INTERHALOGEN COMPOUNDSOR INTERHALOGENS
Each halogen combines with another halogen to form several compounds
first. In
as interhalogen compounds. The less electronegative element is written
naming also, the less electronegative element is mentioned first.
They are divided into four types.
CIF
BrF CIF3
BrF5
BICI BrF3
ICI IC13
1Br
They can all be prepared by direct combination or by the action of a halogen
on a lower interhalogen, the product formed depends on the conditions.
473K
C12+F2 (equal 2ClF (AX type)
12+ C12liquid (equi molar) 21Cl(AX type)
573K
C12+ 3F2 2 CIF3 (AX, type)
Br + 3F2(diluted with nitrogen) 2Br F3
+ (excess) 2Br (AXs Type)
12+ (Excess) (AX, Type)
573K
IFS+ F2 (Excess) (AX, Type)
The bonds are essentially covalent because of the small electronegativity
difference,and the melting and boiling points increase as the difference in
electronegativity increases.
The interhalogens are generally more reactive than the halogens (except F)
because the A-X bond is weaker than the X—Xbond in the halogens. The reactions
are similar to those of the halogens. Hydrolysis gives halide and oxyhalide ions,
the oxyhalide ion being formed from the larger halogen present.
BrF5+3 OH- ---—>5É+Br03- +3
Bromate
ICI + Cl¯+ + H+
hypoiodite
70
3m, ITO .
structures of interhalogen
compounds
Interhalogen compounds
are generally covalcnt
halogen forms thc central atom. compounds in which the larger
l. Type AX. As excepted,
the compounds of the type AX are
[Link], IBr and ICI are linear] Thus CIF,
all linear in structure.
Electronic structure of
Chlorine atom, in the ground state and hybridised state
isrcprcsented as in Fig. 3.4.
sp-3 b •
oöo ooÖoo
ATOMIN GROUND
STATE x
Linear Molecule
Fourspl hybrid orbitals
00000
tn- Cyc
Figure 3.4 Linear structure of the interhalogen compounds
of the type AX
Although the spatial arrangementof the four electron pairs (bV = 1 and
3) round the central chlorine atom is tetrahedral, due to the presence of three
lonepairs of electrons in three hybrid orbitals, th@shapeof AX molecule gets
distortedand become linear.
2. , Type AX3 Compounds of the typefAX3have trigonal bipyramidal structure,
Fig.3.5 for the CIF3molecule.
Bipyramidal structure arises out ofsp 3dhybridisation involved in the formation
ofthis compound, as illustrated in the Fig.3.6. The three dotted arrows indicate
electronscontributed by the three fluorine atoms (without lone pair it is T-shaped).
Fig. 3.5 Bi pyramidal structure of CIF molecule
71
Only one unpaired
electron permits one
covalent bond. oöo ooÖoo ATOMIN GROUNDSTATE
Three unpaired electrons
permit three covalent
bonds.
O 000 00000 ATOM'N EXCITED STATE
Formation of CIF
molecule by sp3d
hybridisation.
sp3d HYBRIDISATION
Fig. 3.6 sp3d hybridisation involved in the formation of Cl FJ molecule
3. Type (IF5, BrFs, etc.) These compounds are formed by sp342
hybridisation and hence have an octahedral structure, as shown in Fig. 3.7 for the
formation of IFSmolecule (without lone pair it is square pyramidal)!
oöo ooöoo
IODINE ATOM 'N GROUND STATE
O 000 00000 IODINE ATOM IN Q(CITÉD STATE
000 OÖOOO
sp3d2HYBRIDISATION
Fig. 3.7 Structure of IF
4. Type ÅV(IF'7). This compound has a pentagonalbipyramidål structure since
this is formed by sp3d3hybridisation.
F
ö oöo
IODINE
ooöoo
ATOM Excrreb STATE
1
@000 000100
%D3d3
Fig. 3.8 Structure of IF
•72
Problem
An element A occupies group number 17 and period number p, shows
anomalous behaviour. A reacts with water forms a mixture of B, C and acid D. B
and C are allotropes. A also reacts with hydrogen violently even in dark to give an
acid D. Identify A,B,C and D. write the reactions.
Solution
i) The element A that occupies group number 17 and period number 2 is fluorine.
ii) Fluorine reacts with water and forms a mixture of B and C
2F2+ 2H20 4HF +02
3F2+ 3H20 + 03
Therefore, B is Oxygen and C is Ozone.
iii) Fluorine reacts with hydrogen to give D.
F + H2 21-1F Dis Hydrofluoric acid.