Unit 3 Inner-Transition Elements

UNIT 3
INNER-TRANSITION
ELEMENTS

Structure
3.1 Introduction Colour of Ions

Expected Learning Outcomes Electrode Potentials

3.2 General Characteristics Magnetic Properties

Electronic Configuration and

Position in Periodic Table
3.3 Separation of
Lanthanoid Contraction
Lanthanoids
Atomic Radii
(Ion-Exchange Method)
Melting and Boiling Points
3.4 Summary
Densities
3.5 Terminal Questions
Ionization Enthalpy
3.6 Answers
Oxidation States

3.1 INTRODUCTION
In the preceding two units, you have studied the main features of the
chemistry of the transition elements which belong to the d-block of the periodic
table. In this unit you will study the salient features of the chemistry of the
transition elements of the f–block of the periodic table. As the electrons are
filled in the antepenultimate f-orbitals which is an inner shell, these elements
are also termed as inner-transition elements. As discussed in Unit 1 of this
course you should recall that the f-block elements comprise two series of
elements - the lanthanoid series and the actinoid series. You will observe that
in comparison to the elements of d-block transition series, the members of
lanthanoid series resemble one another much more closely. Usually they have
one common stable oxidation state and they occur together in the same ores
in nature. Because of the similarity in their chemical properties their separation
from each other is very difficult. The chemistry of the actinoids is more
complicated because they exhibit more than one oxidation state and their
radioactive nature creates problems in the study of their properties. In this unit
you will study the general features of the chemistry of lanthanoids and
actinoids with emphasis on periodicity in their properties. 49
Block 1 d and f Block Elements

Expected Learning Outcomes

After studying this unit you should be able to:

 understand the electronic configuration and position in periodic table of

the inner-transition elements;

 understand lanthanoid contraction and its consequences;

 follow the trends in the atomic radii, melting and boiling points, densities
and ionization enthalpy of the inner-transition elements;

 get an idea about the various oxidation states of the inner-transition

elements;

 have knowledge about the colour of the ions;

 discuss the electrode potentials;

 understand the magnetic properties; and

 discuss the separation of lanthanoids by Ion-Exchange method.

3.2 GENERAL CHARACTERISTICS

The lanthanoids are silvery white soft metals and tarnish very fast in air.
Although lanthanoid means 'like lanthanum' and so should not include
The lanthanoids are lanthanum, lanthanum has become included by common usage. Similarly
referred as “rare earth actinium is included in the actinoid series. The ending 'ide' normally indicates a
elements” sometimes, negative ion, and therefore the terms lanthanoid and actinoid are preferred to
but this name is lanthanide and actinide. However, lanthanide and actinide are still allowed
inappropriate as they owing to wide current use. The f-block consists of the two series, lanthanoids
are not rare, except
(the fourteen elements following lanthanum) and actinoids (the fourteen
for promethium,
elements following actinium). The lanthanoids resemble one another more
which does not have
a stable isotope. closely than do the members of ordinary transition elements in any series. In
Unit 1 of this course, in Fig. 1.1, you can see that the inner-transition elements
(lanthanoids and actinoids) are placed as two rows separated out from the
main periodic table. The lanthanoids have only one stable oxidation state and
their chemistry provides a study on the effect of small changes in size and
nuclear charge along a series of elements which are quite similar in many
respects. The chemistry of the actinoids is, on the other hand, much more
complicated. Many of the actinoids form compounds similar to those of the
transition metals. Their complication is to some extent due to the wide range
of oxidation states in these elements and to also their radioactivity. The earlier
members have quite long half-lives compared to the others later in the series.
The latter members can only be prepared in nanoscale (nanograms). All
these make the study of actinoids very difficult. A general lanthanoid is
represented by the symbol Ln and an actinoid by An.

3.2.1 Electronic Configuration and Position in Periodic

Table
Now let us look at the electronic configurations and some salient physical
properties of the inner-transition elements. The actual ground state electronic
50
Unit 3 Inner-Transition Elements

configurations of lanthanoids have been determined from atomic spectroscopy

and are given in Table 3.1 along with the metallic and ionic radii, electrode
potential and colour of the trivalent lanthanoid ions.
Table 3.1: Some properties of lanthanum and the lanthanoids

Electronic configuration Metallic

Ionic radius Colour of
Z Name Symbol outside the [Xe] core radius E0(V) M3+/M
M3+ pm Ln3+
Ln Ln3+ pm

57 Lanthanum La 5d16s2 -- 187 106 -2.52 Colourless

58 Cerium Ce 4f15d16s2 4f1 183 103 -2.48 Colourless

59 Praseodymium Pr 4f 36s 2 4f 2 182 101 -2.46 Pale Green

60 Neodymium Nd 4f 46s 2 4f 3 181 100 -2.43 Lilac

61 Promethium Pm 4f 56s 2 4f 4 -- 98 -2.42 Pale Yellow

62 Samarium Sm 4f 66s 2 4f 5 179 96 -2.41 Yellow

63 Europium Eu 4f 76s 2 4f 6 204 95 -2.41 Pale pink

64 Gadolinium Gd 4f 75d16s2 4f 7 180 94 -2.40 Colourless

65 Terbium Tb 4f 96s 2 4f 8 178 92 -2.39 Pale pink

66 Dysprosium Dy 4f 106s 2 4f 9 177 91 -2.35 Yellow

67 Holmium Ho 4f 116s 2 4f 10 176 89 -2.32 Yellow

68 Erbium Er 4f 126s 2 4f 11 175 88 -2.30 Rose pink

69 Thulium Tm 4f 136s 2 4f 12 174 87 -2.28 Pale green

70 Ytterbium Yb 4f 146s 2 4f 13 194 86 -2.27 Colourless

71 Lutetium Lu 4f 145d16s2 4f 14 174 85 -2.26 Colourless

The ground-state electron configurations of the lanthanoids may be

represented as [Xe]4fn5d0-16s2. Lanthanum which has the electronic
configuration [Xe]5d16s2 is excluded from this generalization, but it is included
in the table as like the other members it has a stable oxidation state of +3 and
has other similarities. The electron configuration of the Ln3+ ions vary regularly
from 4f1 for Ce3+ to 4f14 for Lu3+. Now look at the Table 3.1 and try to
understand the examples given below.

EXAMPLE 3.1: In the lanthanoids, which atoms have an electron in the 5d

orbital? In other elements where has this electron been shifted
to?

SOLUTION: By looking at the electronic configurations of atoms in Table 3.1,

it can be said that there is an electron in the 5d orbital only in Ce,
Gd and Lu, in all other elements this electron is shifted to the 4f
orbital. This sort of shuttling of electrons can be understood in
terms of the comparable energies of the 4f and the 5d orbital.
51
Block 1 d and f Block Elements

EXAMPLE 3.2: Does the presence of an electron in the 5d orbital affect the
properties of the lanthanoids?
SOLUTION: Now, at this stage you should follow that the presence of an
electron in 5d orbital is not important as the lanthanoids have the
prevalence of +3 oxidation state in ionic compounds. So, the
Ln3+ ions have electronic configurations which varies in a regular
manner from [Xe]4f1 for Ce3+ to [Xe]4f14 for Lu3+ as seen from
Table 3.1.

EXAMPLE 3.3: The lanthanoids have the general pattern of electronic

configuration as [Xe]4fn5d06s2, can you find the three
exceptions to this case?
SOLUTION: Among the lanthanoids, exceptions to the 4fn5d06s2 pattern are
found in three cases:
(a) At Ce, where the electron configuration is [Xe]4f15d16s2. The 4f orbitals
cannot be contracted as the nuclear charge is not sufficient and thus
their energy cannot be lower than 5d.
(b) Gadolinium has the [Xe]4f75d16s 2 configuration, which may be due to
the extra stabilization as expected in a half-filled f-shell.
(c) Lutetium also has the[Xe]4f 145d16s2 configuration where the last electron
is added beyond the capacity of the 4f-shell.

Table 3.2: Some properties of actinium and the actinoids

0
Z Name Symbol Electronic configuration Metallic Ionic radius E (V) Colour of
3+ 3+ 3+
outside the [Rn] core radius pm M pm M /M An
3+
An An
89 Actinium Ac 6 d 17 s 2 5f 0 -- 112 - 2.6 Colourless

90 Thorium Th 6 d 2 7s 2 5f 1 179 -- -- --

91 Protactinium Pa 5f 2 6d 1 7s 2 5f 2 163 104 -1.95

92 Uranium U 5f 3 6d 1 7s 2 5f 3 156 103 -1.80 Colourless

93 Neptunium Np 5f 4 6d 17s 2 5f 4 155 101 -1.86 Red brown

94 Plutonium Pu 5f 6 7s 2 5f 5 155 100 -2.03 Purplish

95 Americium Am 5f 7 7s 2 5f 6 159 98 -2.38 Blue violet

96 Curium Cm 5f 7 6d 1 7s 2 5f 7 173 97 -- Pink

97 Berkelium Bk 5f 9 7s 2 5f 8 174 96 -- Pale

Yellow
98 Californium Cf 5f 10 7s 2 5f 9 170 95 -- --

199 Einstenium Es 5f 11 7s 2 5f 10 186  2 -- -- --

100 Fermium Fm 5f 12 7s 2 5f 11 186  2 -- -- --

101 Mendelevium Md 5f 13 7s 2 5f 12 -- -- -- --

102 Nobelium No 5f 14 7s 2 5f 13 -- -- -- --

103 Lawrencium Lr 5f 14 6d 17s 2 5f 14 -- -- -- --

52
Unit 3 Inner-Transition Elements

Now let us discuss the electronic configuration of the actinoids and this we will
do based on the data given in Table 3.2. The ground state electronic
configuration of actinium, [Rn] 6d 17s 2 has similarities with that of lanthanum
and this maybe the reason that they show similar chemical properties. The
electronic configurations of the actinoids following actinium are not known
exactly and not as certainly as those of lanthanoids. The difference in energy
between 5f and 6d orbitals in the beginning of actinoids is less than that
between 4f and 5d orbitals for the lanthanoids. Thus both the 5f and 6d
orbitals are involved in accommodating successive electrons. So, if you give a
closer look at the data in Tables 3.1 and 3.2 you will see that the filling of 5f
orbitals in actinoids is not much regular compared to the filling of the 4f orbitals
in lanthanoids. As you move to the heavier actinoids, i.e. plutonium onwards
the 5f orbitals become more stable and seem to be of lower energy than the
6d orbitals, so the electrons would prefer occupying the 5f orbitals.

SAQ 1
Explain briefly:

a) What are inner-transition elements?

b) What are lanthanoids and actinoids? Why are they so called?

c) Write the electronic configurations of the elements of atomic number 61

and 95.

3.2.2 Lanthanoid Contraction

The atomic and ionic radii (Table 3.1 and Fig. 3.1) of lanthanum and the
lanthanoids show a steady decrease along the series; this is commonly known
as lanthanoid contraction. The 4f orbitals of the lanthanoids make very little
contribution to bonding: their radial distribution functions lie within the 6s and
5d orbitals. Electrons are removed much easily from the 6s and 5d orbitals
when the lanthanoids form the +3 ion. Lanthanoids thus show mainly ionic
bonding. The underlying reason for this has been mentioned earlier – poor
shielding by the 4f electrons causes the effective nuclear charge to rise
steadily across the series. It has already been discussed in Unit 1 of this
course that as a consequence of lanthanoid contraction, elements of 4d and
5d transition series show similarity in properties.

3+
Fig. 3.1: Variation of Ionic radii for the Ln ions in pm (picometer). 53
Block 1 d and f Block Elements

3.2.3 Atomic Radii

You have studied in previous courses that the atomic size decreases with
increase in atomic number along any period due to increase in effective
nuclear charge. However, the decrease in atomic radius is small when the
differentiating electron enters an inner orbital. This is because the additional
inner electron screens the size-determining outer electrons from the nucleus
much better than an additional outer electron. For example, decrease in the
covalent radius from Sc to Zn, i.e., across ten elements of the 3d transition
series, is 19 pm. This decrease is almost one-third of the decrease in the
covalent radius of the seven elements of s and p blocks of the period 3.

The rate of decrease in atomic radius along the lanthanoids (Table 3.1) and
also along the actinoids (Table 3.2) is even less than that in the transition
series, since the difference in the electronic configurations of these elements
is in the number of electrons in the antepenultimate (last but two) shell of
electrons. But the cumulative effect of decrease in atomic radius across the
fourteen elements of lanthanoids is quite substantial. This decrease in atomic
radius across the lanthanoids is known as lanthanoid contraction. Similarly,
there is an actinoid contraction across the actinoids. In the actinoids, due to
poor shielding by 5f electrons, the actinoid contraction is greater from element
to element. As a result of lanthanoid contraction, the normal increase in size
from Sc – Y – La disappears after the lanthanoids, and pairs of elements such
as Zr and Hf, Nb and Ta, Mo and W, etc., possess nearly similar sizes
(Table 3.3). The properties of these elements, therefore, are very similar. The
similarities in properties within these pairs make their separation very difficult.
Thus, due to lanthanoid contraction, the elements of 5d and 4d transition
series resemble each other much more closely than do the elements of 4d and
3d series.

Table 3.3: Atomic (covalent) radii of the elements preceding and

following the lanthanoids in pm(picometer)

21 22 23 24 25 26 27 28 29 30

Sc Ti V Cr Mn Fe Co Ni Cu Zn

144 132 122 118 117 117 116 115 117 125

39 40 41 42 43 44 45 46 47 48

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

162 145 134 130 127 125 125 128 134 144

57 58-71 72 73 74 75 76 77 78 79 80

La Ce-Lu Hf Ta W Re Os Ir Pt Au Hg
165-156
169 144 134 130 128 126 127 130 134 147

SAQ 2
Explain the term lanthanoid contraction and its consequences.
54
Unit 3 Inner-Transition Elements

3.2.4 Melting and Boiling Points, Densities

Table 3.4: Melting and boiling points, densities of lanthanum and the
lanthanoids

o o -3
Element M. P. C B. P. C Density g cm
La 920 3420 6.20
Ce 798 3433 6.77
Pr 931 3520 6.77
Nd 1021 3074 7.01
Pm 1042 - -
Sm 1074 1794 7.52
Eu 822 1429 5.23
Gd 1313 3273 7.90
Tb 1365 3230 8.23
Dy 1412 2567 8.55
Ho 1474 2700 8.80
Er 1529 2868 9.10
Tm 1545 1950 9.30
Yb 819 1196 6.97
Lu 1663 3402 9.84

In general lanthanoids have high melting points and boiling points. The melting
points of the lanthanoids increase at a very fast rate with increasing atomic
number from 798 °C for cerium to 1,663 °C for lutetium (more than doubling of
the melting point temperatures takes place). The low melting points for the
light to middle lanthanoids are thought to be due to a 4f electron contribution to
the bonding, which is a maximum at cerium and decreases with increasing
atomic number to about zero at erbium. The low melting points of europium
and ytterbium are due to their divalency.

EXAMPLE 3.4: Now look at Table 3.4, what is the pattern in the variation of
the densities and melting and boiling points of the elements?
Explain the reason of low values as shown by some.

SOLUTION: The densities and melting and boiling points of the elements
show a periodic variation, reaching minima at Eu and Yb.
Europium and ytterbium have inner core stable configurations 4f7
and 4f14 to participate in metallic bonding. This leaves only the
two outer 6s electrons to enter the conduction bands, thus
leaving larger cores and weaker binding forces.

3.2.5 Ionization Enthalpy

Now we will discuss about the ionization enthalpies of the lanthanoids which is
related to their electronic structures. You already know that 4f electrons are
poorly screened from the nuclear charge. When an atom of the lanthanoids 55
Block 1 d and f Block Elements

ionizes, first the two valence 6s electrons and one further electron (from either
the 4f or 5d orbital) are removed. Thereafter, the remaining 4f electrons are
held tightly by the nucleus. From Table 3.5 and Fig. 3.2 we can see how the
ionization energies vary across the lanthanoids.

There are no compounds with Ln(+4) as the fourth ionization enthalpy I4 is

approximately the same as the sum of the first three ionization enthalpies
(I1 + I2 + I3). The nuclear attraction increases across the lanthanoid series
which leads to the ionization enthalpies increasing gradually which is related to
the electronic structure of the particular atom. If you look at Fig. 3.4 you can
see that the variation of I3 shows three sharp discontinuities, the largest of
which are seen between Eu and Gd. Ionisation of Eu2+ correspond to removal
of an electron from the half-filled 4f7, whereas ionization from Gd2+involves a
less tightly bound d- electron. The stable oxidation states shown by the
elements is largely determined by their ionization enthalpies. We shall discuss
them later.
Table 3.5: Ionization enthalpies for the lanthanoids in kJ/mol

Element I1 I2 I3

La 538 1067 1850

Ce 528 1047 1949

Pr 523 1018 2090

Nd 530 1034 2128

Pm 536 1052 2140

Sm 543 1068 2260

Eu 547 1085 2425

Gd 592 1172 1999

Tb 564 1112 2122

Dy 572 1126 2220

Ho 581 1139 2200

Er 589 1151 2190

Tm 597 1163 2284

Yb 603 1175 2415

Lu 524 1341 2022

56 Fig. 3.2: Variation of ionization enthalpies for the lanthanoids.

Unit 3 Inner-Transition Elements

3.2.6 Oxidation States

As discussed in the section 3.2.5, the first three ionization enthalpies of the
lanthanoids is comparatively low and they are strongly electroposive with a
principal oxidation state of +3. Refer to the Table 3.1 and follow their electronic
configurations to understand that the elements adjacent to lanthanum (4f0),
gadolinium (4f7) and lutetium (4f14) also exhibit other oxidation states. The
oxidation states commonly encountered for the elements are shown in Table
3.6 given below:
Table 3.6: Oxidation states of Lanthanum and Lanthanoids

La Ce Pr Nd Pm Sm Eu Gd

3 3, 4 3, (4) 3 3 3 (2) 3 (2) 3

Tb Dy Ho Er Tm Yb Lu

3 (4) 3 (4) 3 3 3 (2) 3, 2 3

*The unstable oxidation states are enclosed in parentheses.

The predominant oxidation state is +3. Some lanthanoids show + 2 or + 4

oxidation states but these are usually less stable than the +3 state. Cerium
(+4) is a notable exception. In Table 3.6 you can see that +2 or +4 also exist
for some lanthanoids which gain extra stability by attaining half-filled or
completely filled configurations, e.g. cerium (+4) and terbium (+4) which have
f0 and f7 configuration respectively. Lanthanum exhibits only the +3 state as
the trivalent ion has a noble gas configuration. Similarly, gadolinium and
lutetium form only the M3+ ion which have the half-filled f7 and filled f14
configuration. The +3 state in the lanthanoids is most common which is very
much striking if compared with the variable oxidation states of the d- block
transition elements dealt in Unit 1.

Following are the examples where number of electrons in ions is different than
those with stable f n configurations:
n

f0: La3  , Ce4  , Ac 3  , Th4  ,Pa5  , V 6 

f 7: Eu2  , Gd3  , Tb4  , Cm3  ,Bk 4 

f 14 : Yb2 , Lu3 

Exceptions are the following:

0 7 14
non - f non - f non - f

Pr 4  (4 f 1) Nd4  (4 f 1), Sm2 (4 f 6 ) Tm2  (4 f 13 )

So you must remember that other factors like ionization enthalpies and
sublimation energies of the metals as well as lattice energies may be
responsible to make the various oxidation states stable. 57
Block 1 d and f Block Elements
Table 3.7: Oxidation states of actinium and the actinoids. The more
stable states are in bold type; unstable states are enclosed in
parentheses.

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
(2) (2) (2) 2 2 2 --
3 (3) (3) 3 3 3 3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4 4 (4)
5 5 5 5 5
6 6 6 6
(7) 7

For the actinoids, there is a great range of oxidation states. Can you guess
why is it so? It is because the 5f, 6d and 7s levels have comparable energies.
Table 3.7 shows the known oxidation states of actinium and the actinoids in
which numbers in bold indicate the most stable oxidation state in aqua
solution. The 5f orbitals are slightly more diffuse and the actinoids have a
chemistry which includes even covalent bonding and a variety of oxidation
states for the earlier members of the series. The 5f orbitals of the actinoids
are more penetrating and provide better shielding from the nuclear charge,
they are thus more diffuse than the 4f orbitals and they can overlap in a better
way with ligand orbitals. The 6d orbitals are similarly expected to be more
effective in covalent bond formation than their 5d counterparts. The most
common oxidation state of actionoids is thus +3 as seen from Table 3.7. From
the Table 3.7 you can also see that the initial elements of the actinoids show
higher oxidation states but not so for those later in the series. Such uneven
distribution of oxidation states among actinoids does not recommend learners
to study their chemistry in terms of oxidation states.

You will be learning that actinoids have significant similarities with transition
metals, form a number of complexes and display a wide multiplicity of
oxidation states. This is in contrast to the lanthanoids which resemble the
Group 2 metals and mostly form ionic bonds.

SAQ 3
Which is the most common oxidation state of the lanthanoids? Give its
configuration.

3.2.7 Colour of Ions

The ions of lanthanoids and actinoids are coloured in the solid state as well as
in aqueous solution, as is the case with the ions of transition metals. You have
studied in the preceding unit that the colours of transition metal ions arise
because of absorption of light due to d-d electronic transitions. The colours of
lanthanoid and actinoid ions arise due to electronic transitions in the 4f and 5f
orbitals. Colours of hydrated lanthanoid and actinoid ions are given in
58 Table 3.1 and 3.2, respectively.
Unit 3 Inner-Transition Elements

Many trivalent lanthanoid ions are strikingly coloured both in the solid state
and in aqueous solution. The colour seems to depend on the number of
unpaired f electrons. Elements with (n)f electrons often have a similar colour to
those with (14 - n)f electrons (see Table 3.1). However, the elements in other
valency state do not all have colours similar to their isoelectronic 3+
counterparts (Table 3.8).

Colour arises because light of a particular wavelength is absorbed in the

visible region. The wavelength absorbed corresponds to the energy required
to promote an electron to a higher energy level.
Table 3.8: Colours of Ln4+, Ln2+ and their isoelectronic Ln3+ counterparts

Ce4  Orange-red 4f0 La 3  Colourless

Sm2  Blood-red 4f6 Eu3  Pale pink

Eu2  Pale greenish yellow 4f7 Gd3  Colourless

Yb2  Yellow 4 f 14 Lu 3  Colourless

Except Lu3+(f14), the lanthanoid ions show absorptions in the visible or UV

region of the spectrum. These colours arise from f-f transitions. Strictly these
transitions are Laporte forbidden (since the change in the subsidiary quantum
number is zero) and so the colours are pale because they depend on
relaxation of the rule. The f orbitals are deep inside the atom and an f electron Ligand is any atom
has the subsidiary quantum number l = 3, so ml may have values 3, 2,1,0,-1,- or molecule attached
2,-3. Thus a large number of transitions are usually possible. You must to a central atom,
remember that for transition elements d-d spectra give absorption bands. For usually a metallic
element, in a
transition metal complexes the ligand play an important role in widening the
coordination
peaks of the absorption bands. It is also possible to get transitions from the 4f or complex
to the 5d level. Such transitions give broader peaks and their position is compound. Examples
affected by the nature of the ligands.The peaks of absorption spectra of of common ligands
lanthanoid ions are narrow and very characteristic. Ce3+ and Yb3+ are are the neutral
colourless because they do not absorb in the visible region. However, they molecules water
show exceptionally strong absorption in the UV region, because of transitions (H2O), ammonia
from 4f to 5d. f-d peaks are broad, in contrast to the narrow f-f peaks.

Charge transfer spectra are possible due to the transfer of an electron from
the ligand to the metal. This is more probable if the metal is in a high oxidation
state or the ligand has reducing properties. Generally charge transfer
produces intense colours. The strong yellow colour of Ce4+ solutions, the blood
red colour of Sm2+are due to charge transfer.

3.2.8 Electrode Potentials

The standard electrode potentials of lanthanoids for the half-reaction,

Ln3+ (aq) + 3e Ln (s)

are given in Table 3.1. The electrode potentials are very low. Therefore, these
elements are highly electropositive and reactive metals. The electrode 59
Block 1 d and f Block Elements

potential increases from Ce to Lu, which is consistent with the slight decrease
in the ionic radius due to lanthanoid contraction. The electrode potentials of
the actinoids also are quite low (Table 3.2) and the actinoids also are highly
electropositive and reactive metals.

In keeping with the gradually decreasing size from lanthanum to lutetium the
standard electrode potentials (M3+/M) of the lanthanoids register an increase
from lanthanum (-2.52 volt) to lutetium (-2.26volt) (Table 3.1). The magnitude
of the standard potentials shows that the lanthanoids are fairly strong basic
elements. Their ionization enthalpies also register an increase from lanthanum
to lutetium (Table 3.5) but not gradually. Generally basic properties increase
with increasing atomic number across a period. But for the lanthanoids it is
not true. Lanthanum (+3) is the most basic while lutetiuim (+3) is the least
basic. The metals tarnish in air and burn to give the oxides Ln2O3. Exception
is for Ce which forms CeO2. They react with halogens to give the trihalides
LnX3. The lanthanoids dissolve rapidly in dilute acids with evolution of H2 to
produce Ln(+3) salt solution.

The electrode potentials of the actinoids also are quite low (Table 3.2).
Therefore, the actinoids also are highly electropositive and reactive metals.

3.2.9 Magnetic Properties

You have learnt in the preceding unit that paramagnetism is associated with
the presence of unpaired electrons in a substance. The lanthanoid and
actinoid ions, other than f0 type (e.g., La3+. Ce4+, Ac3+, Th4+, Pa5+, U6+) and f14
type (e.g. Yb2+, Lu3+, Lr3+), are all paramagnetic, because each of the seven f
orbitals characterising inner-transition metal species (lanthanoid and actinoid)
must contain a single electron before any pairing can take place (Hund’s rule).

You have also studied that in case of transition elements, the contribution of
orbital motion of electrons to paramagnetism is negligible and can be ignored.
The magnetic moments of transition metal ions can be explained in terms of
the spin contribution of the unpaired electrons present in d-orbitals. However
in case of the lanthanoids the magnetic moments of only those ions, which
have f0, f7 and f14 configuration agree with the spin only value. In all other
cases, the magnetic moment values are higher than those calculated on the
basis of spin only formula. This can be explained by taking orbital contribution
to magnetic moment also into account. In lanthanoid ions, the 4f orbitals are
comparatively better shielded from the surroundings by the overlying 5s and
5p orbitals than the d orbitals in transition metal ions. Therefore, the
contribution of orbital motion to paramagnetism is not quenched.

The actinoids display magnetic properties similar to that of the lanthanoids,

however the magnetic properties of the actinoid ions are complicated than
those of the lanthanoid ions. This partially arises from (i) the fact that the 5f
electrons are nearer the surface of the atom and are easily influenced by the
chemical environment, although not to the same extent as do the d electrons,
and (ii) the less sharply defined distinctions between 5f and 6d electrons as
compared with 4f and 5d electrons. From the above discussion it is clear that
the magnetic moments of the f-block (inner transition) metal ions must be
60 calculated taking into account both spin and orbital contributions.
Unit 3 Inner-Transition Elements

The magnetic moment of transition elements may be calculated from the

equation.

(S  L )  4S(S  1)  L(L  1)

(µS+L) is the magnetic moment in Bohr magnetons calculated using both the
spin and orbital momentum contributions. S is the resultant spin quantum
number and L is the resultant orbital momentum quantum number. In the
previous unit you have calculated the magnetic moment of the first row
transition elements using the spin only formula. This is because the orbital
contribution is quenched out by interaction with the electric fields of the ligands
in its environment. µs is the spin only magnetic moment in Bohr magnetons. S
is the resultant spin quantum number and n is the number of unpaired
electrons.)

s  4S(S  1)

s  n (n  2)

La3+(f 0), and two of the lanthanoids Gd3+ (f 7) and Lu3+ (f14).

SAQ 4
Gd3+ has seven unpaired electrons, find its spin only magnetic moment.

The magnetic moments of the other lanthanoid ions do not obey this simple
relationship. Their magnetic moment arises from the unpaired electron spins
and that from the orbital motion. This also happens with the second and third
row transition elements. Here you must note that the magnetic properties of
the lanthanoids are basically not the same as those of the transition elements.
In the lanthanoids the spin contribution S and orbital contribution L couple
together to give a new quantum number J.
J = L – S when the shell is less than half full
(as per Hund’s third rule)
and J = L + S when the shell is more than half full

so the expression for magnetic moment is

μ  g J(J  1)

where

1 S(S  1)  L(L  1)
g 1 
2 2J(J  1)

Fig. 3.3 shows the calculated magnetic moments for the lanthanoids using
both the simple spin only formula, and the coupled spin plus orbital momentum
formula. You can see that the calculated values using the coupled spin +
orbital momentum formula and experimental values measured at 300 K (26.85
o
C) match in most cases. The range of experimental values are shown as
bars. 61
Block 1 d and f Block Elements
Two cases Eu3+and Sm3+ do not show good match. The reason is that with
Eu3+ the spin orbit coupling constant is very low.

3+
Fig. 3.3: Paramagnetic moments of La and the lanthanoid ions at 300K
o
(26.85 C). Theoretical (Spin-only) values are shown as broken
line(green), theoretical (spin + orbital) values are shown as broken
line(red) and the observed values as solid line (purple). The range of
experimental values are shown as bars.

Table 3.9: Magnetic moments of La3+ and the Ln3+ ions

Electronic Magnetic moment

Structure Calculated Observed
3+
of M (BM) (BM)
0
La [Xe]4f 0 0
1
Ce [Xe]4f 2.54 2.3-2.5
2
Pr [Xe]4f 3.58 3.4-3.6
3
Nd [Xe]4f 3.62 3.5-3.6
4
Pm [Xe]4f 2.68 2.7
5
Sm [Xe]4f 0.84 1.5-1.6
6
Eu [Xe]4f 0 3.4-3.6
7
Gd [Xe]4f 7.94 7.8-8.0
8
Tb [Xe]4f 9.72 9.4-9.6
9
Dy [Xe]4f 10.63 10.4-10.5
10
Ho [Xe]4f 10.60 10.3-10.5
11
Er [Xe]4f 9.57 9.4-9.6
12
Tm [Xe]4f 7.63 7.1-7.4
13
Yb [Xe]4f 4.50 4.4-4.9
14
Lu [Xe]4f 0 0
62
Unit 3 Inner-Transition Elements

3.3 SEPARATION OF LANTHANOIDS

The separation of lanthanoids is very difficult as most of them generally occur Deposit of monazite
together. Although a large number of minerals are known to contain occur in Southern
lanthanoids, only three of them, viz., monazite, bastnaesite and xenotime are India, South Africa
of commercial importance. Both monazite and bastnaesite are richer in the and Brazil.
lighter lanthanoids,

As all the lanthanoids occur together in nature, their extraction involves two
main steps: (i) separation from one another and (ii) reduction of their
compounds to metals. Since the lanthanoids are all typically trivalent and are
almost identical in size, their chemical properties are almost similar. Therefore,
the separation of lanthanoids from one another is almost as difficult as the
separation of isotopes. Only cerium and europium can be separated from the
remaining lanthanoids by employing conventional chemical methods because
of stabilities of Ce4+ and Eu2+ in aqueous solution. Cerium can be separated
from a mixture of lanthanoids by oxidising Ce3+ to Ce4+ with permanganate or
bromate or hypochlorite in an alkaline medium and subsequently precipitating
it as CeO2. Europium can be reduced to Eu2+ either by electrolytic reduction
with a mercury cathode or by using zinc amalgam. It is then precipitated from
the solution as EuSO4.

Earlier the lanthanoids used to be separated from each other by selective

precipitation or by fractional crystallization. These processes need to be
repeated several times and thus are very tedious and not very efficient.
However, the individual elements can now be separated with much less
difficulty on a large scale by employing more efficient techniques of solvent
extraction and ion exchange chromatography.

The process of ion exchange chromatography is the most important, rapid and
effective method for the separation and purification of the lanthanoids. In this
process, a solution of lanthanoid ions is run down a column of a synthetic ion
exchange resin. Ion exchange resins are organic polymers consisting of
functional groups such as – COOH, -SO3H or –OH. In these resins, hydrogen
ions are mobile and can be exchanged with other cations. Thus, the
lanthanoid ions replace the H+ ions and get bound to the resin:

Ln3+ + 3R-SO3H Ln(SO3R)3 + 3H+

After the H+ ions have passed through the column, a solution of a complexing
agent such as citric acid, α-hydroxyisobutyric acid or EDTA at the appropriate
pH is passed through the column to elute, i.e., to wash off the metal ions in a
selective manner:

Ln(O3SR)3 + (NH4)3EDTAH Ln(EDTAH) + 3NH4O3SR

As the EDTA solution flows down the column, the lanthanoid ions come off the
resin and or a complex with EDTA and then go back on the resin a little lower
down the column. This process is repeated many times as the metal ions
gradually travel down the column. The smaller lanthanoid ions like Lu3+ form
stronger complexes with EDTA than the larger ions like La3+. Thus, the smaller
and heavier ions spend more time in solution and less time on the column. 63
Block 1 d and f Block Elements

Therefore, the heavier ions are eluted from the column first and the lighter
ones the last. Using suitable conditions, all the individual elements can be
separated. The eluates are then treated with an oxalate solution to precipitate
lanthanoids as oxalates which are then ignited to get the oxides:

2Ln(EDTAH) + 3(NH4)2C2O4 Ln2(C2O4)3 +2(NH4)3EDTAH

Ln2(C2O4)3 Ln2O3 + 3CO + 3CO2

Samarium, europium and ytterbium are prepared by reduction of the oxides

with La at high temperatures:

Ln2O3 + 2La Ln2O3 + 2Ln, Ln=Sm and Eu

Other lanthaniods are obtained by the reaction of LnCl3 or LnF3 with Ca metal
at 1300 K. LnCl3 or LnF3 are prepared by heating Ln2O3 with appropriate
ammonium halide:

Ln2O3 +6NH4X LnX3-6NH3+ 3H2O

2LnX3 + 3Ca 2Ln + 3CaX2

SAQ 5
Why is the separation of the lanthanoids so difficult? List three important
methods used for the separation of lanthanoids.

3.4 SUMMARY
In this unit, you have studied electronic configuration and position of inner-
transition elements in the periodic table. Thereafter you have come across the
concept of lanthanoid contraction, atomic radii, melting and boiling points,
densities, ionisation enthalpy, oxidation states, colour of ions, electrode
potentials and magnetic properties of lanthanoids and actinoids which can be
summarized as following:

 The lanthanoids and actinoids are characterized by filling of 4f and 5f

subshells, respectively

 For the lanthanoids, actinium and transamericium elements, the tripositive

oxidation state is the most stable in every case. However, the oxidation
states higher than +3 are quite common for the early actinoids.

 The lanthanoids exhibit greater similarities in their properties in their most

prominent oxidation state, +3. Cerium and europium are the only
lanthanoids to be stable as Ce4+ and Eu2+ in aqueous solution.

 All the lanthanoid and actinoid ions which have unpaired electrons are
paramagnetic. The magnetic moment of lanthanoid and actinoid ions
depends on both spin and angular momentum of the unpaired electrons.

 All the lanthanoids and actinoids are highly electropositive and reactive
64 metals. They react with oxygen, halogens, hydrogen, water and acids.
Unit 3 Inner-Transition Elements

Also in this unit you have learnt how separation of lanthanoids by ion-
exchange method is carried out. Since the lanthanoids are all typically trivalent
and are almost identical in size, their chemical properties are almost similar.
As all the lanthanoids occur together in nature, their separation is extremely
difficult.

3.5 TERMINAL QUESTIONS

1. What are f-block elements?

2. Discuss the ways in which the actinoids resemble their lanthanoid

congeners.

3. Discuss the ways in which the early actinoids more closely resemble the
transition elements.

4. Discuss the position of lanthanoids and actinoids in the periodic table.

5. Why are most of the lanthanoid and actinoid compounds paramagnetic?

6. Why the lanthanoids show very few oxidation states compared to the
early actinoids?

7. Compare the chemistry of actinoids with that of the lanthanoids with

special reference to: (i) electronic configuration (iii) oxidation state (ii)
atomic and ionic sizes.

8. Which is the last element in the series of the actinoids? Write the
electronic configuration of this element. Comment on the possible
oxidation state of this element.

9. Name the members of the lanthanoid series which exhibit +4 oxidation

states and those which exhibit +2 oxidation states. Try to correlate this
type of behaviour with the electronic configurations of these elements.

10. Why the actinoid contraction is greater from element to element than the
lanthanoid contraction?

3.6 ANSWERS
Self Assessment Questions

1. (a) Two series of elements from cerium (atomic number 58) to Iutetium
(atomic number 71) and thorium (atomic number 90) to lawrencium
(atomic number 103) are known as inner-transition elements. The term
transition is used because they exhibit transition behavior by exhibiting
variable oxidation states, forming coloured ions and exhibiting
paramagnetism. The prefix inner is used because in the building up
process of their atoms the differentiating electron enters the f-orbitals of
an inner shell.

(b) The 14 elements form cerium (atomic number 58) to lutetium (atomic
number 71) which follow lanthanum (atomic number 57) in the periodic
table are called lanthanoids. Similarly, 14 elements from thorium 65
Block 1 d and f Block Elements

(atomic number 90) to lawrencium (atomic number 103) which follow

actinium (atomic number 89) in the periodic table are called actinoids.

(c) The electronic configuration of the elements of atomic number 61 and 95

is [Xe]4f56s2 and [Rn]5f7s2, respectively.

2. The gradual decrease in atomic size of the lanthanoid starting form

cerium to lutetium is known as lanthanoid contraction. Because of
lanthanoid contraction, the elements from hafnium to mercury that follow
the lanthanoids have unusually small sizes.

3. The most common oxidation state of lanthanoids is +3. This oxidation

state of the lanthanoid ions arises due to the loss of two 6s electrons
and the lone 5d electron if present, from the atom of the elements. If no
electron is present in the 5d orbital, then one of the electrons from the 4f
shell is lost. The lanthanoid ions in this oxidation state have the general
configuration [Xe]4f1-14.

4. μ s  7(7  1)  63  7.9 BM

5. The most stable oxidation state of the lanthanoids is +3. The ionic radius
of Ln3+ ions is quite comparable and varies very little from one element
to another. Therefore, the chemical properties of the lanthanoids are
almost similar due to which the separation of lanthanoids is very difficult-
almost as difficult as the separation of isotopes.

Terminal Questions
1. Those elements, in the building up process of whose atoms the
differentiating electron enters the f- orbitals of an inner shell, are called
f-block elements. There are two series of f-block elements containing 14
elements each. The lanthanoid series contains elements from cerium to
lutetium and the actinoid series contains elements from thorium to
lawrencium.

2. Actinoids resemble their lanthanoid congeners in the following way:

 They have the similar electronic configurations.,

 They exhibit a common oxidation state of +3,

 They form complexes,

 Most of them form coloured ions and exhibit paramangnetism.

3. The early actinoids exhibit a large number of oxidation states, in this

respect they resemble transition elements.

4. There is no separate place for lanthanoids and actinoids in the periodic

table. Therefore, the lanthanoids are placed along with lanthanum and
actinoids along with actinium in the periodic table.

5. Most compounds of lanthanoids and actinoids are paramagnetic

because they contain lanthanoid and actinoid ions which possess
unpaired electrons. Presence of unpaired electrons gives rise to
66 paramagnetism in the compound.
Unit 3 Inner-Transition Elements

6. The range of oxidation states is much more restricted in the members of

lanthanoid series as compared to those of the actinoid series. This is a
result of stabilising effects exerted on 4f orbitals by increasing ionic
charge. By the time an ionic charge of +3 is developed on a lanthanoid
ion, the 4f orbitals are so stabilized that they become part of the inner
core of the electrons. It becomes increasingly difficult to remove further
electrons to give rise to higher oxidation states. On the other hand, in
the beginning of the actinoid series, the difference in energy of the 5f
and 6d orbitals is much less. Therefore, 5f electrons along with 6d and
7s electrons participate in bonding, resulting in a wider range of
oxidation states. However, later the 5f orbitals also become more stable
and show reluctance to involve themselves in bonding.

7. Lanthanoids Actinoids

n 0-2 2
(i) Electronic configuration: [Rn] 5f 6d 7s
n 0-1 2
[Xe] 4f 5d 6s

(ii) Oxidation states: Variable oxidation states for early

actinoids like transition metals.
mostly +3

(iii) Atomic and ionic sizes: Actinoid contraction takes place which
lanthanoid contraction takes is greater than lanthanoid contraction.
place

8. Lawrencium, Lr, 5f146d17s2, +3 oxidation states as 6d17s2 can be

removed easily and completely filled 5f14 configuration will be achieved.

67