THE INNER TRANSITION ELEMENTS ( f-BLOCK)

The f-block consists of the two series

i) Lanthanoids (the fourteen elements following lanthanum)
ii) Actinoids (the fourteen elements following actinium).
General Electronic Configuration - (𝑛−2)𝑓1−14(𝑛−1)𝑑0−1𝑛𝑠2
Lanthanoids – these are 14 elements between Lanthanum (La) and Hafnium (Hf)
in which 4f orbitals are successively filled. Ce(58) to Lu(71)
Atomic and Ionic Sizes – The decrease in atomic radii (derived from the structures
of metals) is not quite regular but it is regular in M3+ ions. Eu has the largest atomic
radius in entire 4f series.

Element Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Ln(pm) 183 182 181 181 180 199 180 178 177 176 175 174 173
Ln3+(pm) 103 101 99 98 96 95 94 92 91 89 88 87 86
Oxidation States
• Common oxidation state is+3.
• Occasionally exhibits +2 and +4 ions in solution or in solid compounds.
This irregularity (as in ionisation enthalpies) arises mainly from the extra
stability of empty, half-filled or filled f subshell.
• Formation of Ce(IV) is favoured by its noble gas configuration. But it is a strong
oxidant reverting to the common +3 state. The Eo for Ce4+/ Ce3+ is + 1.74 V. It
can oxidise water. However, the reaction rate is very slow and hence Ce(IV) is a
good analytical reagent.
• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO 2
• Yb2+(f14 ) is a reductant & Tb4+(f 7 ) is an oxidant.
• Eu2+(f 7 ) is a strong reducing agent changing to the common +3 state.
• Samarium (like europium) exhibits both +2 &+3 oxidation states.
. General Characteristics
• All the lanthanoids are silvery white soft metals and tarnish rapidly in air. The
hardness increases with increasing atomic number,
• Samarium is steel hard & has the highest melting point 1623 K.
• Their melting points range between 1000 to 1200 K.
• They have typical metallic structures and are good conductors of heat and
electricity.
• Density and other properties change smoothly except for Eu and Yb and
occasionally for Sm and Tm.
• Many trivalent lanthanoid ions are coloured both in a solid state and in
aqueous solutions. Color is due to f - f transition.
La3+(4f0), Ce4+(4f0), Lu3+(4f14) & Yb2+(4f14) are colourless.
• The lanthanoid ions are all paramagnetic.

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Exception - f 0 type (La3+ & Ce4+) & f 14 (Yb2+& Lu3+).

• The first ionisation enthalpy of the lanthanoids are around 600 kJ mol–1
The second ionisation enthalpy is about 1200 kJ mol–1 comparable with those
of calcium.
Abnormally low value of the third ionisation enthalpy of La, Gd & Lu due to
extra stability of empty, half-filled and completely filled orbitals f level.

Z Name Electronic configuration

Ln Ln2+ Ln3+ Ln4+
57 Lanthanum (La) 5d16s2 5d1 4f0
58 Cerium (Ce) 4f2 4f2 4f1 4f0
59 Praseodymium (Pr) 4f 36s2 4f 3 4f2 4f1
60 Neodymium (Nd) 4f 46s2 4f 4 4f3 4f2
61 Promethium (Pm) 4f 56s2 4f 5 4f4
62 Samarium (Sm) 4f 66s2 4f 6 4f5
63 Europium (Eu) 4f 76s2 4f 7 4f6
64 Gadolinium (Gd) 4f 75d16s2 4f 75d1 4f7
65 Terbium (Tb) 4f 96s2 4f 9 4f8 4f7
66 Dysprosium (Dy) 4f 106s2 4f 10 4f9 4f8
67 Holmium (Ho) 4f 116s2 4f 11 4f10
68 Erbium (Er) 4f 126s2 4f 12 4f11
69 Thulium (Tm) 4f 136s2 4f 13 4f12
70 Ytterbium (Yb) 4f 146s2 4f 14 4f13
71 Lutetium (Lu) 4f 145d16s2 4f 145d1 4f14

USES
• For the production of alloy steels for plates and pipes.
Ex- mischmetall (lanthanoid metal (~ 95%), iron (~ 5% )and traces of S, C, Ca
and Al).
mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
• Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
• Some individual Ln oxides are used as phosphors in television screens and
similar fluorescing surfaces.
Chemical propeties
• In their chemical behaviour, in general, the earlier members of the series are
quite reactive similar to calcium but, with increasing atomic number, they
behave more like aluminium.
• For the half-reaction: Ln3+(aq) + 3e– → Ln(s) EO = 2.2 to –2.4 V
Exception – Eu EO = –2.0 V.

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Note- Oxides and Hydroxides are basic like alkaline earth metal oxides and
hydroxides.
Actinoids – these are 14 elements after Actinium (Ac) in which 5f orbitals are
successively filled. Th(90) to Lr(103)
• The actinoids are radioactive elements and the earlier members have relatively
long half-lives, the latter ones have half-life values ranging from a day to 3
minutes for lawrencium (Z =103).
• The latter members could be prepared only in nanogram quantities.
Electronic configuration
Z Name Electronic configuration
Ln Ln3+ Ln4+
89 Actinium (Ac) 6d17s2 5f0
90 Thorium (Th) 6d27s2 5f1 5f0
91 Protactinium (Pa) 5f 2 6d17s2 5f2 5f1
92 Uranium (U) 5f 36d17s2 5f3 5f2
93 Neptunium (Np) 5f 46d17s2 5f4 5f3
94 Plutonium (Pu) 5f 67s2 5f5 5f4
95 Americium (Am) 5f 77s2 5f6 5f5
96 Curium (Cm) 5f 76d17s2 5f7 5f6
97 Berkelium (Bk) 5f 97s2 5f8 5f7
98 Californium (Cf) 5f 107s2 5f9 5f8
99 Einstenium (Es) 5f 117s2 5f10 5f9
100 Fermium (Fm) 5f 127s2 5f11 5f10
101 Mendelevium (Md) 5f 137s2 5f12 5f11
102 Nobelium (No) 5f 147s2 5f13 5f12
103 Lawrencium (Lr) 5f 146d17s2 5f14 5f13

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• All the actinoids have common 7s2 configuration and variable occupancy of 5f
and 6d subshells.
• The fourteen electrons are being added into 5f, though not in thorium (Z = 90)
but from Pa onwards the 5f orbitals are complete at element 103.
• The configuration of Am is [Rn] 5f77s2 (due to the stability of f7) and
Cm [Rn] 5f76d17s2(due to the stability of f7).
• Although the 5f orbitals resemble the 4f orbitals in their angular part of the
wave-function, they are not as buried as 4f orbitals and hence 5f electrons can
participate in bonding to a far greater extent.
Ionic Sizes
• There is a gradual decrease in the size of atoms or M3+ ions across the series.
This is called actinoid contraction.
• The actinoid contraction is greater from element to element in this series as
compared to lanthanoid contraction resulting from poor shielding by 5f
electrons.
Oxidation States
• There is a greater range of oxidation states, which is due to the comparable
energies of 5f, 6d and 7s levels.
• The actinoids show in general +3 oxidation state.
• The elements, in the first half of the series frequently exhibit higher oxidation
states. For example, the maximum oxidation state increases from +4 in Th to
+5 in Pa, +6 in U and +7 in Np but decreases in succeeding elements.
• The actinoids resemble the lanthanoids in having more compounds in +3 state
than in the +4 state. However compounds in +3 and +4 state tend to hydrolyse.

General Characteristics
• The actinoid metals are all silvery in appearance.
• They display structural variability due to irregularities in metallic radii. (which
are far greater than in lanthanoids)
• The magnetic properties of the actinoids are more complex than those of the
lanthanoids. The variation in magnetic susceptibility of actinoids with the
number of unpaired 5f electrons is similar to that of lanthanoids, the latter have
higher values.

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• The ionisation enthalpies of the early actinoids are lower than for the early
lanthanoids. Because 5f is less penetrating than 4f and hence is more
effectively shielded from the nuclear charge.
Chemical properties
The actinoids are highly reactive metals, especially when finely divided.
• They react with boiling water to give a mixture of oxide and hydride.
• They combine with most of the nonmetals at moderate temperatures.
• Hydrochloric acid attacks all metals
• Most of the nonmetals are slightly affected by nitric acid due to the
formation of protective oxide layers.
• Alkalies have no action on them.
Comparison with Lanthanoids
Similarity-
• Both show mainly an oxidation state of +3.
• Both are electropositive and are very reactive.
• Both exhibit magnetic properties.
• Actinoids exhibit actinoid contraction like lanthanoid contraction shown by
lanthanoids.

Differences
Lanthanoids Actinoids
Besides +3 oxidation state they show +2 Besides +3 oxidation state they show
and +4 oxidation states in few cases. higher oxidation states of +4, +5,+6,+7
Most of their ions are colourless. Most of the ions are coloured.
They have less tendency towards They have greater tendency towards
complex formation complex formation
Lanthanoid oxides and hydroxides are Actinoid oxides and hydroxides are more
less basic basic
Except promethium all are non- All are radioactive
radioactive.
Magnetic properties can be explained Magnetic properties cannot be explained
easily. easily as they are more complex.