2P32 Principles of Inorganic Chemistry Dr. M.

Pilkington

Lecture 33 Group 18 (8A)

The Noble Gases

Elements
Compounds
The Noble Gases

He balloons
Ne Neon lights
Ar lazers
l
Kr
Xe gas from which the first compounds were discovered.
Rn radioactive

Theses six noble gases are found in group 18 of the periodic table. These
elements were considered to be inert gases until the 1960's, because their
oxidation number of 0 p
prevents the noble gases
g from formingg compunds
p readily.
y

All of these gases have the greatest number of electrons possible in their outer
energy lever, (2 for Helium, 8 for the rest) making them stable and for the most
part,, unreactive.
p
Helium

Helium is the second lightest element, with an atomic mass of 4.0026. It is used
i helium
in h li baloons,
b l blimps,
bli zepelins,
li deep
d sea diving,
di i low
l ttemperature
t experiments
i t
etc, to make high voices.... It was discovered by Sir William Ramsey in 1895. It's
name comes from the Greek word helios which means sun.

At room temperature, helium is a colorless and odorless gas. It has 2 electrons

and 2 protons. It is the only nonreactive element without eight electrons. The
most common helium atom has 2 neutrons but it can have 3 or even 4. All isotopes
are stable.

Helium has one energy level with two electrons and has a hexagonal structure. It
has a density (at 283 K) of 0.1785 grams per centimeter cubed.
 Helium has the lowest melting point of any element, and its boiling point is close
to absolute zero. Helium can never be a solid (unless you dramatically change the
pressure).
)
The heat of helium is very high. It is the 2nd most abundant element in the
universe and is often found on very hot stars.
Helium makes up about 23% of the mass of the universe. In fact, it was found on
th sun b
the before
f it was di
discovered d on earth!
th! It iis very rare on earth.
th Th
The earth's
th'
gravity isn't strong enough to trap a lot of helium. It does not conduct
electricity (very very little). It doesn't react with air or fire. It is unreactive
but has formed compounds with flourine.
The sun is constantly producing helium.
helium
 We often use the word neon to refer to color. Neon orange, neon yellow, and
neon green. This is because neon is used to create such bright colors. when
electricity moves through it, it glows red. However, it is a bad electrical
conductor.
Neon is a nonreactive colorless and odorless ggas. It was discovered byy Sir
William Ramsey and Morris William Travers in 1898. It is obtained in the form of
liquid air.
Its name comes from the Greek word neos which means new.
Neon has 10 pprotons, 10 electrons, and (most commonly)y 20 neutrons. It has two
energy levels. The first energy level has two electrons, and the second one eight.

It has an atomic mass of 20.1797 amu and a cubic structure.

Its density (at
( 293K is 0.901 grams per centimeter cubed. It
was thought to be inert, but has been reported to have form
highly, unstable compounds with flourine. Its existance is still
questioned.
 Neon is often used in lights. It gives off a orangish red (see picture at the
bottom) glow. When combined with other gases and elements such as argon, you
end
d up with
ith all
ll sorts
t of
f "neon"
" " colors
l ((see b
below).
l )

Neon is found in the atmoshere( very little because it is lighter than air. It only
makes upp 0.0018%),
), in rocks in the earth's crust,, and in space(where
p ( it is a lot
more abundant than it is here on earth.
Argon

Argon was discovered in 1894 by Sir Willian Ramsey and Lord Rayleigh. It's
name comes from the greed word argon, meaning inactive.

Argon is used for lighting, and is obtained from the air.

Argon has 6 isotopes. Of these 6, the stable isotopes of Argon are Ar-36, Ar-
38, and Ar
Ar-40.
40.

Argon is the third most common gas in the atmosphere. It takes up 1% of the
atmosphere, which is an increase since the Earth was created. This happens
because potassium that is radioactive eventually decays into argon. Argon is a
colorless,
l l ss and
nd odorless
d l ss gas.
s

Argon is used in fluorescent and electric lighting. It is also used as an inert gas
for certain types of welding. Another use is a blanket for the production of
reactive elements.
Krypton

Krypton was discovered in 1898 by Sir William Ramsey. Krypton comes from the
greek word, kryptos, meaning hidden.

It is g
gathered by
y distillation from
f m liquid
qu air..

Krypton is one of the rarest gasses in the world, making up only 1/ 1 mil of the
volume of the atmosphere.

Krypton is an odorless, colorless gas, and is non-reactive to all elements except

for fluorine gas.

Krypton is used as a low-pressure filling gas for fluorescent lights. It can also
be used in specific camera flashes.
flashes
Xenon
Date of Discovery: 1898

Discoverer: Sir William Ramsay.

Name Origin: From the Greek word xenon (stranger).
Uses: power lamps, bubble chambers.
Obtained From: liquid air.

Isolation of xenon:
Xenon is present to a small extent in the atmosphere (less than one ppm by
volume) and is obtained as a byproduct from the liquefaction and separation of
air. This would not normally be carried out in the laboratory and xenon is
available commercially in cylinders in high pressure.
pressure

Metallic xenon is produced by applying several hundred kilobars of pressure.

Xenon in a vacuum tube produces a blue glow when excited by an electrical
discharge and finds use in strobe lamps. It is an odorless, colorless, inert gas.
Radon

The name comes from the Latin radius for ray or beam

Various names were first associated with this element but radon became the
ff
official name
m in 1923.

Friedrich Dorn is generally associated with its actual discovery.

In 1908 Ramsay and his co-workers

co workers isolated and determined the density of
the last of the noble gases, which is the densest gaseous element known.

In 1904, a most unusual Nobel Prize ceremony occurred. The winner in physics
for his work in the densities of gases and the discovery of argon was Lord
Rayleigh.

The winner in chemistry for his work in discovering the inert gaseous elements
in air and their places in the periodic table was William Ramsay.
Ramsay

Sometimes the divisions between two scientific fields are very small.
Fundamental Properties and the Network
Table 19.1 in Rogers gives you a table of the fundamental properties of the group
18 elements.
l t

With very high effective nuclear charges operating on the valence electrons of
the group 18 elements, their ionization energies are exceedingly high.

The IEs do slowly decrease as we move down the group, as expected as it gets
easier to remove an electron from the heavier elements.

The elements have little ability to attract electrons to themselves and no

electronegativities are listed in the table for this reason.

Electron aff
affinities
n t es can be est
estimated
mated and become more positive
pos t ve going
go ng down the
group, a trend that is consistent with the idea that electrons are being added to
orbitals farther and farther removed from the effective nuclear charge.

As m
more
r electrons
ctr n arare a
associated
c at w with
th th
the h
heavier
a r noble
n ga
gases,, the
th atoms
at m are
ar
more polarizable and the van der Waals interactions between them become
stronger.

Consequently
q y the boiling
g and melting
m g pts
p increase going
g g down the group.
g p
 The inertness of these elements provided a vital link in the empirical and
theoretical understanding of the periodic table.

A 0 valence was immediately recognized as providing a bridge between the

halogens (-1) and the alkali metals (+1).

Since these compounds are essentially unreactive only a few compounds exist:

Noble-gas hydrates in which the atoms are trapped in an ice-like lattice when
water is frozen under high pressure of the gas have been prepared.

A few organic compounds also form similar structures called clathrates.

The hydrates
y are of general formula E.6H2O, where E = Ar, kr, Xe, but these are
not compounds in the usual sense of the term since they neither contain ionic nor
covalent bonds.

There has been over the years, spectroscopic evidence for a few fleetingly stable
cations involving
l the
h noble
l gases, HeH+, ArH+ , He2+ Kr2+, NeXe+ and Xe2+.

Until 1962 NO stable neutral compounds of the noble gases were known, hence
the name inert gases was an appropriate group name.
 Neil Bartlett an English Chemistry working at UBC was interested in fluorides of
Pt and related metals.

Bartlett was investigating PtF6 a deep red gas that is a strong oxidizing and
fluorinating agent.

It had to be manipulated in a completely air- and water- free environment.

He noticed that it appeared to be reacting with the glass of his apparatus to
give a brown-orange solid.

Closer investigation revealed small amounts of oxygen present in his vacuum line,
and that the orange brown solid was a compound called dioxygen
hexafluoroplatinate(V).
p ( )

O2(g) + PtF6(g) O2+PtF6-(s)

The diatomic oxygen is being oxidized by the platinum hexafluoride.

It occurred to Bartlee that the ionization energies of molecular oxygen and the
xenon atom (1180 KJ/mol and 1167 KJ/mol respectively) were remarkably similar.
 He decided to try the same reaction with xenon replacing the diatomic oxygen and
carefully noted the pressure of each.
When he allowed the two gases to mix, an orange-yellow solid was immediately
formed, and the pressure of the remaining xenon was consistent with the
formation of a 1:1 compound.
The reaction was initially
y represented
p as:
Xe(g) + PtF6(s) Xe+PtF6-
colourless red orange-yellow solid

Further investigations demonstrated that the reaction was more complicated and
this is still not well understood to-date:

Xe(g) + 2PtF6(g) 250C [XeF+][PtF6-] + PtF5

[XeF+][PtF6] + PtF5 600C [XeF+][Pt2F11-]

The exact nature of this reaction, though important was not significant as the
fact that it was no longer correct to regard xenon as an inert gas.
Noble perhaps it was, but no longer inert!
Fluorides
A flurry
y of activity
y followed Bartletts announcement of the preparation
p p of the
first xenon compound.
A few months later a group was able to prepare xenon tetrafluoride by direct
reaction of the elements.
They places a 1:5 Xe/F2 ratio in a nickel container and after an hr at 4000C and
6atm, the xenon was completely consumed.
They sublimed the mixture to produce brilliant, colourless crystals of XeF4

Xe(g) + 2F2(g) 4000C XeF4(s)

6 atm
The tetrafluoride is the easiest to make, the most stable and the best
characterized xenon fluoride compound.
compound It is an excellent fluorinating agent.
agent
Many other compounds e.g. XeF2, XeF6, XeO2, XeO3, XeO4.
Aqueous solutions of XeO3 are often referred to as xenic acid.
Xenic acid can be oxidized by
y ozone, for example
p to the perxenates
p
3XeO3 + 12NaOH(aq) + O3 3Na4XeO6 + 6H2O
A powerful and rapid oxidizing agent, the XeO64- anion has an octahedral
configuration.
 Krypton difluoride can be synthesized by passing an electrical discharge through
the constituent elements at -1960C. It is a volatile white solid containing
g
molecules of KrF2 units.

A few compounds with bonds to nitrogen are known. Both kr and Xe have been
reported to form a compound of general formula
formula, where E = Kr,
Kr Xe.
Xe

HC N EF+ AsF6-

The krypton compound detonates violently with a flash white light.

Radon
R d reacts spontaneously l at room temp, with
i h fl
fluorine
i or chlorine
hl i trifluoride
ifl id to
form radon trifluoride. This compound is not well-characterized due to the
difficulties working with the extremely radioactive radon.