JEE-Chemistry

LECTURE NOTES f-BLOCK COMPOUNDS

LECTURE-1/2
Inner Transition Elements :
The elements in which the additional electron enters in (n – 2)f orbitals are called inner transition
elements or f-block elements.
Position in the periodic table :
The lanthanides resemble with Yttrium in most of their properties. So it became necessary to accomodate
all the fifteen elements together at one place. This has been done by placing the first element, lanthanum
below yttrium and placing the remaining fourteen elements separately in the lower part of the periodic
table.
Lanthanide series ( Z = 58 – 71) (Ce – Lu)
Actinide series (Z = 90 – 103) (Th – Lr)
LANTHANIDES (RARE EARTHS OR LANTHANONES)
(i) Lanthanides are reactive elements so do not found in free state in nature.
(ii) Most important minerals for lighter Lanthanides are – Monazite, cerites and for heavier lanthanides –
Gadolinite and Xenotime
Electronic configuration :
(i) The general configuration of lanthanides may be given as 4f1–145s25p65d0–16s2.
Atomic Element Symbol Outer electronic configuration
Number Atomic +3 ion
58 Cerium Ce 4f 5d 6s
1 1 2
4f1
59 Praseodymium Pr 4f3 6s2 4f2
60 Neodymium Nd 4f4 6s2 4f3
61 Promethium Pm 4f5 6s2 4f4
62 Samarium Sm 4f6 6s2 4f5
63 Europium Eu 4f7 6s2 4f6
64 Gadolinium Gd 4f7 5d1 6s2 4f7
65 Terbium Tb 4f9 6s2 4f8
66 Dysprosium Dy 4f10 6s2 4f9
67 Holmium Ho 4f11 6s2 4f10
68 Erbium Er 4f12 6s2 4f11 D:\TEACHING NOTES-2016-17\CHEMISTRY\IOC\FINAL\11. Hydrogen & its compound & f-block\2. f-Block Compounds.p65

69 Thulium Tm 4f13 6s2 4f12

70 Ytterbium Yb 4f14 6s2 4f13
71 Lutetium Lu 4f14 5d1 6s2 4f14
(ii) It is to be noted that filling of 4f orbitals in the atoms is not regular. A 5d electron appears in gadolinium
(Z = 64) with an outer electronic configuration of 4f75d16s2 (and not 4f86s2). This is because the 4f
and 5d electrons are at about the same potential energy and that the atoms have a tendency to retain
stable half filled configuration.
(iii) On the other hand, the filling of f-orbitals is regular in tripositive ions.
(iv) After losing outer electrons, the f-orbitals shrink in size and became more stable.
(v) Pm is the only synthetic radioactive lanthanide.

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Oxidation states :
Lanthanides Oxidation Actinides Oxidation state
Ce58 +3, +4 Th90 +4
Pr59 +3, (+4) Pa91 (+4), +5
Nd60 +3 U92 (+3), (+4), (+5), +6
Pm61 +3 Np93 (+3), (+4), +5, (+6), (+7)
Sm62 (+2), +3 Pu94 (+3), +4, (+5), (+6), (+7)
Eu63 +2, +3 Am95 +2,(+3),(+4),(+5),(+6)
Gd64 +3 Cm96 +3, (+4)
Tb65 +3, +4 Bk97 +3, (+4)
Dy66 +3, (+4) Cf98 +3
Ho67 +3 Es99 +3
Er68 (+2), +3 Fm100 +3
Tm69 (+2), +3 Md101 +3
Yb70 +2, +3 No102 +3
Lu71 +3 Lr103 +3
(Oxidation states in brackets are unstable states)
(i) The lanthanides contains two s electrons in the outermost shell, they are therefore expected to exhibit
a characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.
(ii) This corresponds to the use of two outermost electrons (6s2) alongwith one inner electron. The inner
electron used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.
(iii) All the lanthanides attains +3 oxidation state and only Cerium, Praseodymium, and Terbium exhibit
higher oxidation state (+4). Eu and Yb exhibit +2 oxidation state.
(iv) Oxidation states +2 and +4 occur particularly when they lead to -
(a) A noble gas configuration Ex. Ce4+ (f 0). The formation of CeIV is favoured by its noble gas
configuration, but it is a strong oxidant reverting to the common +3 state. The Eº 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.
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(b) A half filled 'f ' orbital Ex. Eu2+, (f7), 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 ƒ7 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 ƒ14 configuration is a reductant.
(c) A completely filled 'f ' orbital Ex. Yb2+ (f 14)
(v) Therefore, in higher oxidation state, they act as oxidising while in lower state as reducing agents.
Magnetic properties :
(i) In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to
Gadolinium (0 to 7) and then continuously decreases upto lutecium (7 to 0).
(ii) lanthanum and lutecium ions are diamagnetic, while all other tripositive lanthanide ions are
paramagnetic. (Exception – Neodyomium is the most paramagnetic lanthanide).

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(iii) Ce+4 and Yb+2 are also diamagnetic ions.
Colour :
(i) The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible region
of light and undergo f–f transition and hence exhibit colour.
(ii) The colour exhibited depends on the number of unpaired electrons in the 4f orbitals.
(iii) The ions often with 4fn configuration have similar colour to those ions having 4f14–n configuration.
(iv) Lanthanide ions having 4f 0, 4f14 are colourless.
Other Properties :
• 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 range between 1000 to 1200 K but samarium melts at 1623 K.
• They have typical metallic structure and are good conductors of heat and electricity.
• Highly dense metals with high m.pts. do not show any regular trend.
• Ionisation Energies : Lanthanides have fairly low ionisation energies comparable to alkaline
earth metals.
• Electro positive character : High due to low I.P.
• Complex formation : Do not have much tendency to form complexes due to low charge
density because of their large size. Lu+3 is smallest in size can only form complex.
• Reducing Agent : They readily lose electrons so are good reducing agent.
• Alloy : Alloys of lanthanides with Fe are called Misch metals, which consists of a lanthanoid
metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al.
• Basic Nature : La(OH)3 is most basic in nature while Lu(OH)3 least basic.
• Carbide : Lanthanides form MC2 type carbide with carbon, which on hydrolysis gives C2H2.
• The lanthanide elements Eu and Yb dissolve directly in very high concentration in liquid ammonia.
Lanthanide contraction :
(i) In the lanthanide series with increasing atomic number, there is a progressive decrease in the size from
lanthanum to lutecium or from La+3 to Lu+3. This contraction in size is known as lanthanide contraction.

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(ii) The general electronic configuration of these elements is 4f1–145s2p6d0–16s2. In these elements the
added electron enters the deep seated f-orbitals and therefore experiences considerable pull by the
nucleus.
(iii) Due to very poor shielding effect of (n-2)f electrons, they exert very little screening effect on the
outermost 6s2 electrons.
Hence with increasing atomic number, the enhanced nuclear charge leads to contraction in the size of
atoms and ions.
(iv) The atomic volumes of Europium and Ytterbium are unexceptely large. The large atomic size of Eu
and Yb suggest weaker bonding in the solid elements. Both these elements have only two electrons
extra than the stable configurations (half filled, f7, and completely filled, f14), hence they utilise two

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electrons in metallic bonding as in the case with barium.
Effects of Lanthanide Contraction :
Close resemblance of Lanthanides : The general decrease in the sizes of the lanthanides with an
increase in their nuclear charges result in a small increase in their ionisation energies. Hence their
basic and ionic nature gradually decreases from La to Lu.This also explains the variations in
properties such as increased tendency for hydrolysis and formation of complex salts and decreased
thermal stability, solubility of their salts.
Similarity of Yttrium with lanthanides : The properties of Yttrium are so similar to the
lanthanides that it is considered more a member of the lanthanide series than a congener of scandium.
Anomalous behaviour of post-lanthanides : The following anomalies may be observed in the
behaviour of post-lanthanide elements.
(a) Atomic size : The ionic radii of Zr+4 is about 9% more than Ti+4. Similar trend is not maintained on
passing from the second to third transition series. The ionic radius of Hf+4, instead of increasing
(because of inclusion of one more electronic shell), decreases (or is virtually equal to Zr+4) as a
consequence of the lanthanide contraction.This explains the close similarities between the members
of the second and third transition series than between the elements of the first and second series.
(b) Ionisation potential and electronegativity : The effect of lanthanide contraction is also seen in the
increase in the ionisation potential values and electronegativities of the elements of the third transition
series, contrary to the general trend.Because of the lanthanide contraction, the post-lanthanide elements
have stronger positive field and thus the electrons are held more tightly.
The greater effective nuclear charge of the former make them more electronegative than the latter.
(c) High density : Because of lanthanide contraction, the atomic sizes of the post lanthanide elements
become very small. Consequently, the packing of atoms in their metallic crystals become so much
compact that their densities are very high.The densities of the third transition series elements are
almost double to those of the second series elements.
(d) Chemical reactions of the lanthanoids.
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Ln2O3 H2
ids
bu
rns

ac
in

th
O2

wi

Ln with halogens
heated with S
Ln2S3 LnX3
N
ith

wi
dw

2773 K

th
with C

H
ate

2
O
He

LnN LnC2 Ln(OH)3 + H2

Ln2C3/Ln3C
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Application of lanthanides :
Cerium is most useful element in the lanthanides –
• Ceramic application – CeO2, La2O3, Nd2O3 and Pr2O3 are used as decolourizing agents for
glasses.
• CeS (m.p. – 20000C) is used in the manufacture of a speciel type of crucibles and refractories.
• Lanthanide compounds like cerium molybdate, cerium tungstate are used as paints and dyes.
• In textile and leather industries (Ce salts).
• Mish metal is pyropheric and is used in cigarette & gas lighter.
ACTINIDES (5f - BLOCK ELEMENTS)
(i) The elements in which the extra electron enters 5f-orbitals of (n – 2)th main shell are known as actinides.
(ii) The man-made eleven elements Np93 – Lr103 are placed beyond uranium in the periodic table and are
collectively called trans-uranium elements.
(iii) Th, Pa and U first three actinides are natural elements.
Electronic configuration :
The general configuration of actinides may be given as 5f 1–14 6d0–1,7s2.
Atomic No. Elements Symbol Electronic Configuration
90 Thorium Th 5f06d27s2
91 Proactenium Pa 5f26d17s2
92 Uranium U 5f36d17s2
93 Neptunium Np 5f46d17s2
94 Plutonium Pu 5f66d07s2
95 Americium Am 5f76d07s2
96 Curium Cm 5f76d17s2
97 Berkellium Bk 5f96d07s2
98 Californium Cf 5f106d07s2
99 Einstenium Es 5f116d07s2
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100 Fermium Fm 5f126d07s2
101 Mandelevium Md 5f136d07s2
102 Nobellium No 5f146d07s2
103 Lowrencium Lr 5f146d17s2

Oxidation states :
(i) In lanthanides and actinides +3 oxidation is the most common for both of the series of elements.
(ii) This oxidation state becomes increasingly more stable as the atomic number increases in the actinide
series.
(iii) Highest oxidation states in the actinides is +7 exhibited by Np93 & Pu94, it is unstable.
(iv) Highest stable oxidation state is +6 shown by U92 .
Other Properties :
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• Physical appearance : Acitinides are silvery white metals. They get tarnished when exposed
to the attack of alkalies.
• Density : All the actinides except thorium and americium have high densities.
• Colour : Actinide ions are generally coloured. The colour of actinide ions depends upon the
number of 5f-electrons. The ions containing no unpaired 5f-electrons (exactly full filled
f-subshell) are colourless, as expected.
• Ionisation energies : Ionisation energies values of actinides are low.
• Electropositive character : All the known actinide metals are highly electropositive. They
resemble lanthanide series in this respect.
• Melting Boiling properties : They have high melting and boiling points. They do not
follow regular gradation of melting or boiling points with increase in atomic number.
• Magnetic properties : The actinide elements are paramagnetic due to the presence of unpaired
electrons.
• Radioactive nature : All the actinides are radiaoactive in nature.
• Actinide contraction : The size of atom/cation decrease regularly along the actinides series.
The steady decrease in ionic radii with increase in atomic number is referred to as actinide
contraction. This is due to poor shielding of 5f-electrons.
Comparision of lanthanides and Actinides
Points of Resemblance :
(i) Both lanthanides and actinides show a dominant oxidation state of +3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanides and actinides are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanides
show lanthanide contraction and actinides show actinide contraction.
Difference between lanthanides & Actinides :
Lathanides Actinides
1. Besides the most common oxidation state of +3 1. Besides the most common oxidation state of +3,
lanthanides show +2 and +4 oxidation states in actinides show +4, +5 and +6 oxidation states
case of certain elements. in case of certain elements.
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2. Lanthanides have less tendency towards 2. Actinides have a stronger tendency towards
complex formation. complex formation.
3. Except promethium, they are non radioactive. 3. All the actinides are radioactive.
4. Oxides and hydroxide of lanthanides are 4. Oxides and hydroxides of actinides are
less basic. more basic
Some important uses of actinides are as follows –
Thorium : Thorium is used in atomic reactors as fuel rods and in the treatment of cancer.
Uranium : Uranium is used as nuclear fuel. Its salts are used in glass industry (for imparting green
colour). textile industry and also in medicines.
Plutonium : Plutonium is used as fuel for atomic reactors as well as in atomic bombs.

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