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TRANSITION METAL
CHEMISTRY
Sc [Ar] 3d14s2
Ti [Ar] 3d24s2
V [Ar] 3d34s2
Cr [Ar] 3d54s1
Mn [Ar] 3d54s2
Fe [Ar] 3d64s2
Co [Ar] 3d74s2
Ni [Ar] 3d84s2
Cu [Ar] 3d104s1
Zn [Ar] 3d104s2
You will notice that the pattern of filling isn't entirely tidy! It is
broken at both chromium and copper.
Masresha Amare (PhD) 7
This is something that you are just going to have to accept.
There is no simple explanation for it which is usable at this
level. Any simple explanation which is given is faulty!
People sometimes say that a half-filled d level as in
chromium (with one electron in each orbital) is stable, and
so it is - sometimes! But you then have to look at why it is
stable. The obvious explanation is that chromium takes up
this structure because separating the electrons minimises
the repulsions between them - otherwise it would take up
some quite different structure.
You have already come across the fact that when the
Periodic Table is being built, the 4s orbital is filled before
the 3d orbitals. This is because before filling orbitals, 4s
orbitals have a lower energy than 3d orbitals.
However, once the electrons are actually in their orbitals,
the energy order changes - and in all the chemistry of
the transition elements, the 4s orbital behaves as the
outermost, highest energy orbital.
Co [Ar] 3d74s2
Co2+ [Ar] 3d7
V [Ar] 3d34s2
V3+ [Ar] 3d2
+2 in Mn2+
+3 in Mn2O3
+4 in MnO2
+6 in MnO42-
-
+7 in MnO 4
Masresha Amare (PhD) 18
Explaining the variable oxidation
states in the transition metals
We'll look at the formation of simple ions like Fe2+ and Fe3+.
When a metal forms an ionic compound, the formula of the
compound produced depends on the energetics of the
process. On the whole, the compound formed is the one in
which most energy is released. The more energy released,
the more stable the compound.
There are several energy terms to think about, but the key
ones are:
The amount of energy needed to ionise the metal (the sum
of the various ionisation energies)
The amount of energy released when the compound
forms. This will either be lattice enthalpy if you are
thinking about solids, or the hydration enthalpies of the
ions if you are thinking about solutions.
The more highly charged the ion, the more electrons you
have to remove and the more ionisation energy you will have
to provide.
But off-setting this, the more highly charged the ion, the more
energy is released eitherMasresha
as lattice enthalpy or the hydration
Amare (PhD) 19
enthalpy of the metal ion.
Thinking about a typical non-transition
metal (calcium)
Fe [Ar] 3d64s2
Fe2+ [Ar] 3d6
Fe3+ [Ar] 3d5
[Fe(H2O)6]2+
[Co(NH3)6]2+
[Cr(OH)6]3-
[CuCl4]2-