those of
nitrogen are stable. (NF3 is stable)
Dinitrogen (N2)
Preparation
 By heating ammonium dichromate:
∆
(NH4)2Cr2O7 
→ N2 + 4H2O + Cr2O3
∆
 Very pure nitrogen: Ba(N3)2  → Ba + 3N2
Sodium azide also gives N2 on heating.
Ammonia
Preparation
 NH2CONH2 + 2H2O → (NH4)2CO3 ∆ 2NH3 + H2O
 + CO2
 2 NH4Cl + Ca (OH)2 → 2NH3 + 2H2O + CaCl2
 (NH4)2 SO4 + 2NaOH → 2NH3 + 2H2O + Na2SO4
 On a large scale, ammonia is manufactured by Haber’s
process.
N2 (g) + 3H2(g) → 2NH3(g) ; Δf H = –46.1 kJ mol–1
Properties
Physical properties
 In the solid and liquid states, it is associated through
hydrogen bonds and that accounts for its higher melting
and boiling points than expected on the basis of its
molecular mass.
 It has three bond pairs and one lone pair of electrons as
shown in the structure.
Fig.: Ammonia
 Its aqueous solution is weakly basic due to the formation
of OH– ions.
NH3(g) + H2O (l)  NH4+ (aq) + OH–(aq)
Chemical properties
 It forms ammonium salts with acids, e.g., NH4Cl,
(NH4)2 SO4, etc. As a weak base, it precipitates the
hydroxides of many metals from their salt solutions.
For example,
 2FeCl3(aq) + 3NH4OH(aq) →
Fe2O3.xH2O(s) + 3NH4Cl (aq)
           (brown ppt)
 NH3 + Cu2+(aq) → [Cu(NH3)4]2+
    (deep blue)
 Key Note
Test of ammonia/ammonium salts
When NH3 gas is passed into the colourless solution of
Nessler’s reagent a brown precipitate or coloration is
formed. This is a test for NH3 gas.
2K2HgI4 + 3KOH + NH3→ H2N·HgO·HgI ↓+ 7KI + 2H2O
(brown)
Uses
 Liquid ammonia is used as a refrigerant.
Oxides of Nitrogen
All these oxides of nitrogen exhibit pπ-pπ multiple bonding
between nitrogen and oxygen.
The p-Block Elements 3

Table: Oxides of nitrogen

Oxidation state Physical appearance

Name Formula Common methods of preparation
of nitrogen and chemical nature
Dinitrogen oxide Heat
N2O +1 NH 4 NO3  → N 2 O + 2H 2 O Colourless gas, neutral
[Nitrogen (I) oxide]
2NaNO2 + 2FeSO4 + 3H2SO4
Nitrogen monoxide
NO +2        ↓ Colourless gas, neutral
[Nitrogen (II) oxide] Fe2(SO4)3 + 2NaHSO4 + 2H2O + 2NO
Dinitrogen trioxide
N2O3 +3 250K
2 NO + N 2 O 4  → 2 N 2 O3 Blue solid, acidic
[Nitrogen (III)oxide]
Nitrogen dioxide
NO2 +4 2 Pb ( NO3 )2 
673K
→ 4 NO 2 + 2PbO + O 2 Brown gas, acidic
[Nitrogen (IV) oxide]
Dinitrogen tetroxide cool Colourless solid/liquid,
N2O4 +4 
2NO 2  
 N 2 O4
[Nitrogen (IV) oxide] Heat acidic
Dinitrogen pentoxide
N2O5 +5 4HNO3 + P4O10 → 4 HPO3 + 2 N2O5 Colourless solid, acidic
[Nitrogen (V) oxide]

 Key Note
Phosphorus Allotropic Forms
In solid state N2O5 exists as [NO2+], [NO3–] ions. It is
known as in solid Nitrosonium Nitrate in solid. Allotropes of phosphorus

White Red Black

Preparation and uses of Nitric acid (HNO3)
Electric arc → Poisonous → Non - Poisonous → Non - Poisonous
 N 2 + O 2  → 2NO; ∆H = +180.7kJ
→ Insoluble in → Insoluble in → 2 forms
 NO is oxidised to NO2 by atmospheric oxygen.
water but soluble water as well as in
2NO + O2 → 2NO2 in CS2 CS2
 NO2 is made to react with further air and water to form
→ Glows in dark → Less reactive α-Black :
HNO3
(Chemilumines - than white Phosphorus has
4 NO2 + O2 + 2H2O → 4HNO3 cence) phosphorus and opaque monoclinic
Properties not glow in dark. or rhombohedral
crystal and can be
 Concentrated nitric acid is a strong oxidising agent and
sublimed in air
attacks most metals except noble metals such as gold
and platinum. β-Black :
Phosphorus has
3Cu + 8 HNO3 (dilute) → 3 Cu(NO3)2 + 2NO + 4H2O layered structure.
Cu + 4 HNO3 (conc.) → Cu(NO3)2 + 2NO2 + 2H2O
 Reactivity of the various allotropic forms of phosphorus
 Zinc reacts with dilute nitric acid to give N2O and towards other substances decreases in the order:
with concentrated acid to give NO2

White > red > black, the last one being almost inert i.e.
4Zn + 10HNO3 (dilute) → 4Zn(NO3)2 + 5H2O + N2O most stable.
Zn + 4HNO3 (conc.) → Zn(NO3)2 + 2H2O + 2NO2

 Key Note
Oxides of Phosphorus

Brown ring test (a) Phosphorus trioxide (P2O3)

NO3– + 3Fe2+ + 4H+ → NO + 3Fe3+ + 2H2O It is dimeric and has formula P4O6
[Fe(H2O)6]2+ + NO → [Fe(H2O)5(NO)]2+ + H2O Preparation
            (brown) P4 + 3O2 (limited supply of oxygen) → P4O6
 4 CUET 2023-24 PW

Properties
 It dissolves in cold water to form phosphorus acid and
in hot water liberating PH3.
 P4O6 + 6H2O(cold) → 4H3PO3
P4O6 + 6H2O(hot) → 3H3PO4 + PH3
Fig.: Phosphorus Trichloride
(b) Phosphorus pentaoxide (P2O5)
Phosphorus Pentachloride
It is dimeric and has the formula P4O10. There are 6 Preparation
bridging oxygen atom present in P4O10
P4 + 10Cl2 → 4PCl5
Properties
Preparation
 It hydrolysis to POCl3 and finally gets converted to
It is obtained by burning phosphorus in excess air. phosphoric acid
P4 + 5O2 → P4O10 PCl5 + H2O → POCl3 + 2HCl
Properties PCl3 + 3H2O → H3PO4 + 3HCl
 When heated it sublimes but decomposes on stronger
 It is a white powder, acidic in nature and is the anhydride
heating
of orthophosphoric acid.
Heat
PCl5  → PCl3 + Cl2

Compounds of Phosphorus

Phosphine Preparation
Ca3P2 + 6 H2O → 3 Ca(OH)2 + 2PH3
Ca3P2 + 6HCl → 3 CaCl2 + 2PH3
In the laboratory
P4 + 3 NaOH + 3 H2O → PH3 + 3NaH2PO2 Fig.: Phosphorus Pentachloride
               (sodium hypophosphite)
In the solid state PCl5 exists as an ionic solid. [PCl4]+
 PH4I + KOH → KI + H2O + PH3 [PCl6]– in which the cation, [PCl4]+ is tetrahedral and the
Properties anion, [PCl6]– octahedral.
 Phosphine on heating at 150ºC burns forming H3PO4
PH3 + 2O2 → H3PO4
Oxoacids of Phosphorus
 Phosphine is weakly basic and like ammonia, gives
phosphonium compounds with acids e.g., Important features about oxoacids of phosphorous
PH3 + HBr → PH4Br  In all these oxoacids, phosphorous is tetrahedrally
Phosphorus Halides surrounded by atoms.

Phsophorus forms two types of halides:  In all these oxoacids, at least one OH group is linked
to the phosphorous atoms. The hydrogen atoms in
PX3 [X = F , Cl , Br, I] and PX5 [X = F, Cl, Br] OH groups are ionisable, and are responsible for the
Phosphorus Trichloride acidic nature.
Preparation  All oxoacids contain at least one P=O and one P–OH
bond.
 P4 + 6Cl2 → 4PCl3
 The phosphorus series of acids contains P-H bonds
Properties
Hypo Phosphorus acid (H3PO2)
 It is a colourless oily liquid and hydrolysis in the
presence of moisture. H3PO2 in monobasic acid and a very strong reducing
PCl3 + 3H2O → H3PO3 + 3HCl agent is basic solutions and it is oxidised to H3PO3
The p-Block Elements 5

Table: Oxoacids of Phosphorus  Atomic radius increases from O to Te.

Oxi- Charac-  Ionisation energy and Electronegativity decreases
dation terstic from O to Po.
Name Formula Structure
num- bonds &  Density increases from oxygen to polonium.
ber of P their No
 Melting points and boiling points changes irregularly as
Meta Phos-
One – follows. O < S < Se < Te > Po.
phorus acid
HPO2 HO – P = O +3 P – OH
(Monobasic The large difference in the melting point of Oxygen
One P = O
acid)
and Sulphur is due to a change from diatomic O2 to
Hypo Phos- One – octaatomic S8 which increases magnitude of Van der
phorus acid P – OH Waal’s forces.
H3PO2 +1
(Monobasic Two O – H
acid) One P = O Electron affinity values decrease from S to Te. Electron affinity
of O < S due to small size of Oxygen atom.
Phospho-
Two P – OH Order of electron affinity: S > Se > Te > Po > O (E.A1)
rous acid H3PO3
+3 One P – H
(Dibasic P2O3.3H2O Electronic configuration
One P = O
acid)
 They have valence shell electronic configuration ns2np4
Ortho Phos- Catenation Capacity
H3PO4 Three
phoric acid
or +5 P – OH
(Tribasic  Oxygen and Sulphur show catenation tendency.
P2O5.3H2O One P = O
acid) Allotropy
Meta Phos-  All VI A group elements exhibit allotropism except Te
phoric acid HPO3 or One – POH Allotropes of Sulphur
+5
(Monobasic P2O5.H2O Two P = O
acid) α-Sulphur or Rhombic sulphur, β-Sulphur or monoclinic
sulphur or prismatic sulphur, γ- Monoclinic sulphur and
Hypo Phos- Four χ-Sulphur or plastic sulphur.
phoric acid P – OH
(Tetrabasic
H4P2O6 +4
Two P = O Allotropes of Oxygen
acid) One P – P  Oxygen occurs in two non metallic forms:-
Four (a) Oxygen (O2) (b) Ozone (O3)
Pyrophos-
H4P2O7 or P – OH
phoric acid
(Tetrabasic
+5 Two P = O Chemical Properties
P2O5.2H2O One P – O
acid) Oxidation States
–P
Peroxy
Two P – OH Oxygen shows positive oxidation states in fluorides.
Phosphoric
One P = O Oxidation state of oxygen in O2F2 is +1 and in OF2 is +2.
acid H3PO5 +5
One P – O
(Tribasic
– OH
acid)  The Oxidation state of oxygen in a peroxide is -1 and in
P-H bonds are responsible for reducing properties of the 1
a super oxide is − .
acids. Phosphoric series of acids do not have P–H bonds. 2
 Oxygen cannot exhibit oxidation number beyond +2,
due to absence of vacant d-orbitals.
Group 16th Elements:
The Oxygen Family Anomalous Behaviour of Oxygen
(i) Hydrides-Reactivity with hydrogen
Introduction
● All these hydrides are covalent compounds.
 Oxygen, sulphur, selenium, tellurium and polonium are
● The ease of formation and thermal stability
the elements of VIA group or 16 vertical column of the
periodic table. decrease from H2O to H2Po (as M-H bond energy
decreases)
Physical properties
● The thermal stability Order:-
 As Atomic weight increases, the formation of multiple
bond between identical atoms decreases. H2O > H2S > H2Se > H2Te
 6 CUET 2023-24 PW

● M-H bond length in the hydrides increases from

H2O to H2Po. Sulphur
● The acidic strength increases from H2O to H2Te.
Order: H2O < H2S < H2Se < H2Te Crystalline Amorphous
● The reducing property increases from H2O to Rhombic sulphur (α-S) most Milk of sulphur
H2Po. stable form Plastic sulphur (γ-S)
● Covalent character increases from H2O to H2Te. Monoclinic sulphur (β-S) Colloidal sulphur
Order: H2O < H2S < H2Se < H2Te
> 95.6° C
 →β − S H2S + 2HNO3 → S + 2NO2
● The bond angle decreases from H2O to H2Po. α − S ← 
< 95° ,6° C + 2H2O
(H2O – 104°28’; H2S – 92°30’)
H2Se – 90° ; H2Te – 90°; H2Po – 90º) 95.6°C = transition temp.
both are soluble in CS2 but
(ii) Reactivity with oxygen insoluble in water
● Order of acidic strength: SO2 > SeO2 > TeO2 and
SO 3> SeO3 > TeO3.  At elevated temperatures S2 is the dominant species and
● Trioxides are more acidic than dioxides. PoO2 is is paramagnetic like O2.
basic. Compounds of Sulphur
● SO3 is more acidic than SO2 Sulphur Dioxide (SO2)
(iii) Reactivity toward the halogens Preparation
● The stabilities of the halides decrease in the order  S(s) + O2(g) → SO2(g)
F > Cl > Br > I.
 SO32 – (aq) + 2H+(aq) → H2O(l) + SO2(g)
 4FeS2(s) + 11O2(g) → 2Fe2O3(s) + 8SO2(g)
Dioxygen (O2) Properties
SO2(g) + H2O(l)  H2SO3(aq)
Preparation  In it reaction with water and alkalies, the behaviour of
 By thermal decomposition of oxygen rich compounds. sulphur dioxide is very similar to that of carbon dioxide.
∆
KClO3  → 2KCl + 3O2 (laboratory method)  Bleaching action: SO2 + 2H2O → H2SO4 + 2H
H+
finely divided metals and MnO2 
coloured matter   colourless matter
 2H2O2(aq.) → 2H2O(l) + Air oxidation
O2(g)  Bleaching is through reduction but it is temporary. It
Use is a more powerful reducing agent in alkaline medium
 In welding and cutting oxy-hydrogen or oxy-acetylene than in acidic medium.
torch is used. Structure of SO2
 In SO2, sulphur atom is sp2 hybridised. It is an angular
Ozone (O3) molecule with a lone pair on ‘S’ atom
 SO2 molecule has two resonance structures.

Properties
Physical properties

 It is a pale blue gas which forms a blue liquid and one Fig.: Resonance structure of SO2
solidification forms violet black crystals. Uses of SO2
 O3 molecule is diamagnetic but O3– ion is paramagnetic
(1 unpaired e–)  Disinfectant and preservative
Chemical Properties Sulphur trioxide SO3

 As Oxidising agent : Due to the ease with which it  2SO2 + O2  2SO3

liberates atoms of nascent oxygen  H2SO4 → SO3 + H2O
(O3 → O2 + O ), it acts as a powerful oxidising agent.
 SO3 + conc. H2SO4 → H2S2O7 (oleum)
Ozone is a stronger oxidising agent in acidic medium.
 H2S2O7 + H2O → 2H2SO4
 O–O bond length decreases in order: H2O2 (1.48 Å) >
O3 (1.28 Å) > O2F2 (1.22 Å) > O2 (1.21 Å)  Fe 2 ( SO 4 )3 
∆
→ Fe 2 O3 + 3SO3
The p-Block Elements 7

Oxoacids of Sulphur  According to Le chatlier’s principle to favour forward

Sulphur forms a number of oxoacid such as H2SO3, H2S2O4, process the following conditions are to be maintained
H2S2O6(x = 2 to 5) H2SO4, H2S2O7, H2SO8, structures of some i.e., high pressure and low temperature.
important oxoacids are shown in figure.  A suitable catalyst is to be used to increase the rate of
formation of SO3
Physical Properties
 High boiling point and high viscosity of H2SO4 is due
to the fact that H2SO4 molecules are associated together
by H-bonding.

:

Fig.: H2SO4 Forms H bonding
Chemical Properties
 Strong affinity for water.
 Ability to act as oxidising agent
 It is very good dehydrating agent.
Fig.: Structures of some important oxoacids of sulphur
E.g., C12H22O11 + Conc. H2SO4 → 12C + 11H2O
Sodium Thiosulphate
 Hydrated sodium thiosulphate (Na2S2O3.5H2O) is
called hypo.
Fig.: Caro’s acid   Fig.: Marshall’s acid  When alkaline or neutral Na2SO3 solution is boiled with
“flowers of sulphur” gives hypo.
Sulphuric Acid (H2SO4)
Na2SO3 + S → Na2S2O3
Contact Process
(Solution) (excess) (hypo)
 The steps involved are :
2S2 O32 − + I 2 
→ S4 O62 − + 2I −
(i) Burning of sulphur (or) sulphide ores (like iron
pyrites) in air to get SO2  Na2S2O3 is also prepared by passing SO2 into sodium
S + O2 → SO2 sulphide solution
4FeS2 + 11O2 → 2Fe2O3 + 8SO2 2Na2S + 3SO2 → 2Na2S2O3 + S
(ii) Conversion of SO2 to SO3 catalytically Chemical Properties
V2O5
2SO 2 + O 2  → 2SO3  Hypo with a dilute solution of AgNO3 gives a white
∆
precipitate which changes to yellow, brown and finally
(iii) SO3 is absorbed in 98% H2SO4 to get oleum black due to the formation of Ag2S.
SO3 + H2SO4 → H2S2O7  With concentrated solution of hypo, AgNO3 gives no
oleum precipitate. This is because silver thiosulphate (a white
 Oleum is diluted with water to get sulphuric acid of ppt) formed in the reaction is easily soluble in excess
desired concentration of Hypo forming a complex, Na3[Ag(S2O3)2] (sodium
argentothiosulphate).
H2S2O7 + H2O → 2H2SO4
 The key step in the process is catalytic oxidation of SO2  Hypo removes excess chlorine in moist condition. So
with O2 to give SO3 in presence of catalyst hypo is used as an antichlor.
 The process is reversible Na2S2O3 + H2O + Cl2→ Na2SO4 + S + 2HCl
Catalyst


2SO 2(g) + O 2( g) ) 
 2SO3(g) ; ∆H =−189kJ Uses of Hypo
 Forward reaction is : Exothermic and Δn = –ve Hypo is used as a Fixing agent in photography
 8 CUET 2023-24 PW
Group 17 Elements:
The Halogen Family
 F, Cl, Br, I are commonly called as halogens.
Melting and Boiling Points
 The melting and boiling points increase gradually from
fluorine to iodine, due to increase in Van der waal’s
forces.
 The non-metallic nature decreases from fluorine to
iodine.
Ionisation Potential
 The Ionisation potentials decreases from fluorine to
iodine, due to the increase in atomic size.
Electron Affinity & Electro Negativity
 The electron affinity of fluorine is less than chlorine
though it is most electronegative. This is due to its small
size. Repulsions between newly added electron and the
electrons already present in its small 2p orbital are high.
 Electron affinity values of Halogens are in the order.
Cl > F > Br > I
Bond Dissociation Energy
 Among halogens the bond dissociation energy is
highest for chlorine
 Bond dissociation energies of halogens are in the order
Cl2 > Br2 > F2 > I2.
 According to Mulliken, the high bond dissociation
energies of Cl2, Br2 and I2 are due to multiple bonds
formed by d - p combinations or overlapping may be
possible.
 The low bond dissociation energy of F2 is due to absence
of d- p combination as it does not possess d-orbitals
Solubility
Halogens are soluble in water which follow the order
F2 > Cl2 > Br2 > I2
Chemical Properties
Oxidation States
 Fluorine always exhibits a fixed oxidation state of -1 in
its compounds because it is the most electro negative
element
 Chlorine, Bromine and Iodine show -1, +1, +3, +5 and
+7 oxidation states. Higher oxidation states are due to
the presence of vacant d-orbitals.
 The higher oxidation states of chlorine, bromine and
iodine are mainly observed when the halogens are in
combination with the small and highly electronegative
fluorine and oxygen atoms, e.g., in interhalogens, oxides
and oxoacids. The oxidation states of + 4 and +6 occur
in the oxides and oxoacids of chlorine and bromine.
 In ground state halogen atom contain one unpaired
electron and three lone pair of electrons. The shape of
XA type molecule is Linear.
(X = less electronegative halogen,
A = more electronegative halogen)
 No hybridisation takes place in XA type halides.
 The possible hybridisation of Cl, Br and I atoms in first
excited state is sp3d.
 In the first excited state halogen atom contain 3 unpaired
electrons and 2 lone pairs.
 The shape of XA3 type of molecules is T.
(X = Cl, Br, I)
 The possible hybridisation of Cl, Br and I in second
excited state is sp3d2.
 In the second excited state halogen atom contain 5
unpaired electrons and 1 lone pair of electrons.
 The shape of XA5 type of molecules is square pyramidal.
(X = Cl, Br, I)
 Cl, Br and I in their third excited state contain 7 unpaired
electrons and exhibit +7 oxidation state forming 7
bonds.
 The possible hybridisation in halogen atom in third
excited state is sp3d3.
 The shape of XA7 type of compounds given by halogens
is pentagonal bipyramid.
Oxidising Power
 As number of covalent bonds increases covalent nature
increases.
 Fluorine is the strongest oxidising agent even though
chlorine has maximum electron affinity.
Chemical Reactivity
Halogens are highly reactive elements they can react with
metals as well as non-metal and other substances. The order
of reactivity of Halogens is F2 > Cl2 > Br2 > I2
(i) Reaction with Water
● Chlorine reacts with water to form HCl and HOCl
Cl2 + H2O → HCl + HOCl
● Chlorine acts as a bleaching agent in the presence
of water or moisture due to formation of HOCl.
F2 + H2O → HF(aq) + O2(g)
Fluorine oxidises water into oxygen
The p-Block Elements 9

Anomalous behaviour of fluorine  Reaction with NaOH

 The anomalous behaviour of fluorine is due to its  2NaOH (cold & dilute) + Cl2 → NaCl + NaClO + H2O
small size, highest electronegativity, low F- F bond  6NaOH + 3Cl2 → 5NaCl + NaClO3 + 3H2O
dissociation enthalpy, and non-availability of d orbitals (hot & conc.)
in valence shell.  Reaction with dry slaked lime, Ca(OH)2: To give
 It forms only one oxoacid while other halogens form a bleaching powder.
number of oxoacids. 2 Ca(OH)2 + 2Cl2 → Ca(OCl)2 + CaCl2 + 2H2O
Hydrogen fluoride is liquid (b.p. 293 K) due to strong  The composition of bleaching powder is
hydrogen bonding. Other hydrogen halides are gases. Ca(OCl)2.CaCl2.Ca(OH)2.2H2O
 Oxidising & bleaching properties
(ii) Reactivity towards oxygen ( Oxides of halogens) Chlorine dissolves in water (Cl2 water is yellow) giving
● Fluorine forms two oxides OF2 and O2F2. HCl (colourless) and HOCl (colourless). Hypochlorous
● These oxides are essentially oxygen fluorides acid (HOCl) so formed, gives nascent oxygen which is
because of the higher electronegativity of fluorine responsible for oxidising and bleaching properties of
than oxygen. chlorine.
● The bromine oxides, Br2O, BrO2, BrO3 are the  It is a powerful bleaching agent; bleaching action is
least stable halogen oxides. due to oxidation.
(iii) Reaction with hydrogen (Hydrides or hydrogen Cl2 + H2O → 2HCl + O
halides) Coloured substance + O → Colourless substance
● All the halogens directly combine with hydrogen
to form hydrides. Oxoacids of Halogens
● The reactivity of halogens with hydrogen decreases
from F2 to I2.  Flourine forms only one oxoacid HOF known as fluoric
● The stability of the hydrides decreases from HF to (I) acid or hypofluorous acid.
HI due to decrease in their dissociation energies. All other forms oxy acids of the type HOX, HXO2,
The stability order of hydrogen halides is HXO3 and HXO4 as shown below.
HF > HCl > HBr > HI Oxoacids of Chlorine
● The order of acidic strengths of hydrogen Table: Oxoacid, Formula & Oxidation State (O.S)
HF < HCl < HBr < HI. The stability of halides Acid Formula O.S
decrease due to decrease of bond dissociation
Hypochlorous acid HClO or HOCl +1
energy.
Chlorous acid HClO2 +3
● The order of bond dissociation energy
Chloric acid HClO3 +5
HF > HCl > HBr > HI
Perchloric acid HClO4 +7
(iv) Reaction with metals
● The order of the ionic character of the halides  Cl – O bond length decreases from OCl– to ClO4–
MF > MCl > MBr > MI where M is a monovalent  Cl – O bond energy increases from OCl– to ClO4–
metal. Halides in higher oxidation state will be except for ClO3–
more covalent than the one in lower oxidation state. The order of acidic strength is
HClO < HClO2 < HClO3 < HClO4
Chlorine Interhalogen Compounds
Due to this difference in electronegativity the halogen atoms
combine with each other and give rise to the formation of
Preparation binary covalent compounds, which are called interhalogen
Deacon’s process compounds. These are of four types.
CuCl Preparation
 4 HCl + O2 
2
→ 2Cl2 + 2H2O
473K
Properties  Cl2 + F2 (equal volumes)  → 2ClF ;
573K
P4 + 6Cl2 → 4PCl3 ; S8 + 4Cl2 → 4S2Cl2  Cl2 + 3F2(excess) → 2ClF3 ;
 10 CUET 2023-24 PW

 I2 + Cl2 → 2ICl ;
(equimolar) Group 18 Elements:
 Diluted with water: Br2(g) + 3F2 → 2BrF3 Noble Gases
−78ºC
 F2 is diluted with N2: I2 + 3F2 → 2IF3
Helium, neon, argon, krypton, xenon and radon are known as
 F2 is taken in freon: Br2 + 5F2 (excess) → 2BrF5 noble gases. Their symbols are He, Ne, Ar, Kr, Xe and Rn.
Properties
Electronic Configuration
Gases : ClF, BrF, ClF3, IF7;
All noble gases have general electronic configuration ns2np6
Liquids : BrF3, BrF5 ; except helium which has 1s2.
Solids : ICl, IBr, IF3, ICl3.
Ionisation Enthalpy
 All interhalogens are covalent molecules and are
Due to stable electronic configuration these gases exhibit very
diamagnetic in nature since all the valence electrons
high ionisation enthalpy.
present as bonding or non-bonding electrons are paired.
Atomic Radii
Interhalogen compounds are more reactive than the Atomic radii increases down the group with increase in atomic
parent halogens but less reactive than F2. number.
Electron Gain Enthalpy
Table: Some properties of inter halogen compound
Since noble gases have stable electronic configurations, they
Type Formula Physical state and colour Structure have no tendency to accept the electron and therefore, have
larger positive values of electron gain enthalpy.
XX′1 ClF Colourless gas –
Chemical Properties of Noble Gases
BrF Pale brown gas –
In general, noble gases are least reactive. Their inertness to
IF Detected spectroscopically – chemical reactivity is attributed to the following reasons :

BrCl gas –  They have high ionisation enthalpy and more positive
electron gain enthalpy.
Ruby red solid (a – form)
ICl – Compounds of Xenon
Brown red solid (b – form)
(a) Xenon–Fluorine Compounds
IBr Black solid –
Xenon difluoride
Bent 673K, 1 bar
XX′3 ClF3 Colorless gas  Xe(g) + F2 (g) → XeF2.(s)
T-shaped sealed nickel tube
(2 :1mixture)
The solution which have pungent smell due to XeF2 are
Bent
BrF3 Yellow green liquid powerful oxidizing agents.
T-shaped
 XeF2(aq) + 2H+ + 2e– → Xe + 2HF(aq); Eº = + 2.64 V
Bent
IF3 Yellow powder
T-shaped  XeF2 + H2 → 2HF + Xe
Bent  Hydrolysis is slow in water due to dissolution of XeF2
ICl3 Orange solid
T-shaped
in HF formed, but is rapid in basic solution.
Colourless gas but solid Square
IF5  2Xe F2(s) + 2H2O(l) → 2Xe(g) + 4HF(aq) + O2(g)
below 77 K Pyramidal
1
Square  XeF2 + 2OH– → Xe + O2 + 2F– + H2O
XX′5 BrF5 Colourless liquid 2
Pyramidal Xenon tetrafluoride

Square 873K, 7 bar

ClF5 Colourless liquid Xe(g) + 2F2 (g)  → XeF4(s)
pyramidal (1: 5 mixture) sealed nickel tube

Pentago-  XeF4 reacts violently with water, giving dangerously

XX′7 IF7 Colourless gas nal bipy- explosive XeO3.
ramidal 6XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
The p-Block Elements 11

Xenon hexafluoride (b) Xenon–Oxygen Compounds

573K,60–70bar  Hydrolysis of XeF4 and XeF6 with water gives XeO3.
 Xe(g) + 3F2 (g)  → XeF6(s)
(1: 20 mixture) sealed nickel tube  6 XeF4 + 12H2O → 4Xe + 2XeO3 + 24HF + 3O2
 XeF4 + O2F2 → XeF6 + O2  XeF6 + 3H2O → XeO3 + 6HF
 XeF6 reacts violently with water but slow hydrolysis Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4
with atmospheric moisture giving XeO3. and XeO2F2.
 XeF6 + 6H2O → XeO3 + 6HF (complete hydrolysis)  XeF6 + H2O → XeOF4 + 2HF
 XeF6 + 2H2O → XeO2F2 + 4HF  XeF6 + 2H2O → XeOF2 + 4HF

Table: Some compounds of Xenon.

Compounds Oxidation State No. of Lone No. of σ No. of π Hybridiza- Molecular Bond Angle
of Xenon of Xenon Pairs Bonds Bonds tion of Xenon Shape

XeF2 +2 3 2 – sp3d Linear 180°

XeF4 +4 2 4 – sp3d2 Square planar 90°

Distorted octa-
XeF6 +6 1 6 – sp3d3 144°, 90°
hedral

XeO3 +6 1 3 3 sp3 Pyramidal 103°

XeO4 +8 0 4 4 sp3 Tetrahedral 109°.28'

Square Pyra-
XeOF4 +6 1 5 1 sp3d2
midal

XeO2F2 +6 1 4 2 sp3d See-Saw

XeOF2 +4 2 3 1 sp3d T-shape