The Group 18 (Noble Gas) elements: Helium, Neon, Argon, Krypton, Xenon and Radon

The noble gasses have also been called the rare gases, and the inert gases. None of the names is gases. particularly suitable; with extensive chemistry, suitable; xenon is not inert, and argon is almost 30 times more abundant than carbon dioxide in air Something to know about: The greater reactivity of xenon compounds compared to the other elements. elements. The stability of xenon compounds containing electronegative elements (O and F) The reactivity of noble gas fluorides as fluoride ion donors and acceptors

Extremely high ionization energy Assumption: Not suitable for making chemical compounds First xenon compounds were synthesized in 1962, since then the 1962, chemistry of xenon is extensive. extensive. A few compounds of krypton have also been reported. The chemistry of many noble gas compounds are analogous to those of heavier Group 17 elements. elements. VSEPR is a powerful technique for rationalizing and predicting the shapes of many noble gas compounds, which have relatively large number of electron pairs in the valence shell of the central atom. atom.

Noble gases have filled shells, and so in order to form chemical compounds, electrons must be promoted into the next shell. shell. Depending on the number of electrons promoted, compounds of the noble gases in oxidation states +2, +4, +6 and +8 have all been synthesized. synthesized. With increase in atomic size, the outer electrons are easily removed and there is decrease in first ionization energy. energy. As a result there are many xenon compounds but a few for krypton, and none have been isolated for argon. argon.

All compounds tend to be strong oxidizing agents, and the fluorides are also powerful fluorinating agents. agents. The formation of anionic noble gas compounds (such as Cesium neonide, neonide, Cs+Ne-) with electropositive metals is an intriguing possibility, though none has yet been isolated. isolated.
G. H. Purser, J. Chem. Educ., 1988, 65, 119

If you are curious to know the historical developments in noble gas chemistry,
See the ref.: P. Laszlo and G. I. Schrobilgen, Angew. Chem. Int. Ed. Engl. 1988, 27, 479. ref.: Schrobilgen, Angew.

Occurrence
All of the elements exist as highly unreactive monoatomic gases, with very low boiling points. points. Argon is the most abundant, comprising of 0.93% of the atmosphere. 93% atmosphere. Helium, neon, krypton and xenon are trace constituents of air. air. All isotopes of radon are radioactive, and are formed naturally from the decay of heavy radioisotopes such as those of radium and uranium. uranium.

Noble Gas Clathrates

In the 1920s and 1930s there was considerable interest in materials 1920s 1930s formed between noble gases (particularly Ar, Kr and Xe) and strongly HAr, Xe) bonding compounds such as water and polyphenols. polyphenols. Later it was shown that they are not chemical compounds but clathrate compounds (also known as inclusion compounds), where the gas atoms occupy voids in the H-bonded lattice of the host compound when the host is crystallized under a noble gas atmosphere. atmosphere.

Xenon forms a clathrate with water of approximate composition Xe(H2O)n (n = 5 or 6), which has a melting Xe(H point of 24 oC.

Noble gas halides

Most important compounds of noble gases Fluorine is the most electronegative element and is able to stabilize the highly oxidizing noble gas compounds. compounds. The vast majority of compounds are fluorides of xenon (a few of Kr) though some chemistry of radon is known, hampered by its radioactivity and availability in only small quantities. quantities.

Ice containing an encapsulated noble gas atom in a void in the lattice. lattice. Hydrogen atoms of water molecules are omitted for clarity

Fluorides are the most important compounds formed by the noble gases

Krypton difluoride
Only known halide is KrF2 synthesized by passing an electrical discharge through a fluorine-krypton mixture. fluorineKrF2 is a powerful fluorinating agent and is more reactive than XeF2. It will oxidize Xe to XeF6 and metallic gold to AuF6-.

3KrF2 + Xe 7KrF2 + 2Au

XeF6 + 3Kr 2[KrF]+[AuF6]- + 5Kr 2[KrF]

Xenon Fluorides
A xenon fluoride, XePtF6, was the first noble gas compound to be synthesized by reaction of Xe with strong oxidant PtF6, and later shown to be probably a mixture of [XeF]+[PtF6]- and [XeF]+[Pt2F11]- . XeF] XeF] Xenon forms three neutral fluorides, XeF2, XeF4 and XeF6, reaction of fluorine and xenon under different conditions. conditions. by the

Simplest method involves exposing a fluorine-xenon mixture (contained fluorinein a dry glass bulb) to sunlight; colorless crystals of XeF2 are deposited on the walls of the flask.

KrF2 is a powerful fluorinating agent and is more reactive than XeF2. It will oxidize Xe to XeF6 and metallic gold to AuF6-.

3KrF2 + Xe 7KrF2 + 2Au

XeF6 + 3Kr 2KrF+AuF6- + 5Kr

The sunlight causes dissociation of the relatively weaker F-F bond in F2 to form F atoms, which then react with Xe. Xe. With larger ratios of F to Xe, higher temperatures and higher pressures, Xe, XeF4 and XeF6 can be synthesized. synthesized. Shapes: Shapes:
F
F F F Xe F F F
XeF6 is fluxional in the gas phase, interchanging between structures where the lone pair points through the centre of an F3 triangle (one face) of a distorted octahedral XeF6 molecule. molecule. The lone pair is in a spherically inactive s-orbital. orbital.

F
Xe

F
F

Xe F

XeF2

XeF4

XeF6

All of the xenon fluorides are powerful fluorinating agents, able to oxidize a wide range of compounds. In many cases XeF2 is a very selective oxidant, able to oxidize the central heteroatom of a main group compound (such as As, P, etc.) but not etc. organic substituents (methyl or phenyl) bonded to it. it.

Me3As + XeF2 Ph2PH + XeF2

Me3AsF2 + Xe Ph2PHF2 + Xe

XeF2 also oxidizes water to oxygen, while XeF4 can oxidize platinum metal to PtF4

2H2O + 2XeF2 XeF4 + Pt

O2 + 4HF + 2Xe

PtF4 + Xe

Reactions of noble gas fluorides with fluoride ion acceptors and donors
Chemistry is extensive

Noble gas fluorides react with strong fluoride ion acceptors, EF5 of AsF5, SbF5, BiF5, Ta, Ru or Pt. Pt. XeF2 forms the greatest number of compounds by this type of reaction followed by XeF6 and XeF4. KrF2 forms many similar compounds. compounds.
While transferring the fluorides, can be fully transferred to the Lewis acid MF5 leaving cationic xenon species, but in most cases fluoride is only partially transferred, resulting in compounds with Xe F E fluoride bridges. Xe bridges.

Different types of cations and anions are formed depending on the stoichiometry of noble gas fluoride to EF5.

XeF2(s) + AsF5(l)

[XeF]+[AsF6]-(s) XeF]
F F Sb F
[Xe2F3]+ cation

(1:1 ratio)

When a 2:1 ratio is used, the adducts tend to contain cations with XeFE bridges. Xe

F F Xe F

F As F

F F

214 pm F 190 pm

Xe
150o

F F F F

Xe

Sb F F

[XeF]+[AsF6] XeF]

[Sb2F11] anion

Noble gas fluorides can act as fluoride acceptors or donors to give anions or cations XeF4 + F[XeF5](also, [XeF7]-, [XeF8]2- from XeF6, XeF7 by adding one or two F- ions) [XeF [XeF

XenonXenon-oxygen compounds
Results from hydrolysis of the fluorides XeF4 and XeF6. Hydrolysis of XeF2 results in oxidation of water to oxygen. 6XeF4 + 12H2O XeF6 + 3H2O 4Xe + 2XeO3 + 24HF + 3O2 XeO3 + 6HF

XeO3 is a highly explosive white solid, soluble in water (not ionized) In strong alkaline solution, however, XeO3 behaves as a weak acid, giving xenate(VI) xenate(VI) anion, [XeO3(OH)]-, by addition of OHXeO3 + OH[XeO3(OH)]-

Xenate(VI) Xenate(VI) anion is unstable in aqueous solution, and undergoes a disproportionation reaction to give xenon gas and the xenate(VIII) anion, xenate(VIII) XeO64-, which contains xenon in +8 oxidation state. state. 2XeO3(OH)- + 2OHXeO64- + Xe + O2 + 2H2O

XeF6 + H2O XeF6 + NaNO3 XeF6 + POFf

XeOF4 + 2HF XeOF4 + NaF + FNO2 XeOF4 + PF5

The reaction of XeF6 with Na4XeO6 gives the oxyfluorides XeOF4 and XeO3F2; XeO2F2 is also known. Other xenon-oxygen compounds can be formed from XeF2, XeF4 and XeF6 by xenonsubstitution of one or more fluorides by reaction of strong oxyacids (XOH) such as CF3SO3H, MeSO3H, CF3COOH, FSO3H or TeF5OH, with elimination of HF

FXeF + XOH Xe

FXeOX (+HF) Xe

XOXeOX (+HF) XOXe

Alternatively, fluoride exchange yields analogous products

XeF6 + 2B(OTeF5)3

Xe(OTeF5)6 + 2BF3 Xe(OTeF

The compounds have similar shapes to fluorides, e.g. XO-Xe-OX and XeF2 are XO-Xeboth linear.

Xenon and Krypton compounds with bonds to elements other than O and F

XeF2 +B(C6F5)3

[C6F5Xe]+[C6F5BF3]- +[C6F5Xe][(C6F5)2BF2]-

Alkynyl species of the type [RCCXe]+, where R can be a range of non[RCCXe] nonfluorinated groups such as ethyl or SiMe3 have been made. Extensive organic chemistry is awaited or awaits discovery. Few xenon compounds containing other elements are:

[C6F5Xe]+ + Cl-

C6F5XeCl
F

F Xe +

The [C6F5Xe]+ cation in MeCN solution get solvated to give [C6F5Xe(NCMe)]+ ; which has a Xe(NCMe)] linear geometry