Sr Inter Chemistry - Xenon Compounds - New Syllabus

Xenon Compounds
Xe directly reacts with F2 under different conditions to form Xenon Fluorides.
XeF2, XeF4 & XeF6 are crystalline & sublime at 298 K. They are readily hydrolysed.
2 Xe F2 + 2 H2 O → 4 HF + O2 + 2 Xe
6 Xe F4 + 12 H2 O → 24 HF + 2 XeO3 + 3 O2 + 4 XeXeF6 + H2O → 2 HF + XeOF4
XeF6 + 2 H2O → 4 HF + XeO2F2
XeF6 + 3 H2O → 6 HF + XeO3
Xenon Fluorides can be prepared by the direct reaction of Xe & F2.
673 K
Xe (g) + F2 (g) → XeF2 (s)
(in excess) 1 bar
873 K
Xe (g) + 2 F2 (g) → XeF4 (s)
(1 : 5 ratio) 7 bar
573 K
Xe (g) + 3 F2 (g) → XeF6 (s)
(1 : 20 ratio) 60 − 70 bar
Xenon Fluorides are powerful fluorinating agents. They react with F− ion
acceptors & form cationicspecies, with F− ion donors & form anionic species.
XeF2 + PF5 → [XeF]+ [PF6]−
XeF4 + SbF5 → [XeF3]+ [SbF6]−
XeF6 + RbF → Rb+ [XeF7]−
XeO3 is a colourless explosive solid.
XeOF4 is a colourless volatile liquid.
The geometry of XeF2, XeF4, XeF6 can easily be understood by VSEPR theory.
XeF2:
Xe = 5s2 5px2 5py2 5pz1 5d1 (First excited state)
Xe undergoes sp3d hybridization.
The shape of XeF2 is linear.
XeF4:
Xe = 5s2 5px2 5py1 5pz1 5d1 5d1 (Second excited state)
Xe undergoes sp3d2 hybridization.
Due to presence of 2 lone pairs, 4 bond pairs in second
excited stae, the shape of XeF4 is square planar.
Xe
F
F
F F
F F
XeF6:
Xe = 5s2 5px1 5py1 5pz1 5d1 5d1 5d1
(Third excited state)
Xe undergoes sp3d3 hybridization.
The shape of XeF6 is distorted octahedral.
XeO3:
Xe = 5s2 5px1 5py1 5pz
1 5d1 5d1 5d1 (Third excited state)
Hybridization Π bonds
Xe has one lone pair and six bond pairs. 3 bond
pairs form 3 pi bonds. Xe undergoes sp3 hybridization.
The shape of XeO3 is Pyramidal. Bond angle is 103°.
XeOF4:
Xe = 5s2 5px1 5py1 5pz1 5d1 5d1 5d1
Hybridization Π bond
(Third excited state)
Xe undergoes sp3d2 hybridization. Due to presence
of one lone pair and 6 bond pairs (1 bond pair forms
Π bond). The shape of XeOF4 is Square Pyramidal.

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