f-block(inner transition elements)

(n-2)f1-14(n-1)d0 or 1 ns2 ( n=6 for lanthanoids and n=7 for Actinoids)

The f-block of the periodic table of the elements consists of those elements (sometimes referred to as the
inner transition elements) for which, in the atomic ground state, the highest-energy electrons occupy f-
orbitals. Unlike the other blocks, the conventional divisions of the f-block follow periods of similar
atomic number rather than groups of similar electron configuration. Thus, the f-block is divided into the
lanthanoid series and the actinoid series.

• Inner transition elements(f -Block elements): • They are present in separate block in the periodic table.
• Last electron enters in pre-penultimate f-subshell, so they are known as f-block elements. •
Lanthanoids: last electron enters one of the 4f orbital. Cerium(at. No. 58) to Lutetium(at. No.71) •
Actinoids: last electron enters one of the 5f orbital. Thorium (at.no.90)to lutetium(at. No.103) • They are
also known as ‘inner transition elements’..

f-block
Period f1 f2 f3 f4 f5 f6 f7 f8 f9 f10 f11 f12 f13 f14 d1
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
6
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
7
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
139 140 141 142 143 144 145 146 147 148 149 150 151 152 153
8
Ute Uqn Uqu Uqb Uqt Uqq Uqp Uqh Uqs Uqo Uqe Upn Upu Upb Upt

LANTHANOIDS

Electronic Configuration: All lanthanoids have electronic configuration with 6s2 common
but with variable occupancy of 4f level in their atoms . ( 6s2, 5d0-1, 4f1-14) However, the electronic
configuration of all the tri-positive ions (the most stable oxidation state of all the lanthanoids)
is of the form 4fn (n = 1 to 14 with increasing atomic number).

Atomic and Ionic sizes: The overall decrease in atomic and ionic radii from lanthanum to
lutetium (the lanthanoid contraction) is a unique feature in the chemistry of the lanthanoids.
It has far reaching consequences in the chemistry of the third transition series of the elements.
The decrease in atomic radii (derived from the structures of metals) is not quite regular while
decrease in ionic radii (M3+) is regular

The shielding of one 4f electron by another is less than one d electron by another with the increase in
nuclear charge along the series. There is fairly regular decrease in the sizes with increasing atomic
number. (lanthanoid contraction)

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 Lanthanoid contraction : In Lanthanoid series, with increasing atomic number, there is progressive
decrease in atomic/ionic radii due to poor shielding effect of 4f-orbitals.
❖ Reason : Due to addition of new electrons into (n-2) f-subshell which shows more poor shielding
effect.
❖ Consequences :
• Their separation is difficult as they have small difference in size.
• Basic strength of hydroxide decreases from left to right.
(La(OH)3 is more basic than Lu(OH)3 )
• 4d and 5d transition series have almost same atomic radii. (Zr and Hf have similar properties due to
similar size
Oxidation States: The possible stable oxidation states of the lanthanoids are tabulated in In the
lanthanoids, La(III) and Ln(III) compounds are predominant species.(+3 OS most stable)
However, occasionally +2 and +4 ions in solution or in solid compounds are also obtained.
This irregularity (as in ionisation enthalpies) arises mainly from the extra stability of empty,
half-filled or filled f subshell. Thus,
• the formation of CeIV is favoured by its noble gas configuration, but it is a strong oxidant
reverting to the common +3 state. The E° value for Ce4+/Ce3+ is + 1.74 V which suggests
that 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, MO2. Eu2+ is formed by losing
the two s electrons and its f7 configuration accounts for the formation of this ion.
However, Eu2+ is a strong reducing agent changing to the common +3 state.
• Similarly Yb2+ which has f14 configuration is a reductant which has f14 configuration is a
reductant.
• TbIV has half-filled f-orbitals and is an oxidant.
• The behaviour of samarium is very much like europium, exhibiting both +2 and +3
oxidation states.

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General Characteristics:
1.Physical State: All the lanthanoids are silvery white soft metals
and tarnish rapidly in air. The hardness increases with increasing atomic number, samarium
being steel hard. Their melting points vary between 1000 to 1200 K but samarium melts at
1623 K. They have typical metallic structure 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.

2.Colour & Magnetic Property: Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be attributed to the excitation of f
electrons on absorption of light in the visible region. Neither La3+ nor Lu3+ ion shows any
colour but the rest do so. However, absorption bands are narrow, probably because of the
excitation within f level. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f14
type (Yb2+ and Lu2+) are all paramagnetic. The orbital motions of the electrons in lanthanoids
are not quenched, so both spin and orbital angular momentum contribute towards μ. This is in
contrast to metal ions of the first transition series where ‘spin only’ formula is used.

3.Ionisation Enthalpy: The first ionisation enthalpies of the lanthanoids are around 600 kJ mol-1, the
second about 1200 kJ mol-1 comparable with those of calcium. A detailed discussion of
the variation of the third ionisation enthalpies indicates that the exchange enthalpy
considerations (as in 3d orbitals of the first transition series), appear to impart a certain
degree of stability to empty, half-filled and completely filled orbitals f level. This is indicated
from the abnormally low value of the third ionisation enthalpy of lanthanum, gadolinium and
lutetium.

4. Some chemical reactions of lanthanoids are

Uses: The best single use of the lanthanoids is for the production of alloy steels for plates and
pipes. A well known alloy is mischmetal which consists of a lanthanoid metal (~ 95%) and
iron (~ 5%) and traces of S, C, Ca and Al. A good deal of 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.

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ACTINOIDS
The actinoids include the fourteen elements from Th to Lr. The names, symbols and some properties of
these elements are given in Table below

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. These facts render their study more difficult.

ELECTRONIC CONFIGURATION: 7s2, 6d0-1, 5f1-14

The fourteen electrons are formally added to 5f, though not in thorium (Z = 90) but from Pa onwards
the 5f orbitals are complete at element 103. The irregularities in the electronic configurations of the
actinoids, like those in the lanthanoids are related to the stabilities of the f 0 , f 7 and f 14 occupancies of
the 5f orbitals. Thus, the configurations of Am and Cm are [Rn] 5f7 7s2 and [Rn] 5f7 6d1 7s2.

IONIC SIZES
There is a gradual decrease in the size of atoms or M3+ ions across the series. This may be referred to as
the actinoid contraction (like lanthanoid contraction). The contraction is, however, greater from element
to element in this series resulting from poor shielding by 5f electrons. There is a greater range of
oxidation states, which is in part attributed to the fact that the 5f, 6d and 7s levels are of comparable
energies.

OXIDATION STATES
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, +6 and +7 respectively in Pa, U and Np but
decreases in succeeding elements.

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The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state.
However, +3 and +4 ions tend to hydrolyse. Because the distribution of oxidation states among the
actinoids is so uneven and so different for the former and later elements, it is unsatisfactory to review
their chemistry in terms of oxidation states.

GENERAL CHARECTERSTICS OF ACTINOIDS

• The actinoid metals are all silvery in appearance but display a variety of structures.
• Its metallic radii are far greater than in lanthanoids.
• The actinoids are highly reactive metals, especially when finely divided
• The magnetic properties of the actinoids are more complex than those of the lanthanoids.
Although the variation in the magnetic susceptibility of the actinoids with the number of
unpaired 5 f electrons is roughly parallel to the corresponding results for the lanthanoids, the
latter have higher values.
• Ionisation enthalpies of the early actinoids, though not accurately known, but are lower than for
the early lanthanoids. This is quite reasonable since it is to be expected that when 5f orbitals are
beginning to be occupied, they will penetrate less into the inner core of electrons. The 5f
electrons, will therefore, be more effectively shielded from the nuclear charge than the 4f
electrons of the corresponding lanthanoids. Because the outer electrons are less firmly held, they
are available for bonding in the actinoids.

Example: Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
Answer: Cerium (Z = 58)

Example: Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Answer: Actinoid contraction is, however, greater from element to element in this series resulting from poor
shielding by 5f electrons.