~ ;

r.· lJ

General Characteristics off-block elements

{Lanthanides and Actinides)

The f-block elements are those in which the electron enters the

11 antepenultimate (n-2) f orbitals. The f-block elements have been divided into two
' series.
t~
i, (a) Lanthanides : last electron enters the 4f subshell (La, Ce ........ . Lu)
\,
r (b) Actinides : last electron enters the 5f subshell (Ac, Th ........... Lr)

Lanthanoids
I) Electronic configuration : (n-2)f "14 (n-1 )d0"1ns2
La [xe] 5d 1 6s2 Yb [Xe] 4f' 4 6s2
Ce [xe] 4f 5d1 6s2
.I
·1
!1 Eu [xe] 4f7 5d0 6s2
Gd [xe] 4f7 5d 1 6s2
Th [xe] 4f 5d0 6s2
t
Sm [xe] 4f 5d° 6s2
Lu [xe] 4f45d1 6s2
2) Physical state : Silvery white metals having low tensile strength and are good
conductors of heat and electricity
3) . Density : Lanthanoids have high densities and it increases with increase in
I atomic .numbers.
4) MP_and BP : Fairly high MP and BP

I S) O~idation state : Main oxidation state exhibited by all lanthanide is +3 in

aqueous solution and solid state. Some elements show +2 and +4 oxidation.
states also but they are less stable than +3 oxidation state.
La, Gd and Lu exhibit only +3 oxidation state because of the extra stability of
empty (La3+-4f°) half filled (Gd3+-4f) and completely filled (Lu3+-4f 4) 4f subshell in
their +3 oxidation states.
. Eu and Yb exhibit +2 oxidation states because of the extra stability of half
filled (Eu +-f7) and completely filled (Yb2+-f 4) 4f subshells. However they are strong
2

·reducing agents changing to +3 oxidation state.

Ce and Tb exh!bit +4 oxidation states because of the extra stability of empty
4
(Ce +-f°) and half filled (Tb4+-f7) 4f subshell in their +4 oxidation states. However
7
' .
.

'
Ce4+ and Th4+ are good oxidants reverting to co~on +3 oxidation states (Sm also
show +2 oxidation state (Sm2+-f).

thennodynamic factors).
Its stability is due to some kinetic and ' if

The stability of +3 oxidation state is due to the fact that the sum of the
,J ionization energies and lattice energies of the tripositive ioruds more negative as
,J1'
f : :t

"\j
+ compared to +2 and +4 ions.
tit
:~ 6) Magnetic properties of M3+ ions. They show paramagnetism due to the
:!. 4
if presence of unpaired electrons inf-orbitals La3+ (4t°) Lu3+ (4f 4), Yb2+ (4f 4) and Ce +
11

I;.l
(4t°) are diamagnetic due to the absence of unpaired electrons.
Paramagnetism-in lanthanoids is due to orbital motion as well as its spinning
around its axis. This is because 4f electrons are deeply seated and cannot interact
l•-
with the surrounding electrons. Thus orbital motion of 4f orbital is not quenched as in
the case of d-block elements.
7) Ionic radii and lanthanoid contraction
3
The size of M + ions decreases as we move from La to Lu. La has the lar~est. ..
· · M El o-mn•u c. JlOL.V. ,

. Lu has the smallest radius. The steady decrease in ionic radii

radius and . A with increase
in atomic number is known as lanthanoid contraction.
As we move along the lanthanide series, as the atomic number increases, for
every proton in the nucleus, the extra electron goes to fill 4f orbital. The 4f electrons
constitute the inner shells and are ineffective in screening the nuclear charge. This
l gradual increase in the effective nuclear charge is experienced by the outer electrons.
,j . .

:1 Therefore the electron cloud shrinks and that results in the gradual decrease in the size
,.
oflanthanides.

ConsC9uences of lanthanoid contraction: (1) Separation of lanthanides. All

lanthanides have similar chemical properties and therefore it is difficult to separate
them(i.);1Yll~l~'L~1~c.-8i2.t.:_;fue:..'1!~.:'.~wq..:.-(;h.~'o/~&~~ch.u. · 1iJ t
_.'.s,9-~AJ~ ~3ti1~~;--bl~w.1_
6 , t \ ~ #-.I ,fo-dt\l&iit · ,~-~ -:l4·~~lf-l:~~=(~-k ie.~ 9i11.. .
<U tw_ lo9-'W>nond..µq. tu-O'U:J\~ ~cv<- ~ - fn >up~Ji Ii..t.?iocl ff> !'w' pWc,tU.L {oii, - Fe> ~- lif-c
•· ~ ~d~'~ :i1rH~~~1.¥<h,<AJk~- ~t,jw.--&l11L~) vanation 1abas1c strength of cs
hydroxides. Due to lanthanoid contractjon, size of M3+ ion decr~es and there is an
increase in the covalent character in M-OH bond. So basic character decreases from
La(OH)3 to Lu(OH)J. La(OH)J is most basic and Lu(OHh is least basic.
8) Colou1 of tlw ions

Mo st of the lanthanide ions are coloured in the solid as well as in the solution
state. The colour arises due to the absorption of visible light leading to electronic

,,
i excitation within the partly filled 4flevel known as f-f transition.
3
La + and Lu 3+ do not show any colour because they ha"e vacant and fully
filled 4f subshells respectively
9) Chemical reactivity : Highly reactive, tarnished easily, react with water to
liberate hydrogen; react with C; N and halogens formmg · t~!.· 17'~
1 - ~; m·tndes and

,\ ,
halides.
!.::9-.
... rl
j 10) Uses

t~
~o/ --
(a) Pyrophoric alloy,misch metal )contains Ce, La and Np . Fe, C, Sis used in
:~i cigarette lighters (~as lighters)
I·
,I
o •~~~'-
(b) Ce- is used- in gl.;: ,ed:cing spectacles because Ce glass cut off heat and
! I <t q UV light.
, ½i ).~~_.lf,2.. d (c) Ceric sulphate is used as oxidizing agent in volumetric analysis
-.f' Actinide~

Actinoids involve the filling of 5f orbitals. They are silvery white metals,
tarnished when exposed to alkalies. All are radioactive and strong reducing agents.
·1

Oxidation state : :t3 is the most common oxidation state, but there is.a greater
range of oxidation states from +2 to +7. This is due to the small energy difference
between 5f, 6d and 7s subshells.
Ionic raddi : The steady decrease in ionic radii with increase in nuclear charge
is called actinoid contraction. This is due to the poor shielding of nuclear charge by

5f electrons.
!;_olour _Qf the ions : Generally .coloured, but ions with St° and sr 4
are

colourless.
Magnetic properties: Paramagnetic due to the presence of unpaired electrons

Uses
Th arid its compounds find use in nuclear chemistry U and Pu are fuels in
nuclear reactors.

Th salts are used as medicines in the treatment of cancer.

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