1274 G R O U P vin A, B A N D C : STANLEY E.

LIVINGSTONE

5.11. C O M P L E X E S OF I R I D I U M ( V )

The only complexes are those containing the [IrF 6 ]" anion. The potassium salt K[IrF 6 ]
can be made by treating a mixture of IrBr3 and KBr with BrF3. Other alkali metal salts are
known 198. The compounds [NO][IrF6], SeF^IrFs and SeF4(IrF5)2 are also known412'41^.

6. PALLADIUM

6.1. GENERAL C H E M I S T R Y

Palladium is a silver-white ductile metal which has a great affinity for hydrogen, being
able to absorb that gas to a greater degree than any other metal. When in the form of
sponge or powder, the metal can absorb up to 900 times its own volume of hydrogen. The
amount absorbed decreases with increase in temperature for a given pressure. The absorp-
tion is accompanied by expansion of the solid and the lattice constant may increase by as
much as 5 %. At the same time the electrical conductivity and magnetic susceptibility fall.
These data and the shape of the pressure-concentration isotherm suggest the existence of
definite hydrides below 300°C. Below this temperature the isotherm exhibits a horizontal
pressure-invariant portion in which the so-termed a- and ß-phase hydrides coexist. Although
it has been suggested that the stoichiometric compound Pd2H is formed, it is now accepted
that the composition of the hydride phase varies continually with temperature and that
there is no simple ratio of hydrogen atoms to palladium atoms in either the a- or the /?-phase.
Hydrogen and deuterium are able to diffuse through heated massive palladium. This is
specific for hydrogen and deuterium ; helium, for example, has no such power.
It has been suggested that interaction between hydrogen and palladium atoms or ions
could yield Pd-H or Pd-H+ entities which could be considered equivalent to an equal
number of silver atoms or ions, since Pd-H is isoelectronic with Ag. This hypothesis is
supported by evidence that the solubility of hydrogen in Pd-Ag alloys decreases more or
less linearly with silver content. However, any approximation to a linear dependence of
hydrogen solubility on silver content breaks down over substantial ranges of reference
pressure when the solubility of hydrogen is more rigorously defined with reference to the
pressure of hydrogen gas in equilibrium.
Another hypothesis which has been proposed is that the hydrogen is dissolved as protons
which are located in interstitial positions in the lattice without being specifically bound to
a particular metal atom. The effects of the electrons from the absorbed hydrogen on the
structure of palladium were then considered. Until 1965 it had been accepted that the mag-
netic susceptibility data were consistent with there being 0.6 "holes" per palladium atom
in the Ad band, and it was proposed that for values of H:Pd up to 0.6, these holes were
filled by electrons from the hydrogen atoms. Furthermore, since the value of H :Pd can,
under certain circumstances, exceed 0.6, it was proposed that the additional electrons were
accommodated in the 5*y band. However, a recent theoretical analysis of the palladium
band structure suggests that there are only 0.36 holes in the Ad band per metal atom. If
the hydrogen is absorbed as protons, it is behaving as an alloying metal and this would
account for the retention of thermal and electrical conductivity and malleability.
Analogies to the Pd-H system are provided by the M-H systems for the Group V
metals (M = V, Nb, Ta), where with absorption of hydrogen there is still a retention of