F block elements

The f block contains the lanthanides and the actinides. Lanthanides are the 14 elements that follow
lanthanum. That is from the atomic number 58 to71. Actinides are the 14 elements that follow the
element actinium. That is from the atomic number 90 to 103.
The lanthanide series
Lanthanides fill up the antepenultimate 4f energy levels. They are very similar to each other in
properties.
Electronic structure
Lanthanum has the electronic structure: core xenon 5d1 6s2. Hence we expect the next 14 elements to
be formed by adding an electron from 1 to 14 into the 4f level. However if the 5d electron is moved to
the 4f level it becomes more energetically favorable. This is the case for most of the 14 elements from
cerium to lutetium. This is not seen in cerium (Ce), gadolinium (Gd) and lutetium (Lu). Gadolinium has a
5d1 arrangement because it leaves a half filled 4f level and this increases its stability. Lutetium is also
more stable with 5d1 arrangement due to a completely filled f shell.
Lanthanides have a uniform oxidation state of (+III) which is shown by all the elements. They typically
form compounds that are trivalent and ionic.
The 4f electrons in the antepenultimate shells are shielded from the chemical environment by the
presence of 5s and 5p electrons. Hence the 4f electrons do not take part in bond formation. This means
that are not removed to produce ions. The octahedral splitting of f orbital is only about 1Kg/mol. Hence
the normal chemical properties are not affected by whether f orbitals are filled or not.
Oxidation states
The sum of the first three ionization energy for the lanthanides is low. Hence as mentioned above the
oxidation state (+III) is most commonly found and it is ionic. Ions of oxidation state (+II) and (+IV) are
also found. But they are less stable then ions of oxidation state (+III).
Oxidation numbers (+II) and (+IV) occur particularly when it leads to a noble gas configuration (Ce4+
with f0), a half filled f shell (Eu2+ and Tb4+ with f7) or a completely filled f shell (Yb2+ with f14 moreover
elements which are close to these states also exist as (+II) and (+IV), Sm+2 and Tm+2 occur as f6 and f13
Just like the other elements the higher oxidation states occurs in fluorides and oxides, while the lower
oxidation states are seen in other halides (particularly bromides and iodides).
As the lanthanides have only one stable oxidation state the elements resemble each other very closely.
This makes it possible to compare the effect of small changes in the size and nuclear charge on the
chemistry of these elements.
Abundance and number of isotopes
Lanthanides are not rare elements. The abundance and the number of naturally existing isotopes vary
regularly.

The elements with even atomic number are more abundant than elements with odd atomic number.
The even numbered elements also have a more stable isotopes. Elements which has an odd atomic
number will have about two stable isotopes. .
General properties
Salts of lanthanides usually contain water of crystallization. But there is no trend in the group. The
solubility of many of the salts follow the pattern group 2 elements. Hence the chlorides and nitrates are
soluble in water and the oxalates, carbonates and fluorides are insoluble. However unlike group 2, the
sulfates are soluble.
Many of the lanthanides form double salts with the corresponding group 1 or the ammonium salts. As
they crystallizes well they are used to separate lanthanum from each other.
Many trivalent lanthanum ions are strikingly colored both in aqueous state and the solid state. All but
one of the lanthanum ions show absorptions in the visible or near UV region of the spectrum.
Absorption spectra of lanthanum ions are used for the quantitative estimation and qualitative detection
of the lanthanum.
La3+ and Ce4+ have an f0 configuration, and Lu3+ has an f14 configuration. These have no unpaired
electrons and are diamagnetic. All other f states contains electrons and are therefore paramagnetic
The contraction in size from one element to another is very small. However the additive effect over the
14 lanthanide elements is about 0.2A and this is known as lanthanum contraction.
The lanthanum ions Ln3+ has a high charge which favors the formation of complexes. However since the
ions are rather large compared with the transition elements they do not form complexes readily/
Actinides
Elements that come after actinium are known as actinides. That is from the atomic number 90 to 103.
Before 1940 the only know actinides were the first there, Th, Pa and U. at that time these 3 elements
were thought to be part of the d block elements as they had some chemical similarities with the
transition elements. For example the increase in the oxidation states found in the elements, Ac, Th, Pa
and U was similar to the inverted pyramid of oxidation states obtained with the d block elements.
Furthermore the increasing stability of the higher states follows the same patterns as that of the d block
elements. All this was found to be very different from the (+III) state found in lanthanums.
After the work on Uranium (the heaviest naturally occurring element) during World War II and during
the following years, at least 12 more elements have been artificially made. Since these elements have a
higher atomic number than uranium they are sometimes referred to as Trans uranium elements.
After the Trans uranium elements were discovered and studies, it started to become apparent that they
were f block elements. This was because of:
1. The sharpness of the lines in the UV visible spectra
2. Magnetic studies.
3. The increasing importance of the (+III) oxidation state
Now it is accepted that actinides are a second inner transition series, from thorium to lawrencium.

Similarities between actinides and lanthanides

The lanthanides and the later actinides are very similar to each other. Cm closely resembles Gd, and
both have the electronic configuration, f7, d1, s2. The elution of Am, Cm, Bk and Cf from an ion
exchange column exactly parallel to that of lanthanides Eu, Gd, Tb and Dy.
The melting points and the densities do not fit the values for the d block.
The elements, Pa, U, Np and Cm have very sharp lines in their absorption spectrum. This is a
characteristic feature of f-f spectra. Spectral lines from actinides are ten times as intense as those from
the lanthanides.
Electronic structure
After Fr and Ra (who enter group 1 and 2 as they have the outer most electron in the 7s orbital) comes
Ac(actinium) and it begin to fill the penultimate d shell and has properties typical to that of Sc, Y and La.
Just like how we saw in La, it is expected that the next 14 elements (from thorium 90 to lawrencium 103)
electrons will enter the 5f shell. However the electronic structure is not the same as that of lanthanums.
After La the 4f has a lower energy than 5d orbital. Hence in the lanthanides the electrons fill in a normal
regular way (apart from some differences due to stability acquired by completely filled or half-filled sub
shell). Hence it is expected that the 5f orbital will have a lower energy than 6d orbital after Ac.
However this is not seen in the first four actinides. The first four actinides, Th, Pa, U and Np the energy
level of the 5f and 6d is similar. As a result the electrons can occupy either of the shells as the difference
is very small. And sometimes it is seen that they occupy both the shells.
After these first elements, in the later elements the energy level of 5f is appropriately lower than that of
6d orbital. Hence after the element plutonium, the 5f shell fills in a normal pattern and the elements
become similar to each other.

Oxidation states
The (+II) state is found rarely in actinides. It is seen in Am2+ with the f7 configuration. It correspondents
to Eu2+ in lanthanides. But it only exists as a solid in fluoride form. On the other hand, Cf2+, Es2+,
Fm2+,Md2+ and No2+ exist as ions in solution. Their properties are similar to that of group II elements,
particularly Ba2+. This is the most stable oxidation state for No as it corresponds to a completely filled
f14 shell.
All actinides have the oxidation state (+III), just like the lanthanides. However as seen from the above
example this may not be the most stable oxidation [Link] fact (+III) is not the most stable oxidation
state for the first four elements. For example U3+ is readily oxidized in air and in solution. The (+III) state
is the most stable state for the later elements that is from Am95 to Lw103 (except 102 No). Their
properties are similar to that of the lanthanides.
The most stable oxidation state for the first four elements are, Th (+IV), Pa (+V) and U (+VI). To be in this
state all the outer electrons, including the f electrons are used for bonding. In Np (+VII) exists, it is

oxidizing and the most stable is (+V). Pu shows all the oxidation states. For Am and the remaining
elements (+III) is the most stable.
Th (+IV) state exists for all the elements from Th to Bk. It is the most stable state for Th and Pu. M4+ ions
are known in acid solutions. The elements all form solid dioxides and fluorides.
The (+V) state occurs from elements Pa to Am. It is the most stable state for Pa and Np. A few solid
compounds are known. M5+ ions do not occur in solutions.
The (+VI) exists as the fluorides for the elements U, Np, Pu and Am. This state is most commonly found
as the dioxo ion. This ion is linear and is stable. It exists both in solution and in crystals.
The lower oxidation states tend to be ionic and the higher ones covalent. M2+, M3+ and M4+ ions are all
known. Hydrolysis of these ions occur quite readily but can be suppressed by using acid solutions.
General properties
The elements are all silvery metals. Their melting points are moderately high, but are considerably lower
than that of transition elements. The size of the ion decreases regularly along the series because the
extra charge on the nucleus is poorly shielded by the f electrons. This results in actinide contractions
similar to the actinides contractions. When the ion M3+ radii are compared with that of the lanthanides,
it is found that they are quite similar. Hence their chemical properties are alike. However actinides have
a much higher densities and a much greater tendency to form complexes.
Actinides are reactive metals like the lanthanides. They react with hot water and tarnish in air, forming
an oxide coating. This is a protective coating for Th but not with the others.
The metals react readily with HCl. But the reaction with other acids is slower than expected.
Concentrated HNO3 passivates Th, U and Pu. The metals are basic and do not react with NaOH. They
react with oxygen, halogens, and with hydrogen. The hydrides are nonstoichiometric, and have ideal
formulae MH2 and MH3.
The metals are usually obtained by electrolysis of fused salts, or by reducing the halides with Ca at high
temperatures