Group 18 elements [Noble gases]

Syed Zaffer Ali

Occurrence
• Except Radon, all occur in the atmosphere
• Main commercial source of He is natural gas
• Xe an Rn are rarest elements.
• Radon is obtained from alpha decay of radium
4𝐻𝑒
226 2
88𝑅𝑎 → 222
86𝑅𝑛
• General electronic configuration ns np except for helium which is ns2.
2 6

• Common called by the following names:

(i) Inert gases
(ii) Noble gases
(iii) Aerogens
(iv) Zero valent elements
(v) M8 elements.

• The names of noble gases are derived from Greek depending upon their
nature and behavior. For example:
(i) Helium from Helios [Greek word for sun]
(ii) Neon [Greek word for new]
(iii) Argon [Greek word for lazy]
(iv) Krypton [Greek word for typical]
(v) Xenon [Greek word for stranger]

Element Description

He • Atomic size increases down the group

Ne • IE decreases down the group due to increase in atomic size.
Ar Ionization energy extremely high due to completely filled
Kr valency shell.
Xe • Large positive electron gains enthalpy or electron affinity.
Rn
Physical properties of noble gases
• All are monatomic gases
• Colourless
• Odourless
• Tasteless
• Sparingly soluble in water
• Exceptionally low melting point and boiling point due to weak dispersion
forces or London forces.
• Can diffuse through rubber, glass, or plastics.
Note: The Noble exists in the atomic state due to the following reasons:
(i) Bond order of Noble gases is zero.
(ii) Specific heat ratio (𝛾) = 1.67
Bond order (B.O.) = ½ (Nb – Na)
Nb = Number of electrons in bonding molecular orbital
Na = Number of electrons in anti – bonding molecular orbital.
He2 (4 electrons)
Molecular orbital configuration: 𝜎1𝑠 2 𝜎 ∗ 1𝑠 2
B.O. = ½ (2 – 2) = 0
𝐶𝑝
Specific heat ratio (𝛾)=
𝐶𝑣

Cp = Molar specific heat at constant pressure

Cv = Molar specific heat at constant volume.
Note:
(i) If 𝛾 = 1.67 → Monoatomic
(ii) If 𝛾 = 1.40 → Diatomic
(iii) If 𝛾 = 1.33 → Polyatomic
Chemical properties of noble gases
• Least reactive due to the following reasons:
(i) Filled valency shell
(ii) Extremely high ionization enthalpy
(iii) Larger positive electron gain enthalpy.

• Noble gases can also react according to Neil Bartlett.

O2 can form O2+PtF6-
IE1 of O2 is 1175 kJ/mol [O2→ O2+ + e-]

IE1 of Xe is 1170 kJ/mol [Xe → Xe+ + e-]

• Therefore, Xe+PtF6- (red coloured compound) could also be prepared.

• After the preparation of XePtF6, many more Xe compounds with F and O
were prepared. Even RnF2 and KrF2 could be prepared.
• Xe – F compounds: [XeF2, XeF4 and XeF6]
O2+ [PtF6] → Oxygen Platinum hexafluoride
Xe+PtF6- → Xenon platinum hexafluoride
Preparation of Xenon compounds
Preparation Description

673𝐾 𝑎𝑛𝑑 1 𝑏𝑎𝑟 Colourless crystalline solids

Xe (g)excess + F2 (g) → XeF2 (s)
573𝐾 𝑎𝑛𝑑 7 𝑏𝑎𝑟 Sublime at 298 K
Xe (g) + 2 F2 (g) → XeF4 (s)
(1:5 ratio)
873𝐾 𝑎𝑛𝑑 60−70 𝑏𝑎𝑟 Powerful fluorination agents and
Xe (g)+ 3 F2 (g) → XeF6 (s)
(1: 20 ratio) readily hydrolyses by water

143 𝐾
XeF4 + O2F2 (g) → XeF6 (s) + O2
Hydrolysis of xenon compounds
• Complete hydrolysis of XeF2 gives Xe.
2 XeF2 + 2 H2O → Xe + 4 HF + O2
• Complete hydrolysis of XeF4 and XeF6 gives XeO3
6 XeF4 + 12 H2O → 2 XeO3 + 24 HF + 3 O2 + 4Xe
XeF6 + 3 H2O → XeO3 + 6 HF
• Partial hydrolysis of XeF6 gives XeO2F2 and XeOF4
XeF6 + H2O → XeOF4 + 2 HF
XeF6 + 2 H2O → XeO2F2 + 4 HF
Reactant # of moles of water Product of hydrolysis
XeF2 (complete hydrolysis) 2 H2O Xe (Xenon)
XeF4 (complete hydrolysis) 12 H2O XeO3 (Xenon trioxide)
XeF6 (completer hydrolysis) 3 H2O XeO3 (Xenon trioxide)
XeF6 (partial hydrolysis) 1 H2O XeOF4
XeF6 (partial hydrolysis) 2 H2O XeO2F2

• Reaction of Xe – F compounds

XeF2 + PF5→ [XeF]+[[PF6]-

XeF4 + SbF5→ [XeF3] +[[SbF6]-

XeF6 + MF → M+[XeF7]- (where, M = Na/K/Rb/Cs)

Shapes of xenon compounds
(i) Xe is sp3d hybridized
(ii) Shape = Linear
(iii) Bond angle = 1800
(iv) Expected shape = trigonal bipyramidal
(v) Expected bond angle = 900 and 1200
(vi) Formula =AB2E3 as per VSEPR theory
(vii) B = Number of bond pairs (bp) = 2
(viii) E = Number of lone pairs (lp) = 3
(ix) A = Central atom (Xe)
(x) B = Fluorine atoms attached to central atom.
(xi) Oxidation state of Xe = +2
(i) Xe is sp3d2 hybridized
(ii) Shape = Square planar
(iii) Bond angle < 900
(iv) Expected shape = Octahedral
(v) Expected bond angle = 900
(vi) Formula =AB4E2 as per VSEPR theory
(vii) B = Number of bond pairs (bp) = 4
(viii) E = Number of lone pairs (lp) = 2
(ix) A = Central atom (Xe)
(x) B = Fluorine atoms attached to central atom.
(xi) Oxidation state of Xe = +4
(i) Xe is sp3d3 hybridized
(ii) Shape = Distorted pentagonal bipyramidal
(iii) Bond angle < 720
(iv) Expected shape = Pentagonal bipyramidal
(v) Expected bond angle = 720 and 900
(vi) Formula =AB6E as per VSEPR theory
(vii) B = Number of bond pairs (bp) = 6
(viii) E = Number of lone pairs (lp) = 1
(ix) A = Central atom (Xe)
(x) B = Fluorine atoms attached to central atom.
(xi) Oxidation state of Xe = + 6
(i) Xe is sp3d2 hybridized
(ii) Shape = Square pyramidal
(iii) Bond angle < 900
(iv) Expected shape = Octahedral
(v) Expected bond angle = 900
(vi) Formula =AB5E as per VSEPR theory
(vii) B = Number of bond pairs (bp) = 5
(viii) E = Number of lone pairs (lp) = 1
(ix) A = Central atom (Xe)
(x) B = Fluorine atoms attached to central atom.
(xi) Oxidation state of Xe = + 6
 (i) Xe is sp3hybridized
(ii) Shape = Pyramidal or Distorted tetrahedral
(iii) Bond angle < 1090 28’
(iv) Expected shape = Tetrahedral
(v) Expected bond angle = 1090 28’
(vi) Formula =AB3E as per VSEPR theory
(vii) B = Number of bond pairs (bp) = 3
(viii) E = Number of lone pairs (lp) = 1
(ix) A = Central atom (Xe)
(x) B = Oxygne atoms attached to central atom.
(xi) Oxidation state of Xe = + 6
Shapes of XeOF4, XeOF2, XeO3 and XeO2F2

Compound Formula O.S. of Xe Hybridization Structure

Xenon difluoride XeF2 +2 sp3d Linear
Xenon tetrafluoride XeF4 +4 sp3d2 Square planar
Xenon hexafluoride XeF6 +6 sp3d3 Distorted pentagonal bipyramidal
Xenon oxydifluoride XeOF2 +4 sp3d T – shape
Xenon oxytetrafluoride XeOF4 +6 sp3d2 Square pyramidal
Xenon trioxide XeO3 +6 sp3 Pyramidal
Xenon tetroxide XeO4 +8 sp3 tetrahedral

Questions: Give reasons for the following

1. No known compounds of He is known.
2. Among noble gases only Xe is known to form compounds.
3. What made Neil Bartlett to think that Xe can form compounds?
4. Helium is used in diving apparatus.
5. Which is the most abundant noble gas in the atmosphere.
6. Which noble gas is not found in air?
7. Who isolated noble gases from fractional distillation of air?
8. Group 18 elements are called inert gases.
9. Group 18 elements are called zerovalent gases.
10. Group 18 elements are called M8 elements.
11. Group 18 elements have large positive electron gain enthalpy.
12. Why has it been difficult to study the chemistry of radon?
13. Noble gases have extremely low boiling points.
14. Why are the elements of group 18 known as noble gases?