INORGANIC CHEMISTRY-II BSCCH-201

UNIT-4 CHEMISTRY OF THE LANTHANIDE

ELEMENTS
CONTENTS:
4.1 Introduction
4.2 Objectives
4.3 Electronic structure
4.4 Oxidation states and ionic radii
4.5 Lanthanide contration
4.6 Complex formation
4.7 Occurrence and isolation
4.8 Lanthanide compounds
4.9 Summary
4.10 Terminal Question
4.11 Answers

4.1 OBJECTIVES
The objectives of this unit are to make the learners understand various aspects
regarding lanthanides or 4f-block elements such as their electronic structure or
configuration, oxidation states, ionic radii and corresponding lanthanide contraction,
complex formation by these elements, etc. It is also aimed at giving the readers an
idea of the occurrence and isolation of these elements along with the discussion of the
lanthanide compounds.

4.2 INTRODUCTION
Lanthanides, also sometimes called lanthanons, are the elements which
constitute a distinct series of fourteen elements from cerium (Ce, Z = 58) to lutetium
(Lu, Z = 71). They are so called because these elements succeed lanthanum (La, Z
=57), the element of Group 3 and lie between it and hafnium (Hf, Z = 72), the
element of Group 4, both belonging to third transition series (or 5d-transition series).
That is why they are also known as inner transition elements. These fourteen
elements belong to f-block and are the members of 4f-series because the last or
differentiating electron in the atoms of these elements enters 4f-subshell, i.e., the f-

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subshell of ante-penultimate shell (here n=6). Thus, f-block elements have partly
filled f-subshells of (n-2)th shell in the elementary or ionic state.

The first and the last elements of the 4f-series have been mentioned above (i.e., Ce
and Lu). The rest twelve elements along with their symbols and atomic numbers are
given below:

praseodymium (Pr, Z = 59), neodymium (Nd, Z = 60), promethium (Pm, Z = 61),

samarium (Sm, Z = 62), europium (Eu, Z = 63), gadolinium (Gd, Z = 64), terbium
(Tb, Z = 65), dysprosium (Dy, Z = 66), holmium (Ho, Z = 67), erbium (Er, Z = 68),
thulium (Tm, Z =69) and ytterbium (Yb, Z = 70). In analogy with various series of d-
block elements, these elements are called first inner transition series elements. All the
fourteen elements of the series resemble closely in their electronic configuration and
chemical properties with one another as well as with lanthanum which may be called
a prototype of lanthanide elements. All these elements said to be the members of
Group 3 i.e., Sc group and have been allotted one single position in the periodic table.

These elements were originally called rare earth elements because the
elements then known occurred as oxides (earths) and were available scarcely. All the
elements have similar physical and chemical properties hence are considered together
for their study.

It is interesting to note that the elements with even atomic numbers are
relatively more abundant and also have a larger number of isotopes but those with
odd atomic numbers are less abundant and do not have more than two isotopes.
Promethium (Z = 61) has been made artificially only and does not occur in nature.

4.3 ELECTRONIC STRUCTURE OF LANTHANIDES

The electronic configurations of the lanthanides have been derived from the
electronic spectra of the atoms of these elements. These spectra have great
complexity thereby inferring to some doubt about the configurations. In the following
table, the expected and alternative probable configurations of the elements have been
listed. The expected configurations have been derived by taking into account the
electronic configuration of lanthanum and supposing that in all the lanthanide
elements succeeding lanthanum, additional electrons are filled in 4f-subshell
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successively from cerium to lutetium. Thus the 4f-electrons are embedded in the
interior while 5d and 6s electrons are exposed to the surroundings. The electronic
configurations of lanthanide elements are given in Table 4.1.

Table 4.1 Electronic structures of lanthanum and lanthanides

Element At. number Expected electronic Alternative

(Z) configuration probable
configuration

Lanthanum (La) 57 [Xe]5d16s2 -

Cerium (Ce) 58 [Xe]4f15d16s2 [Xe]4f26s2

Praseodymium (Pr) 59 [Xe]4f25d16s2 [Xe]4f36s2

Neodymium (Nd) 60 [Xe]4f35d16s2 [Xe]4f46s2

Promethium (Pm) 61 [Xe]4f45d16s2 [Xe]4f56s2

Samarium (Sm) 62 [Xe]4f55d16s2 [Xe]4f66s2

Europium (Eu) 63 [Xe]4f65d16s2 [Xe]4f76s2

Gadolinium (Gd) 64 [Xe]4f75d16s2 [Xe]4f75d16s2

Terbium (Tb) 65 [Xe]4f85d16s2 [Xe]4f96s2

Dysprosium (Dy) 66 [Xe]4f95d16s2 [Xe]4f106s2

Holmium (Ho) 67 [Xe]4f105d16s2 [Xe]4f116s2

Erbium (Er) 68 [Xe]4f115d16s2 [Xe]4f126s2

Thulium (Tm) 69 [Xe]4f125d16s2 [Xe]4f136s2

Ytterbium (Yb) 70 [Xe]4f135d16s2 [Xe]4f146s2

Lutetium (Lu) 71 [Xe]4f145d16s2 [Xe]4f145d16s2

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According to the latter view, as is evident from the table, the solitary 5d-
electron shifts into the 4f-subshell in all the cases except in Gd (64) and Lu (71)
because it is favourable energetically to move the single 5d-electron into 4f-orbital in
most of the elements and give more appropriate electronic configuration which in
widely accepted. In Gd such a shift would have destroyed the symmetry of a half
filled f-subshell and the resulting configuration would have been less stable than the
probable configuration i.e., 4f7 is more stable than 4f8 configuration. In lutetium, the
f-subshell is already completely filled and cannot accommodate any additional
electron.

From the above, it may be concluded that the general electronic configuration
of lanthanide elements could be written as [Xe](n-2)f1-14(n-1)d0,1ns2 where n is the
principal quantum number, i.e., 6. The three subshells, viz., (n-2)f, (n-1)d and ns
together form the valence shell of these elements, i.e., 4f.5d.6s = valence shell.

4.4 OXIDATION STATES

It has been shown that the lanthanide elements are highly electropositive and
form essentially ionic compounds. It is observed for these elements that +3 (i.e.
formation of tripositive ions, Ln3+) is the principal or common oxidation state
exhibited by all of them. This is said to be the most stable oxidation state of the
lanthanides. Some of these elements also show + 2 and +4 oxidation states but except
a few such ions, they have the tendency to get converted to +3 state. For example, Sm
and Ce form Sm2+ and Ce4+ ions but are easily converted to +3 states. That is why
Sm2+ is a good reducing agent while Ce4+ is a good oxidising agent, i.e.,

Sm2+ → Sm3+ + e (electron provider, a reductant)

Ce4+ + e → Ce3+ (electron acceptor, an oxidant)

It means Ln2+ and Ln4+ ions are less frequent than Ln3+ ions among the lanthanides.
+2 and +4 oxidation states are shown by the elements particularly when they lead to:

(a) Noble gas electronic configuration, e.g., Ce4+ (4f0),

(b) Half-filled f-orbital, e.g., Eu2+ and Tb4+ (4f7), and
(c) Completely filled f-orbital, e.g., Yb2+ (4f14) in the valence shell.

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Among the above, +2 and +4 oxidation states, which exist only in aqueous solutions,
are exemplified by Sm2+, Eu2+, Yb2+ and Ce4+.

There are some exceptions also, i.e., sometimes +2 and +4 oxidation states are also
shown by the elements which are close to f0, f7 and f14 states, e.g., the valence shell
configurations of the ions given below are 4f1, 4f2, 4f3, 4f6 and 4f8, etc.:

Ce3+: 4f1; Ce2+: 4f2 ; Sm2+: 4f6 ; Pr4+: 4f1; Pr3+ : 4f2; Dy2: 4f8 ; Nd4+: 4f2; Tm2+:
4f13.

No satisfactory explanation for these exceptions has yet been given. These
oxidation states have only been explained on the basis of thermodynamic and kinetic
factors, that too arbitrarily. Due to the only one stable oxidation state (i.e., +3),
lanthanide elements resemble each other much more than do the transition (or d-
block) elements. It has also been observed that the higher oxidation states of the
lanthanides are stabilized by fluoride or oxide ions, while the lower oxidation sates
are favoured by bromide or iodide ions. Among the lanthanides, in addition to +3
states, +2 states is shown by Nd, Sm, Eu, Tm, and Yb only whereas +4 state is
exhibited by Ce, Pr, Nd, Tb and Dy elements. Rest five elements show only +3 states.

4.5 IONIC RADII AND LANTHANIDE CONTRACTION

Here, ionic radii of tripositive ions (i.e., Ln3+) have only been considered
because +3 is the most stable and common oxidation state of all the lanthanides, in
general. It has been observed that the atomic as well as the ionic radii of lanthanides
decrease steadily as we move from Ce to Lu. The ionic radii have been listed below
(for Ln3+ ions):

Ln3+ Ce3+ Pr3+ Nd3+ Pm3+ Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3 Yb3+ Lu3+
+
ions
Ionic
radii 103 101 100 98 96 95 94 92 91 90 89 88 86 85
(pm)

From the above list it is clear that the ionic radii decrease steadily all along
the series amounting in all to 18 pm. This shrinking in the ionic size of the Ln3+ ions
with increasing atomic number is called lanthanide contraction. The term steadily

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decrease means the values decrease regularly and with a very small difference though
the nuclear charge increases by +14 units from the first to the last element.

The atomic radii of these elements also decrease from Ce to Lu (Ce : 165 pm,
Lu : 156 pm) but the overall shift is only of 165-156 = 9 pm. These values do not
decrease regularly like ionic radii rather there are some irregularities at Eu and Yb
which have abnormally high atomic radii. (Eu : 185 pm, Yb : 170 pm).

The atomic radii for the metats are actually the metallic radii which are
recorded for the metal atoms surrounded by 8 or 12 nearest neighbors (in bulk).
Various metal atoms in metal crystal are bonded together by metallic bonding. In Eu
and Yb, only two 6s-electrons participate in metallic bonding, 4f-subshells being
stable. For other lanthanides, three electrons are generally available for this purpose.
This results in larger atomic volumes for Eu and Yb because of weaker bonding
among atoms. The larger values ultimately give rise to the larger size to the atoms of
the elements.

Cause of Lanthanide Contraction

As we move along the lanthanide series from Ce to Lu, the addition of

electrons takes place to the 4f-orbitals, one at each step. The mutual shielding effect
of f-electrons is very little, being even smaller than that of d-electrons, due to the
scattered or diffused shape of these orbitals. However, the nuclear charge (i.e. atomic
number) goes on increasing by one unit at each step (i.e., each next element). Thus,
the attraction between the nucleus and the outermost shell electrons also goes on
increasing gradually at each step. The 4f-electrons are not able to shield effectively
the attraction of the nucleus (i.e. inward pull) for the electrons in the outer most shell
as the atomic number of lanthanide elements increases.This results in the increased
inward pull of the outer most electrons by the nucleus, finally causing the reduction
in the atomic or ionic size of these elements. The sum of the successive reductions
gives the total lanthanide contraction.

It may be concluded that the lanthanide contraction among the 4f-sereies

elements and their ions takes place due to the poor shielding effect of 4f-electrons
and gradual increase in the nuclear charge.

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Consequences of Lanthanide Contraction

Lanthanide contraction plays an important role in determining the chemistry

of lanthanides and heavier transition series elements. Some important consequences
of lanthanide contraction are discussed below:

(a) Basic character of lanthanide hydroxides, Ln(OH)3

Because the size of tripositive lanthanide ions (Ln3+) decreases regularly with
increasing atomic number (or nuclear charge), the process being called
lanthanide contraction, therefore, the covalent character between Ln3+ ion and
OH- ions increases from La(OH)3 to Lu(OH)3 (Fajans’ rules). As a result, the
beasic character of the hydroxides decreases with increasing atomic number.
Consequently, La(OH)3 is the most basic while Lu(OH)3 is the least basic.
(b) Resemblance between the atomic radii of the second and third transition
series elements
The lanthanide contraction is an important factor in allowing the separation of
lanthanides from one another. Also it has significant effect on the relative properties
of the elements which precede and succeed the lanthanides. Normally in the same
group, the atomic (or covalent) radii increase as the value of n (principal quantum
number) increases due to increased distance between the nucleus and the outermost
shell of the electrons which counterbalances the increased nuclear charge. This fact is
evident when the values of atomic radii are compared for the elements of first and
second transition series. On the same analogy, the atomic radii of the elements of
third transition series should be greater than those of the second transition series
elements. This statement is valid only for the elements of Group 3, i.e. Sc, Y and La
in terms of their atomic radii (see the table given below). But, when these values are
compared for the elements of 4d and 5d series in the next group, viz. Group 4, 5
……………..12, it is observed that the values are unexpectedly almost equal. The
similarity in the values of atomic radii for the elements of second and third transition
series is attributed to the inclusion of 14 lanthanides between La (Z = 57, Group 3)
and Hf (Z = 72, Group 4) of third transition series which due to “lanthanide
contraction” cancel the increase in the values of atomic radii. Due to the similarity in
the size of the elements of the two series (i.e., second and third), the elements of a
particular Group resemble each other more closely in their properties than do the

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elements of first and second transition series. The examples of the pairs of elements
which show similar properties and hence are difficult to separate are Zr- Hf, Nb-Ta,
Mo-W, Ru-Os, Rh-Ir, Pd-Pt and Ag-Au. The atomic radii of the elements of the three
transition series are given below to justify the above statement.

Groups 3 4 5 6 7 8 9 10 11 12

Elements of 3d- Sc Ti V Cr Mn Fe Co Ni Cu Zn
sereis

Atomic radii (pm) 144 132 122 117 117 117 116 115 117 125

Elements of 4d- Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
sereis

Atomic radii (pm) 162 145 134 130 127 125 125 128 134 148

Elements of 5d-
La-Ln Hf Ta W Re Os Ir Pt Au Hg
sereis

Atomic radii (pm) 169 144 134 130 128 126 127 130 136 150

From this table, it is evident that due to lanthanide contraction, the atomic and ionic
radii of second and third transition series elements do not differ much though they are
appreciably higher than those of first transition series elements. It is also observed
that the atomic radii of the elements falling immediately after the lanthanide series
are closer to those of their 4d-congeners and the effect slowly decreases along the
series of 5d-elements as we move away from it.

(a) Densities of the elements of the three transition series

The density and atomic volume are inversely proportional to each other. All
the transition metals have low values for their atomic volumes and hence their
densities are high. In a given transition series, the atomic volumes of the
elements first decrease on proceeding from left to right and generally attain a
minimum value for the elements of group VIII (i.e., Groups 8,9,10). They
then start increasing further up to Group 12 elements. Accordingly, the

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density of the elements increases from left to right up to the elements of

Group VIII (Groups 8,9,10) and then decreases up to Group 12.

Down the group, the densities of the elements increase regularly. But the
striking feature that has been observed on moving from the first element to the
last element in every group is that the densityes of the elements belonging to
second transition series are only slightly higher than those of the
corresponding elements of 3d-series while the values for the elements from Hf
(Z =72) to Hg (Z =80) (i.e., 5d-sereis) are almost double of those for the
elements from Zr (Z=40) to Cd (Z=48), respectively (4d-sereis). This analogy
does not apply to Y(Z=39) and La (Z=57). This can be explained as follows:

Because of lanthanide contraction, the atomic sizes of the elements of third

transition series after La (Z=57) i.e. form Hf onwards become very small and
as a result, the packing of atoms in their metallic crystals becomes much
compact which results in high densities. Also, there is only a small difference
in the atomic sizes of the elements of the two series, viz., 4d-and 5d-series but
the atomic masses of the elements of 5d-series are almost double to the
corresponding elements of 4d-series. This makes the densities of 5d-series
elements almost double to those of the elements of 4d-series.
(b) Similarities among lanthanides
There is very small change in the radii of lanthanides and hence their
chemical properties are quite similar. This makes the separation of these
elements using the usual physical and chemical methods difficult.
Consequently new methods like ion exchange technique, solvent extraction
etc. have now been used for their separation which are based on slight
difference in the properties like hydration, complex ion formation, etc.

4.6 COMPLEX FORMATION BY LANTHANIDES

The lanthanides have low charge density due to their larger size in spite of
having high charge (+3). Hence, they do not cause much polarization of the ligands
and have a weak tendency for complex formation. This reluctance for complex
formation may be attributed mainly to:

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(i) The unfavourable electronic configuration on the lanthanide ions.

(ii) The larger size which leads to little attraction for electron rich species.

Because of the above reasons, only the high energy 5d, 6s and 6p-orbitals are
available for coordination, the 4f-orbitals being screened, so that only strong (usually
chelating) coordinating groups can interact. Thus, only a few complexes with
unidentate ligands are formed but stable complexes are formed by Ln3+ ions with
chelating ligands such as (i) oxygen containing, viz., EDTA, β-diketones, citric acid,
oxalic acid, acetyl acetone, oximes, (ii) nitrogen containing, viz., ethylene diamine,
NCS, etc. The Ln3+ ions do not form complexes with π-bonding ligands such as CO,
NO, CNR, etc., at all. The complex forming tendency and the stability of the
complexes increases with increasing atomic number. This fact is taken as a basis to
take advantage in their separation from one another. Ce(IV) complexes are relatively
common, an example of high oxidation state ion seeking stabilization through
complexation.

The most important class of lanthanide complexes are the anionic type.
Complexation with hydroxycarboxylic acids such as citric and tartaric acid is used in
the separation procedure of lanthanides. The EDTA complexes have achieved
importance in the recent years. The coordination number of lanthanide complexes is
usually six.

4.7 OCCURRENCE AND ISOLATION OF LANTHANIDE

ELEMENTS
Except promethium which is unstable and occurs only in traces, all the
lanthanides occur in nature to a considerable extent, cerium being the most abundant
of all the elements. There are more than hundred minerals known to contain
lanthanides but very few are of commercial importance. Monazite sand is the best
known and most important mineral of lanthanide elements which is essentially a
mixture of orthophosphates, LnPO4 containing upto 12% thorium, the element of 5f-
series, small amounts of Zr, Fe and Ti as silicates, lanthanum and about 3% yttrium.
Among lanthanides contained in monazite, the bulk is of Ce, Nd, Pr and others occur
in minute quantities.

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Extraction of lanthanide metals

After conventional mineral dressing which gives minerals of more than 90

percent purity, the mineral is broken down by either acidic or alkaline attack. By
making use of different solubilites of double salts: Ln2(SO4)3.Na2SO4.xH2O for light
and heavy lanthanides and low solubility of hydrated oxide of thorium, the lanthanide
fractions and thorium containing portions are separated in acidic medium.

Monazite is treated with hot conc. H2SO4 when thorium, lanthanum and
lanthanons dissolve as sulphates and are separated from insoluble material
(impurities). On partial neutralisaion by NH4OH, thorium is precipitated as ThO2.
Then Na2SO4 is added to the solution. Lanthanum and light lanthanides are
precipitated as sulphates leaving behind the heavy lanthanides in solution. To the
precipitate obtained as above, is added hot conc. NaOH. The resulting hydroxides of
light lanthanides are dried in air at 1000C to convert the hydroxides to oxides. The
oxide mixture is treated with dil. HNO3. This brings CeO2 as precipitate and other
lanthanides in solution. From the solutions obtained as above for heavy and light
lanthanides, individual members of lanthanide series are isolated by the following
methods:

Isolation of Individual Lanthanide Elements:

All the lanthanides have the same size and charge (of +3 unit). The chemical
properties of these elements which depend on the size and charge are, therefore,
almost identical. Hence, their isolation from one another is quite difficult. However,
the following methods have been used to separate them from one another.

1. Fractional Crystallization Method:

This method is based on the difference in solubility of the salts such as
nitrates, sulphates, oxalates, bromates, perchlorates, carbonates and double salts
of lanthanide nitrates with magnesium nitrate which crystallize well and form
crystals. Since, the solubility of these simple and double salts decreases from La
to Lu, the salts of Lu will crystallize first followed by those of lighter members.
The separation can be achieved by repeating crystallization process a number of

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times. A non-aqueous solvent, viz., diethyl ether has been used to separate
Nd(NO3)3 and Pr(NO3)3.
2. Fractional Precipitation Method:
This method is also based on the difference is solubility of the precipitate
formed, which is formed on addition of the precipitant, i.e. Precipitating agent.
If a little amount of precipitant is added, the salt with lowest solubility is
precipitated most readily and rapidly. For example, when NaOH is added to a
solution of Ln(NO3)3, Lu-hydroxide being the weakest base and having the
lowest solubility product is precipitated first while La-hydroxide which is the
strongest base and has the highest solubility product is precipitated last. By
dissolving the precipitate in HNO3 and reprecipitating the hydroxides a number
of times, it is possible to get the complete separation of lanthanide elements.
3. Valency change Method:

This method is based on the change of chemical properties by changing the

oxidation state of the lanthanide elements. The most important application of
this method is made in the separation of cerium and europium elements from
mixture of lanthanides.

(i) The mixture containing Ln3+ ions if treated with a strong oxidising agent
such as alkaline KMnO4, only Ce3+ ion is oxidized to Ce4+ while other
Ln3+ ions remain unaffected. To this solution alkali is added to
precipitate Ce(OH)4 only, which can be filtered off from the solution.
(ii) Eu2+ can be separated almost completely from Ln3+ ions from a solution
by reducing it with zinc-amalgam and then precipitating as EuSO4 on
adding H2SO4 which is insoluble in water and hence can be separated.
The sulphates of other Ln3+ ions are soluble and remain in solution.

4. Complex Formation Method:

This method is generally employed to separate heavier lanthanide elements

from the lighter ones by taking the advantage of stronger complexing tendency
of smaller cations with complexing agents. When EDTA is added to Ln3+ ion
solution, lanthanides form strong complexes. If oxalate ions are added to the
solution containing EDTA and Ln3+ ions, no precipitate of oxalates is obtained.

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However, on adding small amount of acid, the least stable complexes of lighter
lanthanides are dissociated and precipitated as oxalates, but the heavier
lanthanides remain in solution as EDTA complexes.

5. Solvent Extraction Method:

This method is based on the difference in the values of partition coefficient of

lighter and heavier lanthanides between two solvents, e.g., water and tri-butyl
phosphate (TBP). Heavier lanthanides are more soluble in TBP than lighter
ones whereas reverse trend of solubility is found in water and other ionic
solvents. La(NO3)3 and Gd(NO3)3 have been separated by this method
because the partition coefficient of Gd-nitrate in water and TBP is different
from that of La-nitrate. Thus, Gd-nitrate can be separated from La-nitrate by
continuous extraction with water from a solution of these salts in TBP in
kerosene oil or by using a continuous counter-current apparatus which gives a
large number of partitions automatically.

6. Modern Ion-Exchange Method:

This is the most rapid and most effective method for the isolation of individual
lanthanide elements from the mixture. An aqueous solution of the mixture of
lanthanide ions (Ln3+aq) is introduced into a column containing a synthetic
cation exchange resin such as DOWAX-50 [abbreviated as HR (solid)]. The
resin is the sulphonated polystyrene containing-SO3H as the functional group.
As the solution of mixture moves through the column, Ln3+aq ions replace H+
ions of the resin and get themselves fixed on it:
Ln3+aq + 3H(resin) → Ln(resin)3 + 3H+aq
The H+aq ions are washed through the column. The Ln3+aq. ions are fixed at
different positions on the column. Since, Lu3+aq. is largest (Lu3+ anhyd. is
smallest and is hydrated to the maximum extent) and Ce3+aq. is the smallest,
Lu3+aq. ion is attached to the column with minimum firmness remaining at the
bottom and Ce3+aq. ion with maximum firmness remaining at the top of the
resin column. In order to move these Ln3+aq. ions down the column and recover
them, a solution of anionic ligand such as citrate or 2-hydroxy butyrate is
passed slowly through the column (called elution). The anionic ligands form
complexes with the lanthanides which possess lower positive charge than the

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initial Ln3+aq ions. These ions are thus displaced from the resin and moved to
the surrounding solutions as eluant- Ln complexes.
For example, if the citrate solution (a mixture of citric acid and ammonium
citrate) is used as the eluant, during elution process, NH4+ ions are attached to
the resins replacing Ln3+aq. ions which form Ln-citrate complexes:

Ln (resin)3 + 3NH4+ → 3NH4- resin + Ln3+aq

Ln3+aq + citrate ions → Ln-citrate complex
As the citrate solution (buffer) runs down the coloumn, the metal ions get
attached alternately with the resin and citrate ions (in solution) many times and
travel gradually down the column and finally pass out of the bottom of the
column as the citrate complex. The Ln3+aq cations with the largest size are,
eluted first (heavier Ln3+aq ions) because they are held with minimum firmness
and lie at the bottom of the column. The lighter Ln3+aq ions with smaller size
are held at the top of the column (with maximum firmness) and are eluted at
last. The process is repeated several times by careful control of concentration of
citrate buffer in actual practice.

4.8 LANTHANIDE COMPOUNDS

The lanthanides are very electropositive and reactive metals, the reactivity
depends on the size. Europium with the largest size is most reactive. All the
lanthanides generally give normal and complex compounds.
Oxides:
If lanthanide elements are ignited in air or O2, they readily form the oxides of
Ln2O3 type except Ce which gives a dioxide, CeO2. The oxides are ionic and
basic. The basic nature of oxides decreases along the series with decreasing
ionic size.
∆
2 Ln + 3O2 → Ln2O3

∆
Ce + O2 → CeO2

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Ytterbium resists the action of air even at 10000C due to the formation of a
protective layer of oxide on its surface.

Hydroxides:

The lanthanides react slowly with cold water but readily with hot water:

2 Ln + 6 H2O → 2 Ln(OH)3 + 3H2

On adding aqueous ammonia to this aqueous solution, hydroxides are precipitated as

gelatinous precipitate. These hydroxides are also ionic and basic, the basic nature
decreasing with increasing atomic number. La(OH)3 is most basic and Lu(OH)3 is
least basic. Their basic character is more than that of Al(OH)3 but less than that of
Ca(OH)2.

Oxo-salts:

Lanthanides form oxo-salts such as nitrates, sulpates, perchlorates and salts of oxo-
acids which are soluble in water but carbonates and oxalates are insoluble. The
difference in basicity is responsible for the difference in thermal stability of the oxo-
salts which decreases along the series. Thus, La(NO3)3 is more stable than Lu(NO3)3.

Halides and Hydrides:

The lanthanides also burn in halogens to produce LnX3 type halides and combine
with H2 at high temperature to give stable MH2 or MH3 type hydrides. Among
halides, fluorides are insoluble but other halides are soluble in water.

Ln also form complexes with chelating ligands, the detailed account has been given
earlier.

4.9 SUMMARY
The present unit covers all the important and interesting aspects of lanthanides
such as their electronic structure, oxidation states, ionic radii and corresponding
lanthanide contraction, consequences of lanthanide contraction, complex formation
by lanthanides, their occurrence, extraction and various methods employed for the

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isolation of the elements and a brief account of the lanthanide compounds. The
readers can understand well all these aspects after going through the unit text.

4.10 TERMINAL QUESTIONS

1. Why are the lanthanides grouped together?
2. Why the f-block elements are also called the inner transition elements?
3. Give a brief account of lanthanide contraction.
4. The number of f-electrons in Eu2+ and Yb2+ ions is
(a) 7 and 14
(b) 7 and 13
(c) 6 and 14
(d) 6 and 13
4+
5. Tb ions are stable, explain.
6. Discuss the ion exchange method of isolation of lanthanides.
Which one is more basic La(OH)3 or Lu(OH)3 and why?

4.11 Answers

4. (a)

5. Due to 4f7 valence shell electronic configuration.

6. La(OH)3 due to larger cationic size

For answers to other questions, please refer to the text.

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UNIT-5 CHEMISTRY OF THE ACTINIDE

ELEMENTS
CONTENTS:
5.1 Objectives
5.2 Introduction
5.3 General features
5.4 Chemistry of actinides
5.5 Separation of Np, Pu and Am from U
5.6 Similarities between the latter actinides and the latter lanthanides
5.7 Summary
5.8 Terminal Questions
5.9 Answers

5.1 OBJECTIVES
The objectives of writing this unit are to make the readers well acquainted
with various aspects of the actinide or 5f-block elements such as the general features
of these elements, e.g., their occurrence and nature, their electronic structure,
oxidation states, complex formation tendency, magnetic and spectral properties,
atomic and ionic sizes, etc. as well as to throw light on the chemistry of the actinides
and the chemistry of separation of Np, Pu and Am from U. It is also aimed at to
discuss the similarities between lanthanides and actinides.

5.2 INTRODUCTION
The group of fourteen elements from thorium (Th, Z = 90) to lawrencium (Lr,
Z=103) are called actinides, actinoids or actinons. These are named so because these
elements succeed the element actinium (Ac, Z = 89). These elements are also known
as inner-transition elements as they lie between actinium and rutherfordium (Rf, Z
=104), i.e., the elements of fourth transition series. Thus, they constitute the second
inner-transiton series of which actinium is the prototype.

In these elements 5f-subshell of the antepenultimate shell (n=7) is successively filled

by the additional or differentiating electrons, one at a time in each step, which are
embedded in the interior while 6d- and 7s-electons are exposed to the surroundings.

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In the outermost and penultimate shell of these elements, the number of electrons
remains almost the same. That is why the actinide elements resemble one another
very closely. The actinides lying beyond uranium, i.e., the elements with Z = 93 to
103 are called transuranium elements. The first and the last elements of 5f-series have
been mentioned above with their names and symbols, i.e., Th and Lr. The remaining
twelve elements are listed below:

protactinium (Pa, Z = 91), uranium (U, Z = 92), neptunium (Np, Z = 93), plutonium
(Pu, Z = 94), americium (Am, Z = 95), curium (Cm, Z = 96), berkelium (Bk, Z = 97),
californium (Cf, Z= 98), einsteinium (Es, Z = 99), fermium (Fm, Z= 100),
mendelevium (Md, Z = 101) and nobelium (No, Z= 102).

These elements of 5f-series are also said to belong to Group 3 and Period 7
and have been allotted a position below those of 4f-series in the periodic table and
thus the elements of both f-series have been placed separately below the main body
of table to avoid unnecessary expansion of the periodic table.

5.3 GENERAL FEATURES OF THE ACTINIDES

(1) Occurrence and Nature

Only the first four elements, viz., Ac, Th, Pa and U occur in nature in uranium
minerals that too only Th and U occur to any useful extent. All the remaining
actinides, i.e. trans uranium elements are unstable and are made artificially. The
elements above Fm (Z =100) exist as short lived species, some of them existing only
for a few seconds. All the actinides are radioactive in nature.

(2) Electronic structure (or Configuration)

The electronic configuration of actinium (Z = 89) which is followed by fourteen

actinides is [Rn]5f06d17s2, the last electron entering the 6d-subshell. In the next
element, Th, the first member of the actinide series, the additional electron must enter
5f-subshell and the filling of 5f-subshell must continue progressively till the last
element, Lr. Thus, 6d-subshell in all the elements must remain singly filled thereby
giving the expected valence shell configuration of 5f1-146d17s2 for these elements.
Since, the energies of 6d- and 5f- subshells are almost the same and the atomic
spectra of the elements are very complex, it is difficult to identify the orbital in terms

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of quantum numbers as well as to write down the configuration. For chemical

behaviour, the valence shell electronic configuration of the elements is of great
importance and the competition between 5fn6d07s2 and 5fn-16d17s2 is of interest. It has
been observed that the electronic configuration of actinides does not follow the
simple pattern as is observed for the lanthanides. For the first four actinde elements,
viz., Th, Pa U and Np, due to almost equal energies of 5f and 6d, the electrons may
occupy the 5f or 6d subshells or sometimes both. From Pu (Z=94) onwards, 6d1
electron gets shifted to 5f-subshell except for Cm (Z=96) and Lr (Z=103) in which
6d1 electron does not shift to 5f due to stable 5f7 and 5f14 configurations. In view of
the above considerations, the general valence shell electronic configuration of the
actinide elements may be written as: 5f0-146d0-27s2. For individual elements the
observed or actual valence shell configurations are listed below:

Element (Z) Valence shell Element (Z) Valence shell

configuration configuration
Thorium (90) 5f06d27s2 Berkelium (97) 5f96d07s2
Protactinium (91) 5f26d17s2 Californium (98) 5f106d07s2
Uranium (92) 5f36d17s2 Einsteinium (99) 5f116d07s2
Neptunium (93) 5f46d17s2 Fermium (100) 5f126d07s2
Plutonium (94) 5f66d07s2 Mendelevium (101) 5f136d07s2
Americium (95) 5f76d07s2 Nobelium (102) 5f146d07s2
Curium (96) 5f76d17s2 Lawrencium (103) 5f146d17s2

From the above valence shell configurations of the actinide elements, it is clear that
Th does not have any f-electron though this element belongs to 5f-series (i.e.,
actinides). For Pa, U, Np, Cm and Lr, both the expected and observed (actual)
configurations are same. For the rest of the actinides, 6d-subshell does not contain
any d-electron.

(3) Oxidation States

The important oxidation states exhibited by actinides are compiled below in the
tabular form. Some of them are stable but most of these oxidation states are unstable.
It may be seen from these oxidation states that the +2 state is shown by Th and Am

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only in the few compounds like ThBr2, ThI2, ThS, etc. The +3 oxidation state is
exhibited by all the elements and it becomes more and more stable as the atomic
number increases. The +4 oxidation state is shown by the elements from Th to Bk,
the +5 oxidation state by Th to Am, the +6 state by the elements from U to Am and
the +7 state is exhibited by only two elements, viz ., Np and Pu. Np in the +7 state
acts as an oxidising agent.

The principal cations given by actinide elements are M3+, M4+ and oxo-cations such
as MO2+ (oxidation state of M = + 5) and MO22+ (oxidation state of M = +6). The
examples of oxo-cations are UO2+, PuO2+, UO22+ and PuO22+ which are stable in acid
and aqueous solutions. Most of the M3+ ions are more or less stable in aqueous
solution. Np3+ and Pu3+ ions in solution are oxidized to Np4+ and Pu4+ by air. The
latter ions are further oxidized slowly to UO22+ and PuO22+ by air. Various oxidation
states of the actinides are listed below:

Element Oxidation states Element Oxidation states

Th +2, +3, +4 Bk +3, +4
Pa +3, +4, +5 Cf +3
U +3, +4, +5, + 6 Es +3
Np +3, +4, +5, +6, +7 Fm +3
Pu +3, +4, +5, +6, +7 Md +3
Am +2, +3, +4, +5, +6, No +3
Cm +3, +4 Lr +3

The lighter elements up to Am show variable oxidation states, the maximum being
for Np, Pu and Am, but the heavier elements show constant oxidation state of +3.

(4) Atomic and Ionic Radii

The atomic (metallic) and ionic radii of cations in common oxidation states (i.e. M3+
and M4+ cations) of some of the actinide elements have been evaluated. A look into
the values of the atomic radii reveals that the metallic radii first decrease from Th to
Np and then increase gradually up to Bk. For the higher actinides the values are not
known. The values of ionic radii for both types of ions go on decreasing. This steady
fall in the ionic radii along the actinide series is called actinide contraction which is
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analogous to lanthanide contraction found in lanthanides. The cause of actinide

contraction is the same as has been discussed for the lanthanides. Here also,
increasing nuclear change and poor shielding effect of 5f-electrons play an important
role. The atomic and ionic radii are listed below:

Element Atomic radius Ionic radius of M3+ ion Ionic radius of M4+ ion
(pm) (pm) (pm)
Th 180 108 96
Pa 164 105 93
U 157 103 92
Np 156 101 91
Pu 160 100 90
Am 174 99 89
Cm 175 99 88
Bk 176 98 87
Cf - 97 -

It is clear from above table that there is only a small variation in the atomic and ionic
radii of the actinide elements; hence they show similar chemical properties.

(5) Magnetic and Spectral Properties

It has already been mentioned that the paramagnetic nature of the substances is due to
the presence of unpaired electrons. The actinide elements like lanthanides show
paramagnetism in the elemental and ionic states. Tetravalent thorium (Th4+) and
hexavalent uranium (U6+) ions are diamagnetic due to the absence of unpaired
electrons. Th4+ = U6+ = Rn (Z= 86) structure (diamagnetic, paired electrons). Since,
actinides constitute second f-series, it is natural to expect similarities with lanthanides
(the first f series) in their magnetic and spectroscopic properties. But, there are some
differences between the lanthanides and actinides. Spin-orbit coupling is strong
(2000-4000cm-1) in the actinides as happens in the lanthanides but because of the
greater exposure of the 5f-electrons, crystal field splitting is now of comparable
magnitude and J is no longer such a good quantum number. It is also noted that 5f-
and 6d-subshalls are sufficiently close in energy for the lighter actinides to make 6d-

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levels accessible. As a result each actinide compound has to be considered

individually. This must allow the mixing of J levels obtained from Russel-Saunders
coupling and population of thermally available excited levels.

Accordingly, the expression µ = is less applicable than for the

lanthanides and magnetic moment values obtained at room temperature are usually
lower and are much more temperature dependent than those obtained for compounds
of corresponding lanthanides.

The electronic spectra of actinide compounds arise from the following three types of
electronic transitions:

(a) f-f transitions: These are Laporte (orbitally) forbidden but the selection rule in
relaxed partially by the action of crystal field in distorting the symmetry of the
metal ion. Because the actinides show greater field, hence the bands are more
intense. These bands are narrow and more complex, are observed in the visible
and UV regions and produce the colours in aqueous solutions of simple actinide
salts.
(b) 5f-6d transitions: These are Laporte and spin allowed transitions and give rise to
much more intense bands which are broader. They occur at lower energies and
are normally confined to the UV region hence do not affect the colours of the
ions.
(c) Metal to ligand charge transfer: These transitions are also fully allowed and
produce broad, intense absorptions usually found in UV region, sometimes
trailing in the visible region. They produce the intense colours which are
characteristic of the actinide complexes.

The spectra of actinide ions are sensitive to the crystal field effects and may change
from one compound to another. It is not possible to deduce the stereochemistry of
actinide compounds due to complexity of the spectra. Most of the actinide cations
and salts are coloured due mainly to f-f transitions. Those with f0, f7 and f14
configurations are colourless. The colours of some of the compounds in different
oxidation states are given below:

NpBr3 : green; NpI3 : brown; NpCl4 : red-brown; NpF6 : brown

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PuF3 : purple; PuBr3 : green; PuF4 : brown; PuF6 : red brown

AmF3 : pink; AmI3 : yellow; AmF4 : dark tan.

The coordination chemistry of actinides is more concerned with aqueous solutions.

Because of the wider range of oxidation states available in actinides, their
coordination chemistry is more varied. Most of the actinide halides form complex
compounds with alkali metal halides. For example, ThCl4 with KCl forms complexes
such as K[ThCl5] and K2[ThCl6], etc. ThCl4 and ThBr4 also form complexes with
pyridine, e.g. ThCl4.py Chelates are formed by the actinides with multidentate
organic reagents such as oxine, EDTA, acetyl acetone, etc.

The actinides with small size and high charge have the greatest tendency to form
complexes. The degree of complex formation for the various ions decreases in the
order: M4+ > MO22+ > M3+ > MO2+. The complexing power of different anions with
the above cations is in the order:

Monovalent anions : F- > NO2- > Cl-

Bivalent anions : CO32- > C2O42- > SO42-

5.4 CHEMISTRY OF ACTINIDES

The actinide elements are highly electropositive and reactive. They show
similar properties to those of lanthanides. But these elements have much higher
tendency to form complexes. They react with water and tarnish in air forming oxide
coating. They react readily with HCl but slowly with other acids. The metals show
basic nature and do not react with NaOH but they react with halogens, oxygen and
hydrogen to form halides, oxides and hydrides. Some of the compounds of the
actinides are discussed below:

(i) Oxides: The metals on reacting with air or oxygen give various oxides under
different experimental conditions. Uranium is one of the reactive elements
and gives the oxides: UO, UO2, U3O8 and UO3:
∆
U + O2 → U3O8

∆
UO3 → UO2
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Similarly, the oxides of Np, Pu and Am are: NpO, NpO2, Np3O8, PuO,
Pu2O3, Pu2O7, PuO2, AmO and AmO2.
(ii) Hydrides, nitrides and carbides: U and Pu form hydrides UH3 and PuH3, by
the direct union of the elements. U reacts with H2 even at room temperature
but the reaction is faster at 250 0C as compared to room temperature:
2U + 3H2 → 2UH3
This compound is reactive and is hydrolysed by water:
2UH3 + 4H2O → 2UO2 + 7H2
This also reacts with Cl2, HF and HCl as follows:
2UH3 + 4Cl2 → 2UCl4 + 3H2
2UH3 + 8HF → 2UF4 + 7H2
UH3 + 3HCl → UCl3 + 3H2
When treated with ammonia, the metals give nitrides of the type : UN,
U2N3, UN2 and PuN.
These metals also give carbides: UC and PuC.
All the MX type compounds where M = U, Np, Pu or Am and X = O, C or
N have the rook-salt (or NaCl) structure.
(iii)Halides: Actinide elements on reacting with halogens or hydrogen halides
form halides, the most common being those of U and Np. Trihalides of
MX3 type are formed by the actinides which are isomorphous with one
another. Some of the actinides also form the tetra, penta and hexa halides
as well. For example, U fluorides are obtained as is shown by the following
reactions:
0
HF F2, 240 c HF
UO2 → UF4 → UF5 → UF6 and UF82-

0
900 c
UF4 → UF3

F2,4000c
UF4 → UF6

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Np, Pu and Am are also reactive similar to U and give the analogous reactions and
products. Some examples of halides are : UF6, UF5, UF4, UF3, UCl4, UCl3, UBr4,
UBr3, NpF6, NpF4, NpF3, NpCl3, NpI3, etc.

5.5 CHEMISTRY OF SEPARATION OF NP, PU AND AM

FROM U
Although several isotopes of Np, Pu and Am elements are known yet only a
few are obtained. But Np237 and Pu239 are found in the uranium fuel elements of
nuclear reactors from which Pu is isolated on a kilogram scale. Np237 is also found in
substantial amounts and is recovered primarily for conversion by neutron irradiation
of NpO2 into Pu238 which is used as a power source for satellites. Am produced from
intense neutron irradiation of pure plutonium. The main problem involved in the
extraction of these elements includes the recovery of the expensive signatory material
and the removal of hazardous fission products that are formed simultaneously in
amounts comparable to the amount of the synthetic elements themselves. There are
various methods available for the separation of Np, Pu and Am which are based on
precipitation, solvent extraction, differential volatility of compounds and ion
exchange. The chemistry of the most important methods of separation is given below:

(a) Method based on stabilities of oxidation states

The stabilities of major ions of these elements involved are UO22+ > NpO22+ >
PuO22+ > AmO22+ and Am3+ > Pu3+ >> Np3+ > U4+. By choosing a suitable
oxidising or reducing agent, it is possible to obtain a solution containing the
elements in different oxidation states. The elements can then be separated by
precipitation or solvent extraction method. For example, Pu can be oxidized to
PuO22+ whereas Am remains as Am3+. Thus PO22+ can be easily removed by
solvent extraction or Am3+ by precipitation as AmF3.
(b) Method based on extraction by using organic regents
It is a well known fact that MO22+ ions can be extracted from nitrate solutions
into organic solvents. The M4+ ions can be extracted into tributyl phosphate in
kerosene from 6M-HNO3 solution. Similarly M3+ ions can be separated from
10-16M HNO3. Thus, the actinides close to each other can be separated by
changing the conditions.

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(c) Method based on precipitation

The actinide ions in M3+ or M4+ state only give insoluble fluorides or
phosphates in acid solution. In the higher oxidation states these elements are
either soluble or can be prevented to get precipitated by complex formation
with sulphate or other ions.
(d) Method based on ion-exchange
This method has been found suitable for small amount of material. In this
method, both cationic and anionic ion ex`changers can be used to separate the
actinide ions. The separation of the actinides by ion-exchange methods is
given below:
1. Isobutyl methyl ketone method: In this method the following scheme is used:

Cr2O72- Al(NO3)3
UO22+ + Ac 4+
→ 2+
UO2 + AcO2 2+
→ Aqueous portion + solvent
SO2 Extract
portion (UO22+ + AcO22+) → solvent (UO22+) + Aqueous (Ac4+)
+ H2 O

The two layers are separated and collected. Here Ac4+ represents the actinide
ions
such as Np4+, Pu4+ and Am4+.
2. Tributyl phosphate method: This method is dependent on the difference in
extraction coefficients from 6N-HNO3 into 30% tributyl phosphate in kerosene.
The order of extraction is :
Pu4+ > PuO22+, Np4+ > Np+O2 >> Pu3+ and UO22+ > NpO22+ > PuO22+.
The Ac3+ ions have very low extraction coefficients in 6M-HNO3 but in 12M-
HCl or 16M-HNO3 the extraction increases. The order of extraction is: Np <
Pu
< Am < Cm, etc. In this method the scheme used is as follows:
Exces H2O
UO22+ + Ac4+ → Aqueous portion + Solvent portion (UO22+ + Ac4+) →
TBP HNO3

solvent portion (UO22+ 4+ 4+

or U ) + aqueous portion (Ac ) → Ac 4+.

Repeat extraction to get Ac4+. Here also, Ac = Actinide particularly Np and Pu.
3. Method Based on Lanthanum fluoride cycle: This method was developed for
the isolation of Np but has been found to be of great utility in the separation of
Pu from U. The scheme used for the separation is given below:

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Extract
Ag.HF
UO22+ + Ac4+ → Solvent (UO22+) + Aqueous soln (Ac4+ + some UO2 2+) →
with hexane
3+
La
Boil with HF
BrO3-
Filtrate (UO22+) 3+ 4+
+ ppt (LaF3 + AcF3) → Ac +Ac → La +AcO2 → 3+ 2+
NaoH, dissolve in
SO2
HNO3

ppt(LaF3) + Filtrate (AcO22+) → Ac4+ →Repeat the cycle to get more and
pure
Ac4+, where Ac carries the usual meaning.

5.6 SIMILARITIES BETWEEN LANTHANIDES AND

ACTINIDES
(i) In the atoms of the elements of both the series, three outermost shells are
partially filled and remaining inner shells are completely filled but the
additional or differentiating electron enters (n-2) f-subshell.
(ii) The elements of both series exhibit +3 oxidation state which is prominent and
predominant state.
(iii) Like Lanthanide contraction found in the lanthanide elements, there occurs
contraction in size in the actinide elements called actinide contration. Both the
contractions are due to poor shielding effect produced by f-electron with
increasing nuclear charge.
(iv) The elements of both the series are quite reactive and are electropositive.
(v) The electronic absorption bands of the elements of both the series are sharp and
appear like lines. These bands are produced due to f-f transitions within (n-2)f-
subshell though such transitions are orbital forbidden.
(vi) Most of the lanthanide and actinide cations are paramagnetic.
(vii) The nitrates, perchlorates and sulphates of trivalent lanthanide and actinide
elements are soluble while the hydroxides, fluorides and carbonates of these
elements are insoluble.
(viii) The lanthanide and actinide elements show similarity in properties among their
series though the lanthanides are closer among them sieves in properties as
compared to actinides.

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5.7 SUMMARY
The text material of this unit contains the introductory part which is quite
interesting and important from the view point of the readers and a detailed account of
the general features of the actinides such as their occurrence, electronic structure,
oxidation states which have greater variability than those of lanthanides, atomic and
ionic radii-the actinide contraction, their magnetic and spectral properties along with
exhibition of colour, formation of complexes, etc has been given.

The chemistry of actinides including the formation of various compounds, e.g.,

oxides, hydrides, nitrides, carbides and halides in various oxidation states has also
been discussed. The unit also contains a detailed account of the chemistry of
separation of Np, Pu and Am from U including the method used for separation. At
last the points of similarities between the lanthanides and actinides have been
mentioned.

5.8 TERMINAL QUESTIONS

1. Why do actinides show higher oxidation states than lanthanides?
2. Oxocations MO22+ are formed by U, Np, Pu and Am only wheras heavier
actinides do not form such ions, why?
3. The elements beyond atomic number 102 are unstable, Explain.
4. Write the electronic configuration of Th, Cm and No.
5. Name the actinides along with their symbols and atomic numbers.
6. Which actinide ion in +3 oxidation state has just half-filled 5f-subshell?
(a) Pu3+
(b)Am3+
(c) Cm3+
(d)Bk3+
7. The first member of the post actinide transition series is:
(a) Rutherfordium
(b)Seaborgium
(c) Meitnerium
(d)Hahnium

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5.9 ANSWERS
1. Due to high charge density actinides are capable of forming oxo cations in
which these elements show higher oxidation states.
2. Because the tendency of disproportionation of these oxocations increases with
increasing atomic number. Hence the oxocations of heavier actinides do not
exist.
3. Beyond atomic number 102, the size of nucleus increases thereby decreasing
the nuclear stability. This causes lower probability of existence of stable
elements beyond this atomic number.
4. & 5. Pl. refers to the text.
6. c
7. a

5.10 BOOKS/REFERENCES CONSULTED

1. Advanced Inorganic Chemistry: F.A. cotton and G. Wilkinson, John Wiley and
Sons, New York.
2. Inorganic Chemistry: Alan G. Sharpe, ELBS and Longman, Essex England.
3. Principles of Inorganic Chemistry: B.R. Puri, L.R. Sharma and K.C. Kalia,
Milestone Publishers & Distributors, Delhi.
4. Selected Topics in Inorganic Chemistry: W.U. Malik, G.D. Tuli and R.D.
Madan, S. Chand and Co. Ltd., New Delhi.
5. Comprehensive Inorganic Chemistry: Suleka Chandra, New Age Inter national
(P) Limited. Publishers, New Delhi.
6. Advance Inorganic Chemistry Vol. II: S. Prakash, G.D. Tuli et al., S. Chand and
Co. Ltd., and New Delhi.

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