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Home , Krypton difluoride, Perxenate, Xenon difluoride, Xenon hexafluoride, Xenon tetrafluoride, Xenon trioxide

Chapter 21 THE NOBLE GASES

21-1 Occurrence, Isolation, and Applications The noble gases (Table 21-1) are minor constituents of the atmosphere, from which Sir William Ramsay was first able to isolate the elements Ne, Ar, Kr, and Xe. William F. Hillebrand had isolated gas from minerals, and Ramsay was able to demonstrate that the gas has the same spectrum as the ele­ ment identified spectroscopically in the sun by SirJ. orman Lockyer and Sir E. Frankland in 1868. Helium occurs in radioactive minerals and, notably, in some natural gases in the United States. Its origin is entirely from the decay of uranium or iso­ topes that emit a-particles. These a-particles are helium nuclei that acquire elec­ trons from surrounding elements, and if the rock is sufficiently impermeable, the helium remains trapped. The gas , all ofwhose isotopes are radioactive with short half-lives, was characterized in the decay series from uranium and tho­ rium. The elements Ne, Ar, Kr, and Xe are obtained from fractionation of liquid air. The gases were originally termed inert, and thought to have no chemical re­ activity at all. They provided the key to the problem ofvalency, the interpretation of the periodic table, and the concept of the closed-electron shell configuration. Although we now know that some of the noble gases can form compounds, they still provide a point of reference in these respects. A main use of helium is as the liquid in cryoscopy. may be used to pro­ vide an inert atmosphere in laboratory apparatus, in welding, and in gas-filled electric light bulbs. is used for discharge lighting tubes, giving the familiar red glow of "neon" signs. Radon, formed from other elements by radioactive decay sequences, is a health hazard in houses in certain granite areas. It is taken into the lungs, where by-products from its decay sequences cause cancer. Thorough ventilation of the houses is important in such areas.

21-2 The of

During studies with the very reactive gas PtF6 , Bartlett found that a crystalline solid, [02+][PtF6"], was formed with . He noted that since the ionization enthalpy of Xe is almost identical with that of 02' an analogous reaction might be expected and, indeed, in 1962 he reported the first compound containing a , a red crystalline solid first believed to be [Xe+] [PtF6"], but now known to be more complex. 483 484 Chapter 21 I The Noble Gases

Table 21-1 Some Properties of the oble Gases

First Ionization Vol. %in Outer Enthalpy Normal atmosphere 1 4 Element Configuration (kJ mol- ) bp(K) (x 10 )

He 1.1 2 2369 4.2 5.2 Ne 2s 2 2p6 2078 27.1 18.2 Ar 3s 2 3p6 1519 87.3 9340.0 Kr 4s 24pG 1349 120.3 11.4 Xe 5s 25p6 1169 166.1 0.08 2 Rn 6s 6p6 1036 208.2

There is now an extensive chemistry of xenon with bonds to F and 0; one compound with a Xe-N bond is known, but compounds with bonds to other el­ ements are highly unstable. A few compounds exist, but while there should be an extensive chemistry of Rn, the short lifetimes of the isotopes make study impossible. Xenon only reacts directly with , but oxygen com­ pounds can be obtained from the . Certain compounds are very stable and can be made in large quantities. Table 21-2 lists some of the more important compounds and their properties.

Table 21-2 Some Xenon Compounds

Oxidation State Compound Form mp(°C) Structure Remarks

Il XeF2 Colorless 129 Linear Hydrolyzed to Xe + 02; very soluble in HF(f)

IV XeF4 Colorless 117 Square Stable crystals

VI XeF6 Colorless 49.6 Complex, Stable crystals see text Cs2XeFs Yellow Archimedean Stable to 400°C solid antiprism

XeOF4 Colorless -46 Square Stable liquid pyramid Xe02F2 Colorless 31 Seesaw Stable crystals F-axial

Xe03 Colorless Pyramidal , crystals hygroscopic; stable in solution

VIIl Xe04 Colorless -35.9 Tetrahedral Explosive gas XeO~- Colorless Octahedral Anions salts HXeO~-, H2XeOi-, H 3 Xe06" also exist 21-2 The Chemistry of Xenon 485

Fluorides Thermodynamic studies of Reactions 21-2.1 to 21-2.3

Xe + F2 = XeF2 (21-2.1)

XeF2 + F2 = XeF4 (21-2.2)

XeF4 + F2 = XeF6 (21-2.3) show that only these three fluorides exist. The three equilibria are established rapidly only above 250°C, and the synthesis of one either from the oth­ ers or instead of the others must be performed above this temperature. The three fluorides are volatile substances, subliming readily at 25°C. They can be stored in vessels, but XeF4 and XeF6 are exceptionally readily hydrolyzed, and even traces of water must be excluded.

Xenon difluoride (XeF2) is best made by interaction of Xe with a deficiency of

F2 at high pressures. The deficiency of F2 insures exclusive formation of the di­ fluoride. It dissolves in water to give solutions with a pungent odor of XeF2 . Hydrolysis is slow in acid solution, but rapid in the presence of bases, due to Reaction 21-2.4.

(21-2.4)

3 Such aqueous solutions are strong oxidizers, converting HCI to Cl 2 and Ce + to 4 Ce +. is also a mild fluorinating agent for organic compounds; for example, benzene forms C6H 5F.

Xenon tetrafluoride (XeF4 ) is the easiest of the three fluorides to prepare. On heating a 1:5 mixture of Xe and F2 at 400°C and about 6-atm pressure for a few hours, XeF4 is formed quantitatively. It resembles XeF2 except for its behavior on hydrolysis, as discussed later. will fluorinate aromatic rings in compounds such as toluene.

Xenon (XeF6 ) is obtained by the interaction ofXeF4 and F2 under pressure or directly from Xe and F2 at temperatures above 250°C and pressures greater than 50 atm. is extremely reactive, attacking even quartz as in Reaction 21-2.5.

(21-2.5)

Xenon hexafluoride is a strong acid according to the Lux-Flood definition that was discussed in Chapter 7. It accepts from other compounds and in­ serts fluoride ion in its place. The order of decreasing Lux-Flood acidity is

Any acid reacts by accepting oxide from any base beneath it in this series, and re­ placing it with fluoride. This can be useful in synthesis, and Reaction 21-2.6 is an example.

(21-2.6)

The colorless crystals of XeF6 contain both tetramers and hexamers, each 486 Chapter 21 I The Noble Gases

made up of XeF; units linked by unsymmetrical and bent F- bridges, as shown

in Fig. 21-1. Monomeric XeF6 in the liquid or the vapor has a distorted octahe­ dral structure because of a lone pair of electrons at Xe.

Xenon Fluoride Complexes

The xenon fluorides will react with strong Lewis acids such as SbFs or 1rFs to give adducts. The three types of adducts formed by XeF2 are XeF2' MFs, 2XeF2' MFs' and XeF2'2MFs, where M = Ru, Ir, Pt, and so on. Although XeF2'1Fs has a mol­ ecular rather than ionic structure, in most cases adduct formation involves fluo­ ride ion transfer to give structures that contain , such as XeF+ (formed by

loss ofF- from XeF2) , Xe2F; (which has a planar Structure 21-1),

F 2.14A ,/"'-..../"'-... Xe 151 0 Xe 1.90 A ,/" "'-... F F 21-1

and XeF; (formed by transfer of F- from XeF6 ). Examples include [XeF;][PtF6] and Reaction 21-2.7.

(21-2.7)

Xenon hexafluoride can act as a Lewis acid toward F- and can be converted to heptafluoro or octafluoro xenates as in Reactions 21-2.8 and 21-2.9.

(a) (b)

Figure 21-1 The tetrameric (a) and the hexameric (b) units that make up the struc­ ture of XeF6 . Each is built up of XeF; units bridged by F- ions. There are at least four crystalline forms of the substance, three of which are built up of tetramers and one which includes both tetramers and hexamers. 21-2 The Chemistry of Xenon 487

XeF6 + RbF -----+ RbXeF7 (21-2.8)

2 RbXeF7 -----+ XeF6 + Rb2XeF8 (21-2.9)

These octafluoroxenates are among the most stable xenon com­ pounds known and decompose only above 400°C.

Xenon-Oxygen Compounds

Xenon trioxide is formed in the hydrolysis of XeF4 and XeF6 according to Reactions 21-2.10 and 21-2.11.

3 XeF4 + 6 H 20 -----+ XeOs + 2 Xe +! O 2 + 12 HF (21-2.10)

XeF6 + 3 H 20 -----+ XeOs + 6 HF (21-2.11)

The colorless, odorless, and stable aqueous solutions of XeOs appear to con­ tain XeOs molecules. On evaporation of water, XeOs is obtained as a white del­ iquescent solid that is dangerously explosive. In basic solution, a xenate(Vl) ion (HXeOi) is formed, as in Reaction 21-2.12.

(21-2.12)

The ion HXeOi slowly disproportionates to give a xenate(VlII) (or ion, XeOt-), as in Reaction 21-2.13.

(21-2.13)

Perxenates are also formed by oxidation of HXe04 with ozone. The perxenate ions are yellow and are both powerful and rapid oxidizing agents. Salts such as

Na4Xe06"8H20 are stable and sparingly soluble in water. In alkaline solution, the main form is the ion HXeO~-, and are only slowly reduced by water. However, in acid solution, reduction by water ac­ cording to Reaction 21-2.14 is almost instantaneous, and the hydroxyl is involved as an intermediate.

(21-2.14)

When perxenate is heated with concentrated , (Xe04 ) is formed as an explosive and unstable gas. The aqueous chemistry of xenon is summarized by the potentials:

2.36 V 2.12V Acid solution H 4 Xe06 ) XeOs ) Xe 2.64 V XeF2 )Xe 0.94 V 1.26 V Alkaline solution HXeO~- )HXeO~ )Xe 488 Chapter 21 I The Noble Gases

21·3 Other Noble Gas Chemistry Radon might be expected to display even more chemistry than xenon, but be­ cause of the radioactivity of all radon isotopes, rather little has been learned about it. Apparently, at least one radon fluoride of uncertain composition does exist. The other noble gas atoms have higher ionization than the xenon atom, and they therefore are much less reactive. In a consistent manner those compounds formed by the lighter noble gases are less stable than those of xenon.

Krypton difluoride (KrF2 ) is obtained when an electric discharge is passed through a mixture of Kr and F2 at -180°C. It resembles XeF2 being a volatile white solid constructed of linear FKrF molecules, but differs in that it is ther­ modynamically unstable, as indicated by Reactions 21-3.1 and 21-3.2.

1 KrF2 (g) = Kr(g) + F2 (g) !:lHO = -63 kJ mol- (21-3.1)

1 XeF2 (g) = Xe(g) + F2 (g) !:lHo = 105 kJ mol- (21-3.2)

Some compounds with Xe-C bonds are known. An example is C6F5Xe+, which is made by Reaction 21-3.3.

(21-3.3)

STUDY GUIDE

Study Questions A. Review 1. What is the origin of terrestrial helium? 2. Why do the boiling points of the noble gases vary systematically with atomic number? What interatomic forces account for this variation?

3. How are XeF2, XeF4 , and XeF6 prepared?

4. Write balanced equations for the hydrolyses of XeF2' XeF4' and XeF6' 5. How are xenates and perxenates made?

B. Additional Exercises. 1. Write balanced equations for (a) The oxidation of HXeO:; by ozone.

(b) The reduction of Xe03 by 1- in acid solution to give Xe. (c) Oxidation ofHCI by XeF2­ 3 (d) Oxidation ~f Ce + by XeF2. (e) Synthesis of [XeY+][SbF6]. 2. Show the electron-pair geometry around each atom in Xe2F; and classifY each atom

using the ABxEy system. 3. Draw the Lewis diagrams and show the electron-pair geometries around each atom in Supplementary Reading 489

(a) XeF4 (b) Xe03

(c) XeOt (d) XeOF4 (e) XeF; (f) HXe0:t (g) XeF~- (h) XeF7"

4. Prepare a MO description of the bonding in XeF2 using only a colinear set of p or­ bitals. 5. Discuss the following reactions in terms of the Lux-Flood definition of acids and bases:

(a) XeF6 + Xe02F2 ------> 2 XeOF4

(b) Xe03F2 + Xe02F2 ------> XeOF4 + Xe04

(c) XeF2 + Na4 Xe06 ------> no reaction C, Questions from the Literature of

1. Consider the work byJ. L. Huston, Inorg. Chem., 1982, 21, 685-688.

(a) Write a plausible sequence of reactions for the hydrolysis ofXeF4 in excess water. (b) Explain Reactions 1, 2, 4,11,12,16, and 17 in terms of the Lux-Flood defini­ tion of acids and bases. Identify the acid and base in each reaction. (c) Prepare an order of base strength for each of the bases featured in the reactions of (b). 2. Consider the series of papers by N. Bartlett et aI., Inorg. Chem., 1973, 12, 1713, 1717, 1722. (a) Explain how each of the following adducts may be considered to arise from flu­ oride ion transfer to give ionic compounds with weak F- bridges in the solid

state: (i) XeF4 '2SbFs; (ii) XeF2 'RuFs and XeF4 'RuFs; (iii) XeF4 'SbFs and XeF4 '2SbFs; and (iv) XeOF4'SbFs and XeOF4 '2SbFs (b) Describe the geometries (ignoring the weak F- bridges) of the cations in the

compounds of (a). Use the ABxE y classification, and pay close attention to the positions of the lone electron pairs.

(c) Do the oxygen atoms in XeOF; and Xe02F2 prefer equatorial or axial positions?

SUPPLEMENTARY READING

Bartlett, N., The Chemistry of the Noble Gases, Elsevier, Amsterdam, 1971. Halloway,J. H., Noble Gas Chemistry, Methuen, New York, 1968. Hawkins, D. T., Falconer, W. E., and Bartlett, N., Noble Gas Compounds, A Bibliography 1962-1976, Plenum, New York, 1978. Hopke, P. K., Ed., Radon and its Decay Products, ACS Symposium Series, American Chemical Society, Washington, DC, 1987. Lazlo, P. and Schrobilgen, G. J., "One or Several Pioneers? The Discovery of Noble­ Gas Compounds," Angew. Chem. Int. Ed. Eng., 1988, 27, 479-489. Moody, G. J., "A Decade of Xenon Chemistry," j. Chem. Educ., 1974, 51, 628. Nazeroff, W. K., Ed., Radon and its Decay Products in Indoor Areas, Wiley, New York, 1988. Ozima, M. and Podosek, F. A., Noble Gas Geochemistry, Cambridge University Press, Cambridge, UK, 1983. Selig, H. and Halloway, J. H. Topics in Current Chemistry No. 124, F. L. Bosche, Ed., Springer-Verlag, Berlin, 1984. Seppelt, K. and Lentz, D. Progress in Inorganic Chemistry, Vol. 29, Wiley-Interscience, New York, 1982.