SESSION

OBJECTIVES
1. f-Block elements

2. Introduction to lanthanides

3. Oxidation state

4. lanthanide contraction

5. Chemical reactivity

6. Introduction of Actinides

7. Comparison of actinides with lanthanides

INNER TRANSITION
ELEMENTS
The elements in which the additional electron
enters (n-2)f orbitals are called inner transition
elements. The valence shell electronic configuration
of these elements can be represented as (n – 2)f0-
14
(n – 1)d0-1ns2.

4f inner transition metals are known as lanthanides

because they come immediately after lanthanum
and 5f inner transition metals are known as
actinoids because they come immediately after
actinium.
ELECTRONIC
CONFIGURATION
Element name Symbol Z Ln Ln3+ Radius
Ln3+/ pm
Lanthanum La 57 [Xe]6s25d1 [Xe]4f0 116
Cerium Ce 58 [Xe]4f16s25d1 [Xe]4f1 114
Praesodymium Pr 59 [Xe]4f36s2 [Xe]4f2 113
Neodymium Nd 60 [Xe]4f46s2 [Xe]4f3 111
Promethium Pm 61 [Xe]4f56s2 [Xe]4f4 109
Samarium Sm 62 [Xe]4f66s2 [Xe]4f5 108
Europium Eu 63 [Xe]4f76s2 [Xe]4f6 107
Gadolinium Eu 64 [Xe]4f76s25d1 [Xe]4f7 105
Terbium Tb 65 [Xe] 4f96s2 [Xe]4f8 104
Dysprosium Dy 66 [Xe] 4f106s2 [Xe]4f9 103
Holmium Ho 67 [Xe] 4f116s2 [Xe]4f10 102
Erbium Er 68 [Xe] 4f126s2 [Xe]4f11 100
Thulium Tm 69 [Xe] 4f136s2 [Xe]4f12 99
Ytterbium Yb 70 [Xe] 4f146s2 [Xe]4f13 99
Lutetium Lu 71 [Xe] 4f146s25d1 [Xe]4f14 98
ATOMIC AND IONIC SIZES:
THE LANTHANIDE
CONTRACTION

As the atomic number increases, each

succeeding element contains one more electron
in the 4f orbital and one proton in the nucleus.
The 4f electrons are ineffective in screening the
outer electrons from the nucleus causing
imperfect shielding. As a result, there is a gradual
increase in the nucleus attraction for the outer
electrons. Consequently gradual decrease in size
occur.This is called lanthanide contraction.
ILLUSTRATIVE
EXAMPLE
Explain the cause and two consequences of lanthanoid
contraction.

Solution:

The poor shielding effect of f-electrons is cause of lanthanoid

contraction.

Consequences
There is close resemblance between 4d and 5d transition
series. Ionization energy of 5d transition series is higher than
3d and 4d transition series. Difficulty in separation of
lanthanides
ILLUSTRATIVE
EXAMPLE

Why Zr and Hf have almost similar atomic radii?

Solution

Zr and Hf have almost similar atomic radii as a

consequence of lanthanide contraction due to which
their properties becomes similar.
ILLUSTRATIVE
EXAMPLE
Size of trivalent lanthanoid cation decreases with increase in
atomic number. Explain.
Solution

It is due to poor shielding effect of f-electrons,

valance electrons are strongly attracted towards
nucleus, therefore, effective nuclear charge
increases, hence ionic size decreases.
IONIZATION
ENTHALPIES
First ionization enthalpy is around 600 kJ mol-1, the
second about 1200 kJ mol-1 comparable with those of
calcium.

Colours:
Colours of these ions may be attributed to the presence
of f electrons. Neither La3+ nor Lu3+ ion shows any colour
but the rest do so.

Absorption bands are narrow, probably because of the

excitation within f level.
MAGNETIC
PROPERTIES
The lanthanoid ions other then the f 0 type (La3+ and Ce3+)
and the f14 type (Yb2+ and Lu3+) are all paramagnetic. The
paramagnetism rises to the maximum in neodymium.
Lanthanides have very high magnetic susceptibilities due to
their large numbers of unpaired f-electrons.

The strongest known magnets contain

lanthanides (eg. Nd-Fe-B, Sm-Fe-N, and Sm-
Co).

Lanthanide complexes are

used in MRI (medical
resonance imaging), eg.
[Gd(III)(dtpa)]2-
OXIDATION
STATES
Predominantly +3 oxidation state.

This irregularity
arises mainly
from the extra
stability of
empty, half filled
or filled f
subshell.

Occasionally +2 and +4 ions in solution or in solid

compounds are also obtained.
ILLUSTRATIVE
EXAMPLE
Why Sm2+, Eu2+, and Yb2+ ions in solutions are good reducing
agents but an aqueous solution of Ce4+ is a good oxidizing
agent?

Solution

The most stable oxidation state of lanthanides is

+3. Hence the ions in +2 oxidation state tend to
change +3 state by loss of electron acting as
reducing agents whereas those in +4 oxidation
state tend to change to +3 oxidation state by gain
of electron acting as a good oxidising agent in
aqueous solution.
LUMINESCENCE OF LANTHANOID
COMPLEXES

Irradiation of some Lanthanide(III) complexes with UV light

causes them to fluoresce

The origin of fluorescence is 4f-4f transitions.

–the excited state produced decays to the ground state with

emission of energy.

Some examples are Eu3+ (red) and Tb3+ (green)

They can be used as phosphors in television sets and

fluorescent lighting.

These applications are specific to lanthanoid ions because of

the sharp transitions observed.
PROPERTIES
 Silvery white soft metals, tarnish in
air rapidly

 Hardness increases with increasing

atomic number, samarium being steel
hard.

 Good conductor of heat and electricity.

CHEMICAL PROPERTIES
Metal combines with hydrogen when gently heated
in the gas.

The carbides, Ln3C, Ln2C3 and LnC2 are formed when

the metals are heated with carbon.

They liberate hydrogen from dilute acids and burn

in halogens to form halides.

They form oxides and hydroxides, M2O3 and M(OH)3,

basic like alkaline earth metal oxides and
hydroxides.
Ln 2O3 H2

Ln 2S3 Heated w ith S W ith helogens

Ln LnX 3

C 2773 K

LnN LnC 2 Ln( O H )3 +H 2

USES
Best single use of the lanthanoids is for the
production of alloy steels for plates and pipes.
A well known alloy is misch metal which consists of
a lanthanoid metal (~95%) and iron (~5%) and
traces of S, C, Ca and Al. A good deal of misch
metal is used in Mg based alloy to produce bullets,
shell and lighter flint.

Mixed oxides of lanthanoids are employed as

catalysts in petroleum cracking.
THE ACTINIDES
Result from the filling of the 5f orbitals.

All isotopes are radioactive, with only 232

Th, 235
U,
238
U and 244Pu having long half-lives.

Only Th and U occur naturally-both are more

abundant in the earth’s crust than tin.

The others must be made by nuclear processes.

SOME CHARACTERISTIC PROPERTIES
OF ACTINIDES

The dominant oxidation state of actinides is +3.

Actinides also exhibit an oxidation state of +4.
Some actinides such as uranium, neptunium and
plutonium also exhibit an oxidation state of +6.

The actinides show actinide contraction (like

lanthanide contraction) due to poor shielding of the
nuclear charge by 5f electrons.

All the actinides are radioactive. Actinides are

radioactive in nature. So the study of their
chemistry is difficult in the laboratory. Their
chemistry is studied using tracer techniques.
ELECTRONIC CONFIGURATION

Element name Symbol Z Ln Ln3+ Radius

Ln3+/ pm
Actinium Ac 89 [Rn] 6d17s2 [Rn]4f0 111
Thorium Th 90 [Rn ]5d27s2 [Rn]4f1
Protactinium Pa 91 [Rn]5f26d17s2 [Rn]4f2
Uranium U 92 [Rn]5f36d17s2 [Rn]4f3 103
Neptunium Np 93 [Rn]5f46d17s2 [Rn]4f4 101
Plutonium Pu 94 [Rn]5f67s2 [Rn]4f5 100
Americium Am 95 [Rn]5f77s2 [Rn]4f6 99
Curium Cm 96 [Rn]5f76d17s2 [Rn]4f7 99
Berkelium Bk 97 [Rn]5f97s2 [Rn]4f8 98
Californium Cf 98 [Rn]5f107s2 [Rn]4f9 98
Einsteinium Es 99 [Rn]5f117s2 [Rn]4f10
Fermium Fm 100 [Rn]5f127s2 [Rn]4f11
Mendelevium Md 101 [Rn]5f137s2 [Rn]4f12
Nobelium No 102 [Rn]5f147s2 [Rn]4f13
Lawrencium Lr 103 [Rn]5f146d17s2 [Rn]4f14
IONIC SIZES
Actinide contraction of trivalent ions is similar
to that of the lanthanides, and is caused
again by the increasing nuclear charge.

Magnetic properties

Magnetic properties are more complex than those of

lanthanoids.
Susceptibility is roughly parallel to the lanthanoids.
PHYSICAL AND CHEMICAL
REACTIVITY
 Silvery in appearance but display a variety of structures due
to the irregularity in metallic radii which are far greater than
are found in lanthanoids.

 Highly reactive metals, especially when finely divided.

 Action of boiling water gives mixture of oxides and hydroxides.

 Combination with most non-metals takes place at

moderate temperature.
 HCl attacks all metals but most are slightly affected by
HNO3 owing to the formation of protective oxide layers.

 Alkalies have no effect.

COMPARISON OF LANTHANIDES AND
ACTINIDES
Similarities
 Lanthanides and actinides involve filling of f-orbitals and
thus are similar in many respects.

 The most common oxidation state is +3 for both

lanthanides and actinides.

 Both are electropositive in nature and thus very reactive.

 Magnetic and spectral properties are exhibited by both

lanthanides and actinides.

 Actinides exhibit actinide contraction just like lanthanides.

DIFFERENCES

Besides +3, lanthanides also show oxidation states of +2

and +4 while actinides show higher oxidation states of
+4, +5, +6 and + 7 as well.

Lanthanide ions are colourless while most of the actinide

ions are coloured.

Actinides have a greater tendency towards complex

formation as compared to lanthanides.
Lanthanide compounds are less basic while actinide
compounds have appreciable basicity

Actinides form few important oxocations such as UO22+,

PuO22+, etc, while such oxocations are not known for
lanthanides.

Almost all actinides are radioactive while lanthanides,

except promethium, are non-radioactive.

The magnetic properties of actinides can be easily

explained while it is difficult to do so in the case of
lanthanides.
ILLUSTRATIVE EXAMPLE
Why do lanthanoids and actinoids have same physical and
chemical properties?

Solution

They have similar electronic configuration and f-orbital

is progressively filled.
Thank you