15.

Chapter 18 – The Group 18 Elements: The Noble Gases Element m.p. (°C) b.p. (°C)
He –– –269
All the elements in Group 18 are colorless, odorless, monatomic gases at Ne –249 –245
room temperature. They neither burn nor support combustion; in fact,
Ar –189 –186
they make up the least reactive group in the Periodic Table with only
xenon forming a variety of compounds. The very low melting and boiling Kr –157 –152
points of the noble gases indicate that the dispersion forces holding the Xe –112 –109
atoms together in the solid and liquid phases are very weak. The
increase in the melting and boiling points with increasing atomic weight is Rn –71 –62

due to the increase in polarizability.

To date, chemical compounds have been isolated at room temperature only for the three heaviest
members of the group: krypton, xenon, and radon. Few compounds of krypton are known and
tend to be very unstable at room temperature, whereas xenon has an extensive chemistry. The
study of radon chemistry is very difficult because all the isotopes of radon are highly radioactive; the
longest lived isotope has a half-life of less than 4 days.

Unique Features of Helium

When helium is cooled to as close to absolute zero as possible, it is still a liquid. At 1.0 K, a
pressure of about 2.5 MPa is required to cause it to solidify. However, liquid helium is an
amazing substance. At ambient pressure, the gas condenses at 4.2 K to form an ordinary liquid
(helium I), but when cooled below 2.2 K, the properties of the liquid (now helium II) are
dramatically different. For example, helium II is an incredibly good thermal conductor, 106
times greater than helium I and much better than even silver, the best metallic conductor at
room temperature. Even more amazing, its viscosity drops to close to 0. When helium II is
placed in an open container, it literally "climbs the walls" and runs out over the edges. These
and many other bizarre phenomena exhibited by helium II are best interpreted in terms of
quantum behavior in the lowest possible energy states of the element. A full discussion is in the
realm of quantum physics.

The Chemistry of the Noble Gases

In 1962 Neil Bartlett and D.H. Lohmann at the University of British Columbia discovered that
PtF 6 was a sufficiently potent oxidizing agent to oxidize dioxygen to the dioxygenyl cation, O2+.

O2 + PtF 6 ÷ [O 2]+ [PtF 6]!

Since the ionization energy of O2 (-1177 kJ/mol) is similar to that of Xe (-1170 kJ/mol),
Bartlett reasoned that PtF 6 might also oxidize Xe. The direct reaction of Xe with PtF6 yielded a
red-orange crystalline product which was insoluble in CCl4 and originally thought to be Xe+
[PtF 6]! . Later work suggested that the product was likely [XeF]+ [Pt2F11]! or a mixture of
[XeF]+ [Pt2F11]! and [XeF]+ [PtF 6]! .
 15.2

Xenon Fluorides

The first binary compounds of Xe to be prepared were fluorides, and since fluorine is the
only element that reacts directly with Xe, the fluorides also serve as starting materials for the
synthesis of other Xe compounds. All of the fluorides are white solids and have negative
free energies of formation at 25°C, that is, they are stable to dissociation at room
temperature

Xenon difluoride is prepared by the reaction of excess xenon with fluorine at high pressure
aided by heating or electromagnetic radiation:

Xe (g) + F2 (g) ÷ XeF2 (s)

The preparation of xenon tetrafluoride is carried out by heating a 1:5 xenon/fluorine mixture to
about 400°C under a pressure of about 6 atmospheres for several hours:

Xe (g) + 2 F2 (g) ÷ XeF4 (s)

These conditions are also employed in the preparation of XeF6, except that a large excess of
F2 is used and pressures of >50 atm are required for quantitative conversion.

Xe (g) + 2 F2 (g) ÷ XeF4 (s)

F
The structures of XeF2 and XeF4 are predictable on the basis of the VSEPR
model. With 8 valence shell electrons from the xenon atom and 2 additional Xe
electrons from the two fluorine atoms, there are 10 electrons surrounding
the xenon atom in XeF2. Thus, XeF2 is a linear molecule. F

The structure of XeF4 is derived from the fact that there are 12 electrons
surrounding the Xe atom in the molecule (8 from the Xe atom and 1 F
from each fluorine atom). Therefore, the 12 electrons reside in six F Xe F
orbitals pointing toward the comers of an octahedron, and the molecular F
structure is square planar.

The structure of XeF6 is not a regular octahedron because the xenon atom
has 14 valence electrons. The IF7 molecule is similar in this regard, and it F
F F
has a pentagonal bipyramid structure. However, with one unshared pair of
Xe
electrons, there is some question as to where the unshared pair resides. F
Also, the molecule is not rigid and it is described as an capped F F
octahedron.
 15.3

In condensed phases, monomeric

XeF6 exists in equilibrium with
tetrameric and hexameric units in
which square pyramidal XeF5+ units
are bridged by F! ions. Thus, the
structure of XeF6 is not nearly as
simple as those of XeF2 and XeF4.

In general, intermolecular forces are

related to the structures of the molecules. Both XeF2 and XeF4 are nonpolar, so it is
interesting that the melting points of XeF2, XeF4, and XeF6 are 129, 117, and 50°C,
respectively, but the solids readily sublime.

Reactions of Xenon Fluorides

All of the xenon fluorides hydrolyze in water, but xenon difluoride hydrolyzes only very
slowly in acidic solutions and a 0.15 M solution can be prepared at 0°C. In basic solution
the hydrolysis occurs rapidly:

XeF2 (s) + 2 OH! (aq) ÷ Xe (g) + ½ O2 (g) + 2 F! (aq) + H2O (R)

The hydrolysis of XeF4 is extremely vigorous, and it undergoes a disproportionation

reaction that is similar to that of the halogens,

6 XeF4 + 12 H2O ÷ 2 XeO 3 + 4 Xe + 3 O2 + 24 HF

which represents Xe(IV) producing Xe(VI) and Xe(0). The oxide, XeO 3, is a very
dangerously explosive compound.
Hydrolysis of XeF6 also produces this oxide by the reaction

XeF6 + 3 H2O ÷ XeO 3 + 6 HF

although the reaction appears to take place in two steps as shown by the following
equations:

2 XeF6 + H2O ÷ 2 XeOF4 + 2 HF

XeOF4 + 2 H2O ÷ XeO 3 + 4 HF

 15.4

The fluorides are strong fluorinating agents. For example, xenon difluoride can be used to
fluorinate double bonds in organic compounds. It is a very “clean” fluorinating agent, in that
the inert xenon gas can be easily separated from the desired product:

XeF2 (s) + H2C=CH2 (g) ÷ H2FC=CFH2 (g) + Xe (g)

A useful derivative of uracil is 5-fluorouracil, which is used in the treatment of some types of
skin cancer. One preparation of the compound is by the fluorination of uracil with XeF2.

O O

H F H

N N
+ XeF2 + Xe + HF

N O N O

The highest oxidation state of many fluorides can be produced by using xenon fluorides as
reagents. For example, xenon tetrafluoride will oxidize sulfur tetrafluoride to sulfur
hexafluoride:

XeF4 (s) + 2 SF4 (g) ÷ 2 SF6 (g) + Xe(g)

Previously, several reactions of interhalogens were shown in which cations were produced
by a reaction with a strong fluoride ion acceptor. A reaction of this type is

ClF 3 + SbF5 ÷ ClF 2+SbF6!

The xenon fluorides undergo similar reactions with fluoride

acceptors Such as SbF5, AsF5, TaF5, and PtF 5. The reaction of F
XeF2 with SbF5 can produce XeF+ Sb2F11! , XeF+SbF6! or Xe Xe
Xe2F3+ SbF6! with F! bridges between Xe centers in the cation. F F
Thus, Xe2F3+ represents a fluoride ion bridging between two 151o
XeF+ ions as shown.

F
In species that contain the XeF+ ion, the Xe is associated
with the MF6! anions by attaching to one of the fluoride ions F F
M
in the complex. F F Xe F
F
 15.5

The XeF3+ cation is generated when XeF4 reacts with BiF 5 as shown by the equation

XeF4 + BiF 5 ÷ XeF3+BiF 6!

Solid XeF6 contains XeF5+ ions that have fluoride ions bridging them. The cation is also
generated when XeF6 reacts with pentafluorides such as RuF5:

XeF6 + RuF5 ÷ XeF5+RuF6!

A cation having the composition Xe2F11+ that has the arrangement

F5Xe+ @ @ @F! @ @ @ XeF5+ has also been identified.

In some cases, XeF6 itself forms anions such as XeF7! and XeF82! by virtue of its Lewis
acidity. A general reaction can be written as

XeF6 + MF ÷ M+XeF7!

When heated, some compounds of this type undergo a reaction to produce M2XeF8 and
XeF6.

Xenon Oxyfluorides and Oxides

Xenon oxides are prepared from the fluorides. As we have already mentioned, hydrolysis
of XeF4 and XeF6 lead to the formation of XeO3 by reactions that can be shown as:

6 XeF4 + 12 H2O ÷ 2 XeO 3 + 4 Xe + 24HF + 3 O2

XeF6 + 3 H2O ÷ XeO 3 + 6 HF

The latter reaction probably involves the steps

XeF6 + H2O ÷ XeOF4 + 2 HF

XeOF4 + 2 H2O ÷ XeO 3 + 4 HF

These reactions are similar to the hydrolysis of PCl5, which can lead to OPC13 when a
limited amount of water is present.

Solid XeO 3 is a violently explosive white solid that has a very high positive
heat of formation of approximately 400 kJ/mol. Since the four atoms in Xe
XeO 3 have a total of 26 valence shell electrons, the predicted structure has O O
three bonds and an unshared pair of electrons surrounding the xenon atom. O
However, the resulting +3 formal charge on the xenon atom indicates that
there should be contributions to the actual structure from resonance
structures having multiple bonds between Xe and O.
 15.6

In the presence of OH! the reaction of XeO 3 leads to the formation of a hydrogen xenate
(HXeO 4! ) ion:

XeO 3 + OH! ÷ HXeO 4!

Disproportionation of this unstable species occurs according to the equation

2 HXeO 4! + 2 OH! ÷ XeO 64! + Xe + O2 + 2 H2O

Solid perxenate (XeO 64! ) salts can be obtained that contain cations of Group IA and IIA
metals. The XeO64! ion has a very weak conjugate acid, so the hydrolysis reactions

XeO 64! + H2O º HXeO 63! + OH!

HXeO 63! + H2O º H2XeO 62! + OH!

are extensive and the solutions are basic as well as very strong oxidizing agents.

In reactions that are very similar to that between PCl5 and P4O10,

6 PCl5 + P4O10 º 10 OPCl3

xenon fluorides react with xenon oxides to produce oxyfluorides:

XeF6 + 2 XeO 3 ÷ 3 XeO 2F2

2 XeF6 + XeO 3 ÷ 3 XeOF4

The Chemistry of Krypton and Radon

Krypton difluoride is obtained when an electric discharge is passed through Kr and F2 at

!183°C, or when the gases are irradiated with high-energy electrons or protons. It is a
volatile white solid that decomposes slowly at room temperature. It is a highly reactive
fluorinating agent.

The linear KrF2 molecule is thermodynamically unstable, whereas XeF2 is stable, as the
following free energies of formation show:

Kr (g) + F2 (g) ÷ KrF2 (s) )Gf° = +95 kJ

Xe (g) + F2 (g) ÷ XeF2 (s) )Gf° = !90 kJ

 15.7

No other molecular fluoride of Kr has been isolated. The cationic species KrF+ and Kr2F3+
are formed in reactions of KrF2 with strong fluoride acceptors such as AsF5 and SbF5, and
compounds have formulas such as KrF+Sb2F11! , KrF+SbF6! , and Kr2F3+AsF6! . The KrF+
salts can be used to fluorinate NF3 to NF4+.

There is some evidence for KrFe(CO)5+ in gamma-irradiated matrices at low temperatures.

Since radon has only a short half-life, study is difficult but tracer studies allow some
properties to be deduced, for example, the formation of RnF 2, RnF+TaF6! , and possibly
RnO3. Oxidation of Rn by ClF 3 and study on a fluorinated ion-exchange material (Nafion)
suggests that Rn+ can displace Na+ or K+.