Chemistry of Noble Gases

Dr. Gurpreet kaur

 History of Noble Gas Compounds

Before 1962:
• all noble gases are inert
• weakly bonded species
• gaseous cationic species: diatomic molecules between
noble gas atoms or other atoms (H, O, N, Hg)
• very short lifetimes
1962, Bartlett and Lohmann:
• demonstrated the great oxidizing strength of PtF6 in producing
O2+PtF6-
• IP(Xe) ≈ IP(O2)
RT
Xe + PtF6 XePtF6 + Xe(PtF 6)2
- dependent on reactant ratio
- red-tinged yellow solid
 Physical Properties Noble gases

Element Outer Vander First m.pt. b.pt. ∆Hfux ∆H vap

electronic Wall's IE (K) (K) (kj mol-1) (kj mol-1)
configuration radius (kj mol-1)
(Å)

He 1s2 - 2372 - 4.2 0.02 0.08

Ne 2s2 2p6 1.31 2080 24.4 27.1 0.33 1.77
Ar 3s2 3p6 1.74 1519 83.6 87.3 1.18 6.5
Kr 4s2 4p6 1.89 1351 116 120 1.64 9.0
Xe 5s2 5p6 2.10 1170 161 166 2.3 12.6
Rn 6s2 6p6 2.15 1037 200 211 2.9 16.4
 Why NOBLE GASES are inert in nature?

Chemical Inertness of these gases is due to following

reasons:
1. The atoms have stable completely field electronic shells
2. They have high ionisation energies
3. The noble have almost zero electron affinities.
Therefore, they do not have any tendency to gain, lose or
share electrons with other atoms.
 Energy Considerations
• Why Fluorine?
– Noble gas will remain bound to ligand if it is so
electronegative that energy required to remove electron from
NG is compensated for by the electron acquisition of the
ligand and the electrostatic attraction energy of Nδ+ and Lδ-

• The atoms of chlorine and other halogens are much larger than
fluorine, so attraction energy for (LN)+L- ion pair is much less.

• In oxides, ionization energy is mostly compensated for by the

electrostatic attraction term (though oxygen atom electron affinity
also contributes).
– Thus only fluorine is stable ligand
 Compounds of noble gases

• Xenon Fluorides
• readily prepared from the elements
• thermodynamically stable
• XeF2
• XeF4
• XeF6
• not known: XeF8
Xenon difluoride , XeF2

XeF2 is best prepared by heating a mixture of xenon and fluorine

in molecular ratio of 2:1 at 4000C in a sealed nickel tube. On
cooling quickly, a colourless solid XeF2 separated out.
Ni
Xe+F2 XeF2
4000C
 Properties
1. Xenon difluoride is a colourless, crystalline solid which
melts at 1290C.
2. It reacts with hydrogen to give hydrogen fluoride and
xenon.
XeF2 + H2 Xe + 2HF
3. It gives substitution reactions with strong protonic acids.
XeF2 + HX FXeX + HF
FXeX + HX XeX2 + HF
Where X= CIO-4 CF3COO-, SO3F- etc.
4. It hydrolyses slowly but completely in
acidic, neutral or alkaline solutions.
2 XeF2 + 2H2O 2 Xe + 4HF + O2
2 XeF2 + 4NaOH 2Xe + 4NaF + O2 + 2H2O
5.It oxidizes iodine in the presence of BF3
to give IF.
6. It is a mild fluorinating agent. It reacts with
benzene to give fluorobenzene.
7. It is also a strong oxidising agent.
 XeF4

 It is prepared by heating a mixture of xenon and fluorine, in a nickel

vassal, at 4000C under pressure of 5-6 atm.
 It can also be synthesized by passing an electric discharge through a
mixture of xenon and fluorine at -78OC.

Properties:

 It is a colorless, crystalline solid, with m.pt. 117. 10c, sublimes readily.

 Oxidized by hydrogen to HF at 300 C.
 A stronger fluorinating agent than XeF2
 XeF6
1. It is prepared by heating xenon with excess of fluorine (in the
molar ratio of 1:20) in a nickel vessel at 250-3000C under pressure
of 50-60 atm.

Xe + 3F2 XeF6
2. It can also be obtained by the oxidation of XeF4 with O2F2 under
pressure.

XeF4 + O2F2 -1300c XeF6 + O2

Why xenon hexafluorides cannot be stored in glass or silica vessels?

Xenon hexafluoride is extremely reactive. It cannot be stored in

glass or quartz vessels because it reacts with silica of the glass and
give the dangerously explosive xenon trioxide.

2XeF6+SiO2 2XeOF4 +SiF4

2XeOF4+SiO2 2XeO2F2+SiF4
2XeO2F2+SiO2 2XeO3+SiF4
(explosive)
2 It reacts with fluoride ion acceptors to form adducts.

XeF6+PtF5 XeOF4+PtF5 [XeF5]+[PtF6]-

XeF6+SbF5 XeF6 .SbF5 [XeF5]+[SbF6]-

XeF6+AsF5 XeF6.AsF5 [XeF5]+[AsF6]-

 XeOF4

(1) Xenon Oxytetraflouride is prepared by partial hydrolysis

of xenon hexaflouride
XeF6 + H2O XeOF4 + 2 HF

(2) By the action of XeF6 on silicon dioxide

2XeF6 + SiO2 XeOF4 + SiF4

Soon as the yellow colour of XeF6 disappears, the contents

are immediately quenched with solid CO2 so as to avoid
the formation of XeO3
Properties

1. It is a colourless compound melting at -46oC.

2 It is reduced by hydrogen to xenon.

XeOF4+3H2 Xe+H2O+4HF

3 It reacts with water or silica to form another oxyfluoride,

XeO2F2, in ;which xenon remains in the same oxidation
state. Further reaction gives explosive compound XeO3
4. Action with water:
XeOF4 + H2O XeO2F2 + 2HF
XeO2F2 + H2O XeO3 + 2HF
2XeOF4 + SiO2 2 XeO2F2 + SiF4
2XeO2F2 + SiO2 2 XeO3 + SiF4
 XeO2F2

1. It is prepared by mixing XeO3 and XeOF4 at temperature

close to -78OC.
XeO3+XeOF4 2XeO2F2
The compound is purified by fractional distillation.
2. It is also formed when XeOF4 is hydrolyzed or
reacted with silica.
2XeOF4+SiO2 2XeO2F2+SiF4
XeOF4+H2O XeO2F2+ 2HF
Properties
1. It is a colourless solid.
2. Its melting point is 30.8OC.
3. It is easily hydrolyzed to give xenon trioxide.
XeO2F2 + H2O XeO3 + 2HF.
 XeO3

Xenon trioxide is prepared by the hydrolysis of XeF6 or XeF4

6XeF4 + 12H2O 2XeO3 + 4Xe +24HF+3O2
XeF6 + 3H2O XeO3 + 6HF
It acts as a powerful oxidizing agent in acidic medium. For
instance, it oxidizes Pu3+ to Pu4+ in the presence of H+ ions.
6Pu+3 + XeO3 + 6H+ 6Pu +4 + Xe + 3H2O
 Structure of Some Xenon Compounds

Formula Name Oxidn Geometry

state
XeF2 Xenon +2 Linear
difluoride
XeF4 Xenon tetra +4 Square Planar
fluoride
XeF6 Xenon +6 Distorted octahedron or
hexafluoride pentagonal bipyramidal
XeO3 Xenon +6 Pyramidal
trioxide
XeO2F2 Xenon dioxy +6 Trigonal bipyramidal
difluoride

XeOF4 Xenon oxy +6 Square pyramidal

tetrafluoride

XeO4 Xenon tetra +8 Tetrahedral

oxide
XeO3F2 Xenon trioxy +8 Trigonal bipyramidal
difluoride
Ba2[XeO6]-4 Barium +8 octahedral
perxenate
 Geometrical Shape

F
.. ..

Xe
XeF2 sp3d

F
. .

F F

XeF4 sp3d2 Xe

F F
. .
 F Geometrical Shape

F F

XeF6 sp3d3
Xe

F F

F
. .

xe
XeO3 sp3
 F

. .
O
xe

XeO2F2 sp3d
O
F
O

F F

F
XeO2F4 sp3d2 Xe

F F

. .
O
 O

F F

XeOF4 sp3d2
Xe

F F

. . -4
O

O O

-4
Xe
XeO6 sp3d2

O O