15.

24 THE GROUP 18/VIII ELEMENTS 659

TA B L E 1 5 . 1 2 The Group 18/VIII Elements (the Noble Gases)

Valence configuration: ns2np6

Normal form: colorless monatomic gas

Molar mass Melting point Boiling point

Z Name Symbol (g)mol!1) (°C) (°C)
2 helium He 4.00 — %269 (4.2 K)
10 neon Ne 20.18 %249 %246
18 argon Ar 39.95 %189 %186
36 krypton Kr 83.80 %157 %153
54 xenon Xe 131.29 %112 %108
86 radon* Rn (222) %71 %62

*Radioactive.

GROUP 18/VIII: THE NOBLE GASES

The elements in Group 18/VIII, the noble gases, get their group name from their very
low reactivity (Table 15.12). Experiments on the gases and, later, recognition of their
closed-shell electron configurations (ns2np6) prompted the belief that these elements
were chemically inert. Indeed, no compounds of the noble gases were known until
1962. That year, the British chemist Neil Bartlett synthesized the first noble-gas com-
pound, xenon hexafluoroplatinate, XePtF6. Soon after, chemists at Argonne National
Laboratory made xenon tetrafluoride, XeF4, from a high-temperature mixture of
xenon and fluorine.

15.24 The Group 18/VIII Elements

All the Group 18/VIII elements occur in the atmosphere as monatomic gases; together they
make up about 1% of its mass. Argon is the third most abundant gas in the atmosphere
after nitrogen and oxygen (discounting the variable amount of water vapor). All the noble
gases except helium and radon are obtained by the fractional distillation of liquid air.
Helium, the second most abundant element in the universe after hydrogen, is rare
on Earth because its atoms are so light that a large proportion of them reach high speeds
and escape from the atmosphere; unlike hydrogen, they cannot be anchored to com-
pounds. However, helium is found as a component of natural gases trapped under rock
formations (notably in Texas), where it has collected as a result of the emission of * particles
by radioactive elements. An * particle is a helium-4 nucleus (4He2'), and an atom of the
element forms when the particle picks up two electrons from its surroundings.
Helium gas is twice as dense as hydrogen under the same conditions. Nevertheless,
because its density is still very low and it is nonflammable, it is used to provide buoy-
ancy in airships such as blimps. Helium is also used to dilute oxygen for use in hospi- 100
Solid
tals and in deep-sea diving, to pressurize rocket fuels, as a coolant, and in helium–neon
lasers. The element has the lowest boiling point of any substance (4.2 K), and it does 10
Liquid
Pressure (atm)

not freeze to a solid at any temperature unless pressure is applied to hold the light, (helium-I)
mobile atoms together. These properties and its chemical inertness make helium useful 1
Liquid
for cryogenics, the study of matter at very low temperatures, such as those used for the (helium-II)
study of superconductivity (Section 6.14). Helium is the only substance known to have 0.1
more than one liquid phase. Its phase diagram indicates the temperature and pressure Gas
ranges over which each phase is stable (Fig. 15.55). Below 2 K, liquid helium-II shows 0.01
the remarkable property of superfluidity, the ability to flow without viscosity.
Neon, which emits an orange-red glow when an electric current flows through it, is 1 2 3 4 5 6
widely used in advertising signs and displays (Fig. 15.56). Argon is used to provide an inert Temperature (K)
atmosphere for welding (to prevent oxidation) and to fill some types of light bulbs, where
FIGURE 15.55 The phase diagram for
it conducts heat away from the filament. Krypton gives an intense white light when an elec- helium-4 shows the two liquid phases of
tric discharge is passed through it, and so it is used in airport runway lighting. Because helium. Helium-II, the low-temperature
krypton is produced by nuclear fission, its atmospheric abundance is one measure of liquid phase, is a superfluid.
660 CHAPTER 15 THE ELEMENTS: THE MAIN GROUP ELEMENTS

FIGURE 15.56 The colors of this fluorescent lighting art by Tom Anthony are due to emission from
noble-gas atoms. Neon is responsible for the red light; when it is mixed with a little argon, the color
becomes blue-green. The yellow color is achieved by coating the inside of the glass with phosphors
that give off yellow light when excited.

2370
worldwide nuclear activity. Xenon is used in halogen lamps for automobile headlights and
in high-speed photographic flash tubes; it is also being investigated as an anesthetic.
2080
The radioactive gas radon seeps out of the ground as a product of radioactive decay
processes deep in the Earth. There is now some concern that its accumulation in build-
ings and its nuclear decay products can lead to dangerously high levels of radiation.
The noble gases are all found naturally as unreactive monatomic gases. Helium
1520 has two liquid phases; the lower-temperature liquid phase exhibits superfluidity.
1350
1170 15.25 Compounds of the Noble Gases
1036 The ionization energies of the noble gases are very high but decrease down the group
(Fig. 15.57). Xenon’s ionization energy is low enough for electrons to be lost to very
electronegative elements. No compounds of helium, neon, and argon exist, except
under very special conditions, such as the capture of atoms of He and Ne inside a
buckminsterfullerene cage. Krypton forms only one known stable neutral molecule,
KrF2. In 1988, a compound with a KrßN bond was reported, but it is stable only below
%50°C. This leaves xenon as the noble gas with the richest chemistry. It forms several
He Ne Ar Kr Xe Rn
compounds with fluorine and oxygen, and compounds with XeßN and XeßC bonds
have been reported, such as (C6F5)2Xe.
FIGURE 15.57 The ionization energies The starting point for the synthesis of xenon compounds is the preparation
of the noble gases decrease steadily
down the group. The values shown are
of xenon difluoride, XeF2, and xenon tetrafluoride, XeF4, by heating a mixture of the
in kilojoules per mole. elements to 400°C at 6 atm. At higher pressures, fluorination proceeds as far as xenon
hexafluoride, XeF6. All three fluorides are crystalline solids (Fig. 15.58). In the gas
phase, all are molecular compounds. Solid xenon hexafluoride, however, is ionic, with
a complex structure consisting of XeF5' cations bridged by F% anions.
The xenon fluorides are used as powerful fluorinating agents (reagents for attach-
ing fluorine atoms to other substances). The tetrafluoride will even fluorinate platinum
metal:
Pt(s) ' XeF4(s) ¡ Xe(g) ' PtF4(s)
The xenon fluorides are used to prepare the xenon oxides and oxoacids and, in a series
of disproportionations, to bring the oxidation number of xenon up to '8. First, xenon
tetrafluoride is hydrolyzed to xenon trioxide, XeO3 in a disproportionation reaction:
6 XeF4(s) ' 12 H2O(l) ¡ 2 XeO3(aq) ' 4 Xe(g) ' 3 O2(g) ' 24 HF(aq)

FIGURE 15.58 Crystals of xenon tetrafluoride, XeF4. This compound was first prepared in 1962 by
the reaction of xenon and fluorine at 6 atm and 400°C.