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f-BLOCK COMPOUNDS

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23 views4 pages

f-BLOCK COMPOUNDS

Uploaded by

wowal21442
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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f-BLOCK COMPOUNDS

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)
LANTHANIDES (RARE EARTHS OR
Actinide series (Z=90−103) (Th−Lr )
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
1−14 2 6 0 −1 2
4f 5 s 5p 5 d 6 s.

(ii) It is to be noted that filling of 4 f orbitals in the atoms is not regular. A 5


d electron appears in gadolinium ( Z=64 ) with an outer electronic
configuration of 4 f ' 5 d 1 6 s2 (and not 4 f 3 6 s2 ). This is because the 4 f and 5 d
electrons are at about the same potential energy and that the atoms have a
tendency to retain stable half filled configuration.
(iii) Qn 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.

OXIDATION STATES

Lanthanid Oxidatio Actinide


Oxidation state
es n s

Ce58 +3 ,+ 4 Th90 +4

Pr 59 +3 ,(+ 4) Pa91 (+ 4),+ 5

Nd60 +3 U 92 (+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 Cm 96 +3 ,(+ 4)

Tb65 +3 ,+ 4 Bk 97 +3 ,(+ 4)

Dy 66 +3 ,(+ 4) Cf 98 +3

Ho67 +3 Es99 +3

Er 68 (+2),+ 3 Fm100 +3

Tm 69 (+2),+ 3 Md 101 +3

Yb70 +2 ,+3 No102 +3

Lu71 +3 Lr 103 +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 ( 6 s 2 ) alongwith
one inner electron. The inner electron used is a 5 d electron (in La, Gd and
Lu ), or one of the 4 f electron if no 5 d 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. Ce 4+¿ (f ) ¿. The formation of Ce Iv is favoured
0

by its noble gas configuration, but it is a strong oxidant reverting to the


common +3 state. The E o value for Ce 4+¿/ ¿¿ 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.
(b) A half filled ' f ' orbital Ex . Eu2+¿ ¿, (f f 7 ), Pr, Nd, Tb and Dy also exhibit + 4
state but only in oxides, MO2 . Eu2+¿ ¿ is formed by losing the two s electrons
2

and its f 7 configuration accounts for the formation of this ion. However,
2+¿ ¿
Eu is a strong reducing agent changing to the common +3 state. Similarly
2 +¿¿
Yb which has f 14 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 diamagneticic, while all other
tripositive lanthanide ions are paramagnetic. (Exception-Neodyomium is the
most paramagnetic lanthanide).
(iii) Ce+ 4 and Yb+2 are also diamagnetic ions.

Colour :
(i) The lanthanide ions have unpaired electrons in their 4 f 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
4 f orbitals.
(iii) The ions often with 4 f n configuration have similar colour to those ions
having 4 f 14−n configuration.
(iv) Lanthanide ions having 4 f 0 , 4 f 14 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 ¿ is most basic in nature while Lu ¿ least basic.
 Carbide: Lanthanides form MC 2 type carbide with carbon, which on
hydrolysis gives C 2 H 2.

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