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Group 18: Xenon - Fluorine Compounds

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Group 18: Xenon - Fluorine Compounds - Lesson Summary

In 1962, Neil Bartlett predicted that xenon should react with platinum hexafluoride He was the first to prepare a compound of xenon, called xenon hexafluoridoplatinate (V).

Later many compounds of xenon were synthesised, including fluorides, oxides and oxy -fluorides.


Methods to prepare xenon-fluorine compounds:

Xenon directly reacts with fluorine to form a binary fluoride, which may be xenon di fluoride, xenon tetra fluoride or xenon hexafluoride. The product depends on the ratio in which xenon and fluorine reacts.

Xenon and fluorine in the ratio of 2:1 heated at 673 K at 1 bar pressure give xenon di fluoride

Xenon and fluorine in the ratio 1:5 heated at 873 K at 7 bar pressure give xenon tetra fluoride.

Xenon and fluorine in the ratio 1:20 heated at 573 K at 60-70 bar pressure give xenon hexafluoride

Xenon hexafluoride can also be obtained by the reaction of xenon tetra fluoride and dioxygen difluoride at 143 K.

                                                                 143 K
          XeF4                +           O2F2               →            XeF6
Xenon tetrafluoride          Dioxygen difluoride              Xenon hexafluoride

Structural aspects of the fluorides of xenon:

Structure of XeF2:

The central atom, xenon, in XeF2 undergoes sp3d hybridisation.

Xenon di fluoride has 5 electron pairs. Of these, 3 are lone pairs and 2 are bond pairs

The structure of xenon di fluoride is linear due to the presence of the 3 lone pairs of electrons on the central xenon atom.

Structure of XeF4:

The central atom, xenon, in XeF4 undergoes sp3 d2 hybridisation.

It has six electron pairs. Of these 4 are bond pairs and 2 are lone pairs.

The structure of xenon di fluoride is square planar due to the presence of the 2 lone pairs of electrons on the central xenon atom.

Structure of XeF6:

The central atom, xenon, in XeF6 undergoes sp3 d2 hybridisation.

It has 7 electron pairs. Of these 6 are bond pairs and 1 is a lone pair.

The structure of xenon hexafluoride is distorted octahedral owing to the presence of the single lone pair of electrons on the central xenon atom.

Properties of xenon fluorides:

All the fluorides of xenon are white crystalline solids.

They are strong oxidising and fluorinating agents.

EX:

      Strong Oxidising Agents

      
XeF2  +      2HCl                     →    Xe      +       2HF      +     Cl2
     Xenon           Hydrochloric              Xenon           Hydrogen        Chlorine
    difluoride             acid                                               Fluoride


       XeF4  +           4HI                     →    Xe      +       4HF      +     2I2
     Xenon              Hydroiodic                 Xenon           Hydrogen       Iodine
    tetrafluoride             acid                                               Fluoride

     Fluorinating Agents

      XeF4  +           2PtF4                     →    Xe      +       2PtF6
     Xenon              Platinum                        Xenon               Platinum
    tetrafluoride             tetrafluoride                                             hexafluoride

      XeF4  +           2SF4                     →    Xe      +       2SF6
     Xenon              Sulphur                        Xenon               Sulphur
    tetrafluoride             tetrafluoride                                             hexafluoride

Xenon tetrafluoride and xenon hexafluoride react violently with water, while xenon difluoride reacts slowly with water.

Very Fast Reaction

       6XeF4          +       12H2O     →    2XeO3     + 4 Xe              + 24HF          + 3O2
       Xenon                    Water            Xenon       Xenon            hydrofluoric         Oxygen
    tetrafluoride                                    trioxide                                  acid

       XeF6         +  3H2O             →       XeO3           + 6HF
     Xenon            water                        Xenon             Hydrofluoric
 hexafluoride                                      trioxide                   acid

Slow Reaction
     
        
2XeF2     +   2H2O         →        2Xe        +   4HF                 +    O2
         Xenon          Water                  Xenon          Hydrofluoric            oxygen
       deifluoride                                                              acid

Xenon fluorides form complexes called xenon fluoride complexes.

They form complexes with covalent penta fluorides, such as phosphorus penta fluoride, antimony penta fluoride and arsenic penta fluoride.

Xenon difluoride reacts with phosphorus penta fluoride, while xenon tetra fluoride reacts with antimony penta fluoride.

     xeF2      +       MF5                → XeF2.MF5          or      [XeF]+[MF6]-
   Xenon            Pentafluoride          Xenon fluoride               Cationic
 difluoride                                               complex                  species

     xeF2      +       PF5                → XeF2.PF5          or      [XeF]+[PF6]-
   Xenon            Phosphorus          Xenon fluoride               Cationic
 difluoride              Pentafluoride             complex                  species

     xeF2      +       SbF5                → XeF2.PF5          or      [XeF]+[SbF6]-
   Xenon            Antimony                  Xenon fluoride               Cationic
 difluoride              Pentafluoride             complex                  species

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