NOBLE GASES

Occurrence and uses, rationalization of inertness of noble gases,

Clathrates; preparation and properties of XeF2, XeF4 and XeF6;
Nature of bonding in noble gas compounds (Valence bond treatment
and MO treatment for XeF2). Molecular shapes of noble gas
compounds (VSEPR theory).
 Where are the noble
gases?
The elements in group 18, on the right of the periodic table,
are called the noble gases.
He helium
Ne neon
Ar argon
Kr krypton
Xe xenon
Rn radon
 Group 18: The Nobel gases
The Nobel gases

• The noble gases, also known as the inert gases

or rare gases, are located in Group VIII A or 18
of the periodic table.
• Group 18 is sometimes called Group 0.
• This group is a subset of the nonmetals.
• The noble gases are; helium (He), neon (Ne),
argon (Ar), krypton (Kr), xenon (Xe) , radon
(Rn) and Oganesson (Og).
• The elements have a [core]ns2 np6 electron
configuration with a complete octet. (n is the
period number)
• Their closed shell electron configuration makes
them have a very low reactivity.
 Group 18: The Nobel gases

The Nobel gases

• Noble gases have a full valence shell.

• The noble gases are the smallest elements in their respective periods, with the
highest ionization energies.

• Noble gases have very low melting and boiling points.

• Only Kr, Xe, and Rn are known to form compounds.

• Xe is the most reactive noble gas and exhibits all even oxidation states from
+2 to +8.
• Very low electronegativities
• No color, odor, or flavor under ordinary conditions
• Nonflammable
• At low pressure, they will conduct electricity and fluoresce
 Group 18: The Nobel gases
The Nobel gases
• All the noble gases occur in the atmosphere as monatomic gases.
 They are monatomic, which means they exist as individual atoms.
Most other gases are diatomic.
• Together they make up 1% (by mass) of the atmosphere.
• Argon is the third most abundant gas in the atmosphere after N and O.
Sources of the Noble Gases
•All of the noble gases except He and Rn are obtained by the fractional distillation
of liquid air.
• The major source of helium is from the cryogenic separation of natural gas.
•Radon, a radioactive noble gas, is produced from the radioactive decay of heavier
elements, including radium, thorium, and uranium.
• Element 118 (Og) is a man-made radioactive element, produced by striking a
target with accelerated particles.
 The gases He, Ne, Ar, Kr and Xe all occur in atmosphere.

 A mixture of noble gases was first obtained by Cavendish in 1784. He removed N 2 from
air by adding excess O2 and sparking. The NO2 formed was absorbed by NaOH solution
and excess O2 was removed by burning with S. This gave small volume of unreactive gas.

 Argon is abundant and cheapest and can be recovered by fractional distillaton of liquid
air.

 Other noble gases are much less abundant.

 The non radioactive noble gases are all produced industrially by fractional distillation of
liquid air.

Rn is radioactive and produced by decay of radium and thorium minerals. The
convenient source is 226Ra.

88
226
Ra 222
86 Rn + 42He
 Group 18: The Nobel gases
Uses of noble gases
• The noble gases are used to form inert atmospheres, to protect specimens, and
to prevent chemical reactions (to prevent oxidation).
• Argon is also used to fill some types of light bulbs, where it conducts heat
away from the filament. The largest use of Argon is to provide an inert
atmosphere for metallurgical processes. Smaller amounts are used in growing
silicon and germenium crystals for transistors and in electric light bulbs,
fluorscent lamps, radio valves.
• Helium has the lowest boiling point of any liquid and it is used in cryoscopy
to obtain very low temp. Required for superconductivity and lasers.
• It is used as cooling gas in nuclear reactor and as the flow gas in gas
liquid chromatography.
• It is used in weather ballons and airships. Though Hydrogen has
lesser density and is cheaper and more readily available than He.
• Hydrogen is highly flammable. Thus on safety guards He is used in
preference of Hydrogen in airship.
• Helium is used in preference to nitrogen to dilute dioxygen in the gas
cylinders used by divers. This is because dinitrogen is quite soluble in
blood so sudden change in pressure causes degassing and gives bubbles of
nitrogen gas in blood. This caused painful condition called “bends”
• Krypton gives an intense white light when an electrical current is passed
through it and it is used in airports for there runway lights used:
In lasers for eye surgery, to stop bleeding on the retina.
In lighthouses and other types of lamps.
• Xenon is used:
In various types of electron tubes, lamps, lasers and in high speed
photographic flash tubes
.
• Small amount of Ne is used in neon discharge tube which give the
familiar reddish orange glow of neon sign.

• Radon is used:
To treat cancer by radiotherapy, because it is radioactive.
However, because radon is radioactive, it is also an environmental
hazard
 Group 18: The Nobel gases

The Atomic and Physical Properties

• Atomic mass, boiling point, and atomic radii INCREASE down a group in
the periodic table. 
• The first ionization energy DECREASES down a group in the periodic
table. 
• The noble gases have the largest ionization energies, reflecting their chemical
inertness.
• Down Group 18, atomic radius and interatomic forces INCREASE resulting
in an INCREASED melting point, boiling point, energy of vaporization, and
solubility. 

• The INCREASE in density down the group is correlated with

the INCREASE in atomic mass.
 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
 Group 18: The Nobel gases

Selected Properties of Group 8 A

Elements
 CHEMICAL INERTNESS OF NOBLE GASES

Chemical Inertness of these gases is supported by the reasons:

i) The atoms have stable completely field electronic shells
ii) They have high ionisation energies
iii) The noble have almost zero electron affinities.
Therefore, they do not have any tendency to gain, lose or share electrons
with other atoms.
 Recent studies have shown that under certain specific condition, they enter into
chemical combinations and form some rare chemical compounds.
 The specific conditions and the types of compounds formed by these gases are
disused below-
 Under excited condition:- Sparking Helium at low pressure in presence of
mercury, tungsten etc. forms compounds like HgHe2, HgHe10, WHe2.
 Helium compounds are also fromed in discharge tubes like BiHe 2, FeHe, Pt3He,
PdHe. These compounds are not considered as true chemical compounds as He is
absorbed on the surface .
• Compounds formed through co-ordination- Argon forms a number of unstable compound with varying no. of
BF3 molecules e.g. Ar.BF3, Ar.6BF3

• In these compounds, argon atoms donates a pair of electrons to Boron atom of BF 3 .

• In case of higher compounds fluorine atoms of BF3 also donate pair of electrons.

• Hydrates of noble gases: The hydrates of these gases are formed by compressing the gases with water e.g.,
Xe.6 H2O.

• Compounds formed by physical trapping (Clathrates) The inert gases Argon, Krypton and Xenon form solid
compounds with certain organic molecules such as phenol and hydroquinone under pressure. In such
compounds the inert gas are enclosed in the crystal lattice of organic compounds known as clathrates or cage
compounds.
•
 Group 18: The Nobel gases
Compounds of the Nobel Gases (Reactivity):
• The elements have a complete octet, predict that there would be no chemistry
for the noble gases.
• However, numerous group 18 compounds are known, although they may be
very unstable and explosive.
• He and Ne are chemically inert and they do not form any compounds.
 Their chemical inertness is due to very high ionization energy, zero
electron affinity and the absence of vacant d-orbitals in valence shell.
• Ar, Kr and Xe will show some reactivity
 due to low ionization potentials and presence of vacant d-orbitals in
valence shell.
• Xe is more reactive than Ar and Kr
 due to it's low ionisation energy.
• Radon is radioactive and it will not show chemical reactivity.
 Group 18: The Nobel gases

Compounds of the Nobel Gases (Reactivity):

• Krypton forms only one known stable neutral molecule KrF2.

• Xe shows tendency to lose electrons in many of it's reactions. Therefore, Xe

combines with only more electronegative elements like F and O or
electronegative groups.
• Xe does not combine with less electronegative elements like Cl2 or N2.
 Group 18: The Nobel gases
The Elements (Xenon)
• Xenon is unique for being the first noble gas element to be synthesized
into a compound.
• Discovered on 1898 by Sir William Ramsay.
• Xenon is present to a small extent in the atmosphere (less than one ppm
by volume).
• Metallic xenon is produced by applying several hundred kilobars of
pressure.
• In 1962 the first noble gas compound was produced by Neil Bartlett,
combining xenon, platinum and fluorine.
• It is now possible to produce xenon compounds in which the oxidation
states range from +2 to +8.
• Most of the known xenon compounds contain the strongly reducing
fluorine or oxygen atoms.
 Group 18: The Nobel gases
on Compounds and their Molecular Structure
Fluorine is the only element that directly reacts with Xenon.
Xenon-fluorine compounds
 XeF2, XeF4 and XeF6
Preparation : By the direct reaction of elements under appropriate
experimental conditions.
Properties: They are readily hydrolysed even by traces of water.

673K, 1bar

873K, 7bar

573K, 60-70bar
 Xenon Compounds andGroup
their18:Molecular Structure
The Nobel gases
• Xenon Halides are reactive with other compounds such as water.
 XeF2+3H2O → XeO3+ 6HF

• The Xe has a total of 8 outside shell electrons while the Fluorine 7 valence
electrons.
• Xe's outside shell electrons are very far away from the center, therefore
Xenon cannot possibly attract all of the electrons.
• Fluorine is smaller, therefore is has a stronger positive attraction to the few
electrons it has left.
• Fluorine is the only element that reacts with Xe because it is the most
electronegative.
• In other words, it is the only element that is strong enough to pull electrons
out of the stable xenon. 
 Group 18: The Nobel gases

Xenon Compounds and their Molecular Structure

Xenon-oxygen compounds

 XeO3 XeOF4 and XeO2F2

XeO3
Hydrolysis of XeF4 and XeF6 with water gives
XeO3.
6XeF4 + 12 H2O → 4Xe + 2XeO3 + 24 HF + 3
O2
XeF6 + 3 H2O → XeO3 + 6 HF
XeO3 is a
colourless
explosive solid
and sp 3

Hybridization
has a pyramidal
molecular
structure
 Group 18: The Nobel gases

Xenon Compounds and their Molecular Structure

XeOF4 and XeO2F2

Partial hydrolysis of XeF6 gives oxyfluorides, XeOF4

and XeO2F2.
XeF6 + H2O → XeOF4 + 2 HF
Xenon oxytetrafluoride

XeF6 + 2 H2O → XeO2F2 + 4HF

Xenon dioxydifluoride

XeOF4 is a colourless volatile liquid and has a square pyramidal

molecular structure

Square pyrami
 Group 18: The Nobel gases

↑
↓

Xe F
F

O
O

sp3d sp3d2
Hybridization Hybridization

XeO2F2 XeOF4
 Group 18: The Nobel gases

Structures of several known xenon compounds

 Compounds of noble gases-

Xenon forms a large no. of compounds with oxygen and fluorine in different
oxidation states . These are xenon fluorides, xenon oxides and xenon
oxifluorides. 1. XeF2
Preparation.
1. Xenon di fluoride 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 is obtained.
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.

 2. XeF4
Preparation.
 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 of XeF4 are:

 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
 3 . XeF6

Preparation.
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
Properties:- Crystalline substance, m.pt. 49.50C, Mostly
volatile, all the fluorides of xenon are greenish yellow
colour vapour . It is extremely reactive. Therefore, it cannot
be stored in glass or quartz vessels because of the
following reactions which finally 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]-

 4. XeOF4

Preparation :
(i) Xenon Oxytetraflouride is prepared by partial
hydrolysis of Xenon hexa flouride
XeF6 + H2O XeOF4 + 2 HF

(ii ) 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. It is
done to avoid the formation of XeO3 (explosive) as:

XeOF4+SiO2 XeO3+SiF4
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 XeOF4 + H2O XeO2F2 + 2HF
XeO2F2 + H2O XeO3 + 2HF
2XeOF4 + SiO2 2 XeO2F2 + SiF4
2XeO2F2 + SiO2 2 XeO3 + SiF4
Valence bond treatment and MO treatment for XeF2
 Structure of Some Xenon Compounds

Formula Name Oxidn m.pt. (oC) Structure

state
XeF2 Xenon +2 129 Linear
difluoride
XeF4 Xenon tetra +4 117 Square Planner
fluoride
XeF6 Xenon +6 49.6 Distorted octahedron
hexafluoride

XeO3 Xenon +6 Explodes

trioxide Pyramidal tetrahedral with
one corner un occupied
XeO2F2 Xenon dioxy +6 30.8 Trigonal lipyramid
difluoride (with one position
unoccupied)
XeOF4 Xenon oxy +6 -46 Square pyramidal
tetrafluoride (octahedral with one
position un occupied
XeO4 Xenon tetra +8 -35.9 Tetrahedral
oxide
XeO3F2 Xenon trioxy +8 -54.1 Trigonal bipyramidal
difluoride
Ba2[XeO6]-4 Barium +8 octahedral
perxenate
 Structure and Bonding in Xenon Compounds

Formula Structure No. No. of VSEPR

of e lone (Explanation of structure)
pairs pairs
XeF2 Linear 5 3 Five electron pairs form trigonal
bipyramidal with three lone pairs at
equatorial positions
XeF4 Square 6 2 Six electron pairs form octahedron with
Planner two positions occupied by lone pairs
XeF6 Distorted 7 1 Pentagonal bipyramidal or capped
octahedron octahedron with one lone pair
XeO3 Pyramidal 7 1 Three π bonds so that the remaining four
electron pairs form a tetrahedron with
one corner occupied by a lone pairs.
Formula Structure No. of No. of VSEPR
e lone (Explanation of structure)
pairs pairs
XeO2F2 Trigonal 7 1 Two π bonds so remaining five
lipyramid electron pair form trigonal
bipyramid with one equatorial
position occupied by a lone pair
XeOF4 Square 7 1 One π bond so remaining six
pyramidal electron pairs form an
octahedron with one position
occupied by a lone pair.
XeO4 Tetrahedra 8 0 Four π bonds so remaining four
l electron pair form a tetrahedron
XeO3F2 Trigonal 8 0 Three π bonds so remaining five
bipyramid electron pairs form trigonal
bipyramid
Ba2[XeO6] Octahedral 8 0 Two π bonds so remaining six
electron pair form an octahedron.
 Geometrical Shape

F
. .
. .

XeF2 Xe

.
.
F
. .
Molecule Type of Hybridization
F F

XeF4 sp3d2 Xe

F F
. .
 F Geometrical Shape

F F

.
.
Xe

Molecules & Type of hybridization

F F
XeF6 sp3d3
F
. .

xe

XeO3 sp3
 F

. .
xe
O

O
XeO2F2 sp d 3 F
O

F F

Xe F

F F

. .
XeOF
XeO 2F
44 sp
Spdd
3 32 2 O
 O
F F

Xe

F F

XeOF4 Sp3d2
. . -4
O

O O

-4
Xe
XeO6 Sp d
3 2

O O
Significance of Noble gases in development of
theoretical chemistry.
1. In Elucidation of distribution of electrons in atom
2. In periodic classification
3. In the development of electronic theory of valency
4. In radioactivity .
Thank you