Chemistry of Lanthanides and Actinides V Semester

Inorganic Chemistry

Chemistry of Lanthanides and Actinides

The elements in which the differentiating electron enters the anti
penultimate energy level (i.e.[ n – 2])f), are called f–block elements.
These are often called as inner transition elements or rare earth
elements. The differentiating electron in transition elements may enter
either 4f or 5f orbitals based upon which they are differentiated into
lanthanides and actinides.

Lanthanides(4f block elements) or first inner transition elements

Lanthanides (also called lanthanoids) are called first inner transition
series or third transition and come immediately after lanthanum. They
are classified as ‘f” block elements along with the actinides. They are
commonly called the rare earths and characterized by the filling up of the
4f energy levels which are not usually involved in bonding. These highly
electropositive elements have a common oxidation state of +3 and
generally resemble each other in their chemical and physical properties.
They have a generic symbol “Ln”. In lanthanides the differentiating
electron enters 4f orbital. These are cerium to lutetium. The name
lanthanide is because they come immediately after lanthanum
Electronic configuration
General electronic configuration of f – block elements is (n–2)f 1–14(n–
1)d0–1ns2
Where n = 6(6th period ) for lanthanides and n= 7(7th period ) for
actinides
Lanthanides [Xe]4f1–145d0–16s2
Electronic configuration of lanthanides(La to ce)
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Oxidation states of lanthanides

Principle oxidation state of lanthanides are +3, some lanthanides
also exhibit other oxidation state like +2 and + 4, since +3 is the most
stable oxidation state for all lanthanides so some of the Ln+2 and Ln+4
readily convert to Ln+3 ions e.g. Sm+2 coverts to Sm+3 therefore Samarium
is good reducing agent and Ce+4 converts to Ce+3 hence Ce acts as good
oxidizing agent
Ce+4 + Fe+2 Ce+3 + Fe+3

Presence of +2, +3 and +4 oxidation states are explained on the basis of

the fact that Ln+2 Ln+3 Ln+4 ions attain 4f0, 4f7, 4f14 configurations
respectively which are very stable configuration for example
i) La and Ce attain 4f0 configuration by exhibiting +3 and +4
oxidation state respectively
La+3 = [Xe]4f0 Ce+4 = [Xe]4f0
ii) Eu, Gd, and Tb get 4f7configuration in +2,+3,+4, oxidation state
respectively

Eu+2= [Xe]4f7 Gd+3 = [Xe]4f7 Tb+4= [Xe]4f7

iii) Yb and Lu get 4f14 on exhibiting +2,+3 oxidation state

Yb+2 = [Xe]4f14 Lu+3= [Xe]4f14

Atomic radii and ionic radii of Ln+3 ions (Lanthanide contraction)

From the below table we can notice that in atomic radii and ionic
radii there is steady decrease in the values as we move from Ce to Lu
and from Ce+3 to Lu+3 these steady decrease is called Lanthanide
contraction.
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Lanthanide contraction “the steady decrease in the atomic and

ionic radii (Ln+3) of lanthanide element with increasing atomic number”
Causes for lanthanide contraction
As atomic number of lanthanide increase by one, the differentiating
electron enters into the 4f-orbital one at each step and the effective
nuclear charge of lanthanide increases from La to Lu,therefore the
attraction between the nucleus and outermost shell electron increases
gradually at each step, since 4f orbitals are diffused shaped the electron
in these orbitals cannot shield effectively (shielding effect of orbitals in
order s>p>d>f) these result in effective attraction between nucleus and
outermost electron which results in decrease of atomic and ionic radii as
atomic number increases.
Consequences of Lanthanide contraction
i) Basic character of lanthanide hydroxide Ln(OH)3 decreases with
increase in atomic number therefore La(OH)3 is highly basic and Lu(OH)3
is less basic this is due to increase in covalent character from La(OH) 3 to
Lu(OH)3
ii) Resemblance between the atomic radii of rhe element of 2nd and 3rd
transition series i.e. Each element beyond lanthanum has same atomic
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

radius as that of the element lying above it in the group (e.g. Zr 145 pm,
Hf 144 pm); Nb 134 pm, Ta 134 pm ; Mo 129 pm, W 130 pm).
iii) similarities among lanthanides, because of very small change in the
radii of lanthanides, their chemical properties are quite similar. Due to
this property separation of lanthanide is difficult in normal methods, they
are separated by other methods like fractional distillation and ion
exchange method
iv) Tendency to form stable complexes from La+3 to Lu+3 increases as the
size decreases in that order.

v) The decrease in chemical reactivity of next transition elements on the

lanthanide Due to lanthanide contraction, the ionization energy of the
next on the lanthanide elements increases. Hence , their
chemical reactivity decreases. For examples, the chemical reactivity of
the element which belong to sixth period such as, gold ( Au ), platinum
( Pt ), mercury ( Hg ) etc are very much less.

vi) The difference of density between the second and third transition
metal series The density of second and third transition metal series are
much more higher due to lanthanide contraction .Because the atomic
volume of two different elements of 4d and 5d series with same group is
near about same , but atomic mass of 5d series elements becomes much
higher. Au is denser than Ag

Magnetic properties of Lanthanide

All lanthanide ions with the exception of Lu+3 Yb+3 and Ce +4 are
paramagnetic because they contain unpaired electrons in the 4 f orbitals.
Magnetic moment of f block elements not only depend upon the number
of unpaired electrons but also on the orbital motion of an electron. So
magnetic moments of lanthanides are calculated by considering both
spin and orbital contributions by using a complex formula
g√ J (J +1)BM (Bohr magneton)
Where g = Lande’s splitting factor which is equal to
S ( S+ 1 )−L ( L+1 ) + J (J + 1)
g = 1+
2 J (J + 1)
S = spin of electron
L= total angular momentum
J = S+L
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Separation of lanthanide by Ion exchange method

This is the most rapid and effective method. when an aqueous solution
containing the mixture of trivalent lanthanide ions Ln+3(aq) is passed
through a column having synthetic cation exchange resin (HR) the
Ln+3(aq) ion replace H+ ion of the resin thus get fixed on it

Ln+3(aq) + 3HR(solid) LnR3 (solid) + 3H+

Since Lu+3(aq) is largest in the size and La +3 (aq) is smallest, La+3(aq) is

attached to the column with maximum and Lu+3(aq) with minimum
firmness.
In order to recover the Ln+3 ion fixed on the resin, the column is eluted
with eluant citric acid-ammonium citrate solution. During elution process
NH+4 ions replace Ln+3 and Ln-citrate complexes are formed

LnR3 + 3NH4+ 3NH4R + Ln+3

Ln+3 + citrate ions Ln- Citrate complex
Lu-citrate complex comes out of the column first and La-citrate comes
out last. The process is repeated several times.
Atypical elution curve of lanthanide ions using citric acid-ammonium
citrate solution as the eluent

Colour of Lanthanides
Many trivalent lanthanide ions are coloured both in solid states and in
aqueous solution. Depends on the number of unpaired f electrons. The
ion having n electrons in 4f orbitals has the same colour as the ion which
has (14-n) electrons in 4f orbitals. For example both Pr+3(4f2, n=2) and
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Tm+3(4f12 n= 14-2=12) have green colour, La+3 (4f0) which has no electron
in f orbital is colourless and Lu+3 ion ( 4f14) which has 14
electrons(completely filled) is also colourless.
Ln+3 ions absorb light of definite wavelength corresponding to certain
electronic transition. Colour is due to the absorption of light of particular
wavelength in the visible region.
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Spectral properties of Lanthanides

Lanthanide ions give absorption spectra which is due to electronic

transition within 4f level (f-f transition). Absorption spectra Ln +3 ions are
very sharp; they are almost line like bands. And become even narrower
as the temperature is lowered. This is due to the fact that electrons
present in the 4f-orbitals are effectively shielded by overlying electrons
present in 5s and 5p orbitals of tri positive lanthanide ions.

Catalytic activity
Lanthanide catalysts have been repeatedly recommended for use in
numerous organic reactions, including the hydrogenation of ketones to
form secondary alcohols, the hydrogenation of olefins to form alkanes,
the dehydrogenation of alcohols and butanes, and the formation of
polyesters, example samarium iodide involved in reduction of aldehyde
and ketones,
O OH
+
SmI2
R R'
R R'
H

Complex formation
Inspite of lanthanide ions having high charge of +3 they a low charge
density due to large laionic size, so they cannot cause large polarization
and have poor tendency to form complex they form very few complex
with unidentate ligand Ln+3 forms complexes of high coordination
numbers. The coordination numbers for [Ln(OH2)n]+3 in aqueous solution
are up to 9 for the early lanthanoids and 8 for the later smaller members.
The Ln+3 ions readily form complexes with F- and O-donor ligands eg
with H2O, EDTA, β-diketonate, citric acid, oxalic acid ligands. Partially
fluorinated β- diketonate ligand CF3COCHCOCF3(Fod) produces
complexes with Ln3+ that are volatile and soluble in organic
solvents(because of their volatility, they are used as precursors for the
synthesis of lanthanide containing superconductors by vapour
deposition). Charged ligands have highest affinity for the smallest Ln+3
ion.

Actinides
Separation of Neptunium (Np), Plutonium(Pu) and Americium (Am)
from Uranium (U) present in spent reactor fuel machine
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

In nuclear reactors the uranium fuel contains 235 238

92 U and 92 U isotopes

of spent uranium. These isotopes of uranium capture neutron (10n )

followed by - emission (−10e ) and give 237 239
93 Np and 94 Pu as shown below

235 1 236 236 1 237

92 U + 0n 92 U ; 92 U + 0n 92 U

237 237 0
92 U 93 Np + −1 e

238 1 239 239 239 0

92 U + 0n 92 U , 92U 94 Np + −1 e
239 239 0
94 Np 94 Pu + −1e

Am is formed by the following reaction

239 1 240 0
94 Pu + 0n 94 Pu + 0ϒ

241 241 0
94 Pu 95 Am + −1 e

Above equations shows that uranium is converted in to Np and Pu and

Pu is converted in to Am. Thus the spent uranium fuel contains a mixture
of unchanged U, Np, Pu, Am and numerous fission products (FP) which
are formed simultaneously.
The separation of Np, Pu and Am from U present in spent uranium
fuel (or spent reactor fuel material) can be done by several methods.
One of the method is discussed below.

Fluoride precipitation method

The spent uranium fuel material is immersed in large cooling

ponds about 100days so that the highly radioactive isotopes with short
half-lives such as 131
53 I lose most of their activity and generation of heat

subsides. The reactor fuel material is dissolved in 7mol HNO 3 and the
solution thus obtained is reduced by SO2 and then treated with HF. This
operation gives a solution of uranyl nitrate, UO 2(NO)3 and precipitates of
fluorides of NP(IV), Pu(IV), Am(III) and FPs.
The precipitate containing fluorides is dissolved in H2SO4, treated
−¿ ¿
with bromate (BrO3 ) (oxidizing agents) at room temperature and then
HF so that Np(IV) fluoride is oxidised to Np(VI) fluoride which passes
into solution while other fluorides remain as precipitate . The precipitate
containing fluorides of Pu(IV) and Am(III) is treated with a very strong
oxidising agent such as persulfate with Ag+ ion catalyst and then with
HF. In this reaction Pu(IV) fluoride is oxidised to Pu(VI) fluoride which
goes in to solution. The precipitate of Am(III) fluoride remain as
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

precipitate with FPs. The precipitate of Am(III) fluoride is dissolved and

Am is separated from FPs by ion exchange method.

Different steps for the separation of Np, Pu and Am from U by fluoride

precipitation method

Spent uranium fuel martials (after immersing in large cooling ponds)

containing U, Np, Pu, Am and FPs
Dissolove in 7M HNO 3

Solution containing nitrates of U, Np, Pu and Am + FPs

i) Reduction by SO 2
ii) HF

Solution containing UO2(NO3)2 Precipitate of fluorides of Np(IV),

Pu(IV),Am(III), FPs

i) Dissolve in H2SO4

ii) Oxidation BY BrO3-

iii) HF

Solution containing Np(VI) fluoride Precipitate of fluorides of Pu (IV), Am (III),

FPs

i) persulfate with Ag+

ion catalyst
ii) HF

Solution of Pu(VI) fluoride Precipitate of Am(III)

Fluoride, FPs

Ion exchange

Am(III)
Properties of actinides
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

(i) Actinides show variable oxidation states because of the smaller

energy gap between 5f, 6 d and 7s orbitals. Though 3+ is the most
stable oxidation state, other oxidation states are possible because of the
good shielding of f-electrons.
The maximum oxidation state first increases up to the middle of the
series and then decreases i.e. it increases from +4 for Th to +5, +6 and
+7 for Pa, V and Np but decreases in the succeeding elements
(ii) Actinide contraction : There is a regular decrease in ionic radii with
increase in atomic number from Th to Lr. This is called actinide
contraction analogous to the lanthanide contraction. It is caused due to
imperfect shielding of one 5f electron by another in the same shell. This
results in increase in the effective nuclear charge which causes
contraction in size of the electron cloud.
(iii) Colour of the ions : Ions of actinides are generally coloured which is
due to f – f transitions. It depends upon the number of electrons in 5 f
orbitals.
(iv) Magnetic properties : Like lanthanides, actinide elements are
strongly paramagnetic. The magnetic moments are lesser than the
theoretically predicted values. This is due to the fact that 5f electrons of
actinides are less effectively shielded which results in quenching of
orbital contribution.
(v) Complex formation : Actinides have a greater tendency to form
complexes because of higher nuclear charge and smaller size of their
atoms. They form complexes even with -bonding ligands such as alkyl
phosphines, thioethers etc, besides EDTA, -diketones, oxine etc. The
degree of complex formation decreases in the order.
 MO22 +¿>M ¿ MO+¿>¿ ¿
3+ ¿> ¿¿

Where M is element of actinide series. There is a high concentration of

charge on the metal atom MO22 +¿¿ in which imparts to it relatively high
tendency towards complex formation.
Electronic configuration
In actinides the differentiating electron enters 5f orbitals. These are
thorium to lawrencium.
These elements come immediately after actinium.
General electronic configuration of actinides elements is
[Rn]5f1–146d0–17s2
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry

Electronic configuration of actinides

Transuranium (transuranic) elements

elements that lie beyond uranium in the periodic table i.e., those
with atomic numbers greater than 92, this elements are also called
Urenides. Thus the actinide elements from Np to Lw are called
transuranic elements. they are synthesised artificially Np and Pu
occur only in trace amounts in nature
Chemistry of Lanthanides and Actinides V Semester
Inorganic Chemistry