Group – 17 : (Halogens)

F 9 [He] 2s2 2p5

Cl 17 [Ne] 3s2 3p5

Br 35 [Ar] 3d10 4s2 4p5

Ι 53 [Kr] 3d10 5s2 5p5

At 85 [Xe] 4f14 5d10 6s2 6p5

Electronic Configuration - ns2 np5

Atomic and Ionic Radii

The Halogens have the smallest atomic radii in the respective periods due to
maximum effective nuclear charge.
 Down the group, atomic and Ionic radii increases.

e- gain enthalpy
Halogens have maximum negative e- gain enthalpy in the corresponding periods. This is due
to the fact that the atoms of these elements have only one e- less than the stable noble gas
configuration. Down the group, e- gain enthalpy becomes less negative. The negative e- gain
enthalpy of F is less than that of Cl. It is due to the small size of F atoms. As a result, these
are strong inter electronic repulsions in the small 2p orbitals of F and thus the increasing e -
doesnot experience much attraction.

All Halogens are coloured

This is due to the absorption of radiation in visible region which results in the
excitation of outer e- to higher s energy level. By absorbing different energy of
radiation, they display different colours.
F2 ⟶ yellow
Cl2 ⟶ greenish yellow
Bl2 ⟶ red
Ι2 ⟶ violet
The colour of Halogens is actually the colour of transmitted light.

Bond dissociation enthalpy :-

Cl2 > Br2 > F2 > Ι2
The F – F Bond dissociation enthalpy is less because F atom is very small and
hence the electron – electron repulsions b/w the lone pairs of e- are very large.
Solubility :-
F2 and Cl2 react with water Br2 and Ι2 are sparingly soluble in H2O but are soluble in
organic solvents.
 Ι2 dissolves in aqueous soln of KΙ due to the formation of complex KΙ3
KΙ + Ι2 ⟶ KΙ3 i.e. K+ [ Ι – Ι ⟵ Ι ]6
Oxidising Power :-
All the halogens have a strong tendency to accept an e- , they act as strong oxidising
agents.
 Oxidising power decreases from F2 to Ι2
F2 + 2X- ⟶ 2F- + X2
Cl2 + 2X- ⟶ 2Cl- + X2
Br2 + 2Ι- ⟶ 2Br- + Ι2
 A halogen of lower atomic no. oxidises halide ions of higher atomic number.

Note :- F is a stronger oxidising agent than Cl. This is due to

― low enthalpy of dissociation of F – F Bond.

― high hydration enthalpy of F-

 2F2 + 2H2O ⟶ 4H+ + 4F- + O2

X2 + H2O ⟶ HX + HOX [X = Cl, Br]
4Ι- + 4H+ + O2 ⟶ 2Ι2 + 2H2O

7 oxidises water to oxygen whereas Cl and Br react water to form corresponding

hydrohalic and hypohalous acids.
The rxn of Ι with H2O is non-spontaneous. In fact Ι- can be oxidised by oxygen in
acidic medium; just the reverse of the rxn observed with F
Oxidation state :-
All the halogens exhibit -1 0.5. However, Cl, Br and Ι exhibit +1, +3, +5 and +7 0.5
 F atom has no d orbitals in its valence shell and therefore cannot expand its
octet. Being the most e- eng. It exhibit only -1 0.5
Reactivity towards hydrogen:-
HF ⟶ Acidic strength of acids
HCl HF < HCl < HBr < HΙ
HBr
HΙ ⟶ Stability decrease down group due to decrease in H – X Bond
dissociation enthalpy.
 Reactivity towards oxygen :-
F forms two oxides : OF2 and O2F2
These oxides are essentially oxygen fluorides because of the higher e-neg of F
than O.

Oxides of flourine
OF2, O2F2
 Both are Fluorinating agents.
 O2F2 oxidises plutonium to PuF6 and the reaction is used in removing Pu from spent
nuclear fuel.
Pu + 3O2F2 → PuF6 + 3O2
Oxides of Chlorine
CI2O, CIO2, CI2O6 and CI2O7
They are highly reactive oxidising agents and tend to explode
→ CIO2 is used as a bleaching agent for paper pulp and textiles and in water treatment.
Oxides of Bromine
Br2O, BrO2, BrO3 are least stable and exist only at low temp.
Note : Stability of oxides formed by halogens
Ι > CI > Br [On the basis of kinetic and thermodynamic factors]
Oxides of Iodine
Ι2O4, Ι2O5, Ι2O7 are insoluble solids and decompose on heating.
→ Ι2O5 is a very good oxidising agent and is used in the estimation of CO.

3) Reactivity towards metals

Halogens react with metals to form metal halides.
e.g. MgBr2, SnCI4, SnCI2, UF4
→ Ionic character
MF > MCI > MBr > MI
→ SnCI4 is more covalent than SnCI2 higher the O.S of metal more will be the
covalent character.
4) Inter halogen compounds:
Halogens combine themselves to form inter halogen compounds of the type MX,
MX3, MX5, MX7 (Where M is large size halogen)

→ Interhalogen compounds are more reactive than halogen itself due to ineffective
overlapping of orbitals of different halogens.
e.g. of Interhalogen compounds CIF3, BrF5, IF7
→ CIF3 and BrF3 are used for the production of UF6 in the enrichment of 235U
U(S) + 3CIF3 (ℓ) → UF6(g) + 3CIF(g)

Structures of some interhalogen compounds

SP3d

BrF5

Square Pyramidal
SP3d2
Chlorine (CI2) (Greenish yellow colour)
(i) MnO2 + 4HCI ⟶ MnCI2 + CI2 + 2H2O
In place of HCI, a mixture of common salt and conc. H2SO4 can used.
4NaCI + 4H2SO4 + MnO2 ⟶ MnCI2 + 4NaHSO4
(ii) By the action of HCI on KMnO4
KMnO4 + HCI ⟶ KCI + MnCI2 +8H2O +5Cl2

Manufacture of CI2
𝐶𝑢𝐶𝐼2
(i) 4HCI + O2 → 2CI2 + 2H2O (Deacon process)
(ii) Electrolysis of brine solution
(Concentrated NaCI solution)
Properties
→ Pungent and suffocating odour
→ Heavier than air
→ Can be liquefied easily
→ Soluble in H2O
→ Reaction with metals
2AI + 3CI2 → 2AICI3
2Na + CI2 → 2NaCI
→ Reaction with non metals
P4 + 6CI2 → 4PCI3
S8 + 4CI2 → 4S2CI2
→ It has great affinity for hydrogen
H2 + CI2 → 2HCI
H2S + CI2 → 2HCI + 5
→ Reaction with NH3
8NH3 + 3CI2 → 6NH4CI + N2
(excess)
NH3 + 3CI2 → NCI3 + 3HCI
(excess) (explosive)
→ Reaction with alkalies
2NaOH + CI2 → NaCI + NaOCI + H2O
(Cold and dilute)
6NaOH + 3CI2 → 5NaCI + NaCIO3 + 3H2O
(hot and conc.)
→ with slaked lime
2Ca(OH)2 + 2CI2 → Ca(OCI)2 + CaCI2 + 2H2O
(Bleaching power)
Composition of Bleaching Power Ca(OCI)2, CaCI2, Ca(OH)2, 2H2O
→ Oxidising and bleaching properties of CI2
CI2 + H2O → HOCI + HCI
HCI + [O]
Bleaching of CI2 is permanent.
CI2 can oxidise
Fe+2 → Fe+3
SO32- → SO42-
SO2 → H2SO4

HCI
Lab Preparation
420 𝐾
NaCI + H2SO4 → NaHSO4 + HCI
(conc.)
823 𝐾
NaHSO4 + NaCI → Na2SO4 + HCI
⟶ HCI gas can be dried by passing through conc. H2SO4
Properties
⟶ Colourless
⟶ Pungent smelling gas
⟶ Easily liquefied
⟶ Extremely soluble in H2O and ionize as follows
HCI(g) + H2O(ℓ) ⟶ H3O+(aq.) + CI-(aq.) Ka = 107
High value of Ka. Therefore it is strong acid
⟶ It reacts with NH3 and gives white fumes of NH4CI
 NH3 + HCI ⟶ NH4CI

⟶ Aqua regia ⟶ HCI + HNO3

(conc) (conc)
3 : 1
It is used for dissolving noble metals. e.g. gold, platinum
Au + 4H+ + NO3- + 4CI- ⟶ AuCI4- + NO + 2H2O
⟶ HCI decomposes salts of weaker acids
Na2CO3 + 2HCI ⟶ 2NaCI + H2O + CO2
NaHCO3 + 2HCI ⟶ NaCI + H2O + CO2
Na2CO3 + 2HCI ⟶ 2NaCI + H2O + SO2
⟶ HCI reacts with finely powdered Fe to form ferrous chloride
Fe + 2HCI ⟶ FeCI2 + H2
H2 Liberated in the product prevents the formation of FeCI3.

Oxoacids of Halogens
⟶ Fluorine form only one oxoacid HOF due to its high electronegativity and small size.
⟶ They cannot be isolated in pure state. They are stable only in aqueous solution or in the
form of their salts.

Acidic nature of hypohalous acids

HOCl ˃ HOBr ˃ HOI
Reason : As E.N of halogens decreases from Cl to I, O of O-halogen bond has more and more
electron density on it. Therefore O in HOCl attract the electrons of O-H bond towards itself
most strongly followed by HOBr and then HOI. As a result, O-H breaks most readily in HOCl
and least readily in HOI.
Acidic strength of oxoacids of same halogen in different oxidation states
HClO4 ˃ HClO3 ˃ HClO2 ˃ HClO
It is due to Stability of anion which is due to dispersal of the negative charge through pπ-dπ
back bonding.
stability of anion ClO4- ˃ ClO3- ˃ ClO2- ˃ ClO-

Polyhalide Ions
Halogens or interhalogens combine with halide ions to form Polyhalide ions

e.g. I3− ICl2−

I2 (s) + I − (aq.) → I3− (aq.)

Structure of 𝑰−
𝟑

(Ι→Ι–Ι)

It has one covalent and one coordinate bond one covalent bond is formed by half filled 5p
Orbital and coordinate bond by empty 5d orbital.

Hybridization – sp³d

Shape – Linear
Pseudohalide Ions
Ιons which consist of two or more electronegative atoms of which at least one is nitrogen.

e.g. CN- , SCN- , OCN-

→ Their properties are similar to those of halide ions.