F-BLOCK ELEMENTS

General Introduction
• The elements in which the last electron (also called differentiating electron) enters the anti-
penultimate energy level, i.e., (n - 2) f-orbitals are called f-block elements.
• These elements have also been called inner transition elements.
• This is because the last electron in them enters into (n - 2) f-orbitals, i.e., inner to the
penultimate energy level and they form a transition series within the transition series (d-block
elements).
• Their general electronic configuration is :
(n - 2)f1·14 (n - 1) <1-1·1 11s.!.
\ I I
\ I I
\ I
\ ! "
• Thus, they have three incomplete shells, viz.. (n-2), (n-1) and nth .

Classiflcation off-block
I
I I
Lanthanoids Actlnoid~

4f
Sf

[Link] earth
Radioactive
cle ment,;; elements

The Lanthanoids

• Electronic Configuration :

1-~;t ~i:; _ Nd Pm
60 61
--·· --·-
Sm
62
-
Eu
63
Gd
---
64
Tb
65
---
I Dy
J._
66
-··
I
Ho
~7
I

1_68
Er Tm
69 __
Yb
_707 1
Lu

Symbol Elec. Configuration

...Element Sd 1 6sl
Lanthanum La [Xe]
Ce rium Cc (Xe l 4ft Sd 1 6s-' exception
l'raseudymium Pr [Xe] 4P 6sJ
Neodym ium Nd fXcl 4f4 6s 2
Promethium Pm [Xe] 4P 6s 2
Samarium Sm [Xe] 4f6 6s1
h 1rop1um Eu IXeJ 41' 6s,, I l 3ff-fillecl
7
Li,i dolrnium Gd [Xej 4f Sd C,s-'
1
::. labi li ty
Terbium Tb [Xe] 4fJ 6s 2
Dy [Xel 4f10 6s·'
Oysprosium
11 6s ~
liulrn ,urn Hu [Xe] 4f
12 6s ·~
Erbium Er [Xel 4f
Thul ium Till [Xe] 4p:i (1s ·'

Ytt i:r hi um Yb (Xel 4f 14 6s· Fully-filbl

[Link]' l l ll lll l.u (Xel 4f14 Sd 1 6s ' st;i bil ity

....
• In the electronic configuration oflanthanoids given in the Tables. ncy
(1) Lanthanoids have the electronic configuration with 6s2 common but with variable occupa
of 4flevel. ·
(2) However, the electronic configurations of all the tripositive ions (the most stabIe 0
xidation
state ofall the lanthanoids) are in the form 4fb (n = 1 to 14) with increasing atomic number.
(3) The electronic configuration of cerium
(Z = 58) is 4fl Sd1 6s2(exception). .
(4) The electronic configuration of europium (Z = 63) is 4f7 6s2 and that of gadolinium (Z = 6 ) is 4
4f7 Sd1 6s 2 and this is explained on the basis of extra stability of the half-filled orbitals. .
(5) The electronic configuration of ytterbium (Z = 70) is 4fl4 6s2 and that of lutetium (Z = 71) IS
4f1 4 Sd1 6s2. This is also explained on the basis of extra stability of the completely filled
orbitals.

Oxidation States
· . . - l' . 1~ · ·· ·· -- ·· · · ·· ---. - : ... -
Element i Symbol . Electronic Configuration ' Oxidation State
Cerium Ce [Xe] 4f1 Sd1 6s2 +3
.P~~~fu~ . -Pr
.. [Xe]... 413
,
'6s2
=-···
...... +3
Neodymium Nd [Xe] 4~ 6s 2 +3
Promethium
. - _. . ·r ~
Pm · [Xe] 4fi 6s2 +3
Samarium .,...._l
Sm [Xe] 4fti 6s2 +3
·Et:1roplum o{
.. ..,. .,
,,_.~.
,.,,). -
Eu [Xe] •4f1 6s-2 ·' +3
- .'
Gadolinium Gd (Xe] 4t7 Sd1 6s2 +3
:,,
Terbium t~ Tb [Xe] 4fJ 6s2 +3
.,.._,
-
Dysprosium Dy [Xe] 4fl 0 6s 2 +3
' .
Holmium 7 Ho [Xe] 4f1 1 6s 2 +3
. '
'
Erbium Er (Xe] 4f1 2 6s2 +3
Thulium .. . Tm [Xe] 4f1 3 6s2 +3
·•T"'

Ytterbium Yb [Xe] 4t1 4 6s2 +3

Lutetium Lu [Xe] 4f14 Sd 1 6s2 +3

• The typical oxidation state of the lanthanoids is +3.

• The oxidation state of +2 and +4 are exhibited by some of the elements.
• These are shown by those elements which by losing 2 or 4 electrons acquire a stable
configuration off 0, f 7 or f 14,
• e.g., Ce• 4 is [Xe] 4f 0
Eu• 2 is [Xe) 4f7
Tb• 4 is [Xe] 4f 7
Yb• 2 is [Xe) 4f 14
• Each case tends to revert to the more stable oxidation state of +3 by loss or gain of an electron.
io . .
• Th at is wh y Sm•z, Eu+z and Yb•Z ns 10 solutions are good reducing age nts and aqu eou s
sol utio n of Ce+4 and Tb+4
• The Eo val ~ are goo d oxidizing agents.
ue aor Ce+4/Ce•3 is+ 1 ·74 V [Link] suggest tha t it can oxidize wa ter.
Ho we ver the rea cti . cal reagents.
•
on rat e is ver y slo w and hence Ce (IV) is used as a good analyti
'

Atomic 3nd Ionic Radii of La ntbanoids 0,anthanolds Contraction)

2 1.1 .. -- -- 1
-
'$.
-19
;YI -
~
1.05
1

.."'
'8
j "8u 0.95
-~gt .8 I
.I ·e 0.9

-
<
Lu ,I
~
;2
0 .85
0.8
11
1.7 57 5~ 61 63 65 67 69 71
;1
57 59 61 '63 ·as 67 69 71
I Atomic num ber
Ato mic n_u m.b er I

Variation or atomic and ionic radii of

lanthanides

in the
ies, wit h inc rea sin g ato mic num ber, the re is a progressive decrease
• In lan tha noi ds ser
ato mic as well as ionic radii. anoids with increasing
s reg ula r dec rea se ( con trac tion ) in the atomic and ionic radii oflanth
• Thi
noi ds contraction.
ato mic num ber is known as lan tha ionic rad ii
tha t the dec rea se in ato mic rad ii is not quite regular wh ere as for the
• It ma y be not ed
of Ln 3• ions, it is quite regular.
ds ser ies, the nuc lea r
n. As we move along the lanthanoi
• Cause of lanthanoids contractio
h successive element.
charge inc rea ses by one unit at eac
e subshell (viz., 4f).
• The new ele ctro n added into the sam ten ds to dec rea se
ult, the attr act ion on the ele ctro ns by the nucJeus increases and this
• As a res
the size. erfect shielding of one
ed into the f-subshell, the re is imp
• Further, as the new electron is add
due to the sha pe of the se f-orbitals.
electron by ano the r in this sub she ll lea r charge.
shi eld ing is una ble to cou nte rba lance the effect of the inc rea sed nuc
• This imp erf ect ll.
net res ult is a con trac tion in the size though the decrease is ver y sma
• Hence, the ius for 14 elements
inte res ting to not e tha t in lan tha noids, the dec rea se in the atomic rad
• It is
m 183 to 172 pm).
[Ce (58) to Lu (71)] is only 11 pm (fro 3 86 pm).
m Ce • to Lu3• is only 17 pm (103 to
• Similarly, dec rea se in ionic rad ii fro
(d block).
tha t obs uve d in any trans!tion series
Note:-The con trac tion is similar to contraction is due to
cau se is also sim ilar, jus t as in the transition ser ies where the
• The
n by ano the r.
imperfect shielding of one d ele ctro the r with
ing of one 4f ele ctro n by ano the r is less than one d electron by ano
• But the shield
series.
increase in nuc lea r charge alo ng the
gre ate r than in d block.
• And so contraction in f block is
3
Consequence of lantb anold s contraction.

(i) Dlfflculty In separ aUon oflant hanol ds. Since the change in ionic
radii (size of the ions) in
lanthanoids is very small. their chemical properties are similar. This makes
the separa tion of
the lanthanoids in the pure state difficult by normal chemical methods.
• However. lantha noids contraction result s in slight difference in the
size of the lantha nolds
which results in the differences in prope rties like solubility. complex ion
formation. hydration.
basic charac ter of their hydroxides. etc.
• These differences enable the separa tion of individual lantha noids eleme
nts by Ion excha nge
methods.

Diyjsion of Elements into s-. p-, d- and {-Blocks and their Electronic Conft&uratlon

18

5 18

-~
' ~ ;a

LANnlAN IDES

A CTIN IOCS

(ii) Similarity in size of eleme nts belon ging to same group of 4d (secon
d transi tion series )
and Sd (third transi tion series ).
In general, we know that the size of the atoms increases down a group.
• However, where as the size of the atom of any element lying in the 4d
is larger than that of the
atom of the eleme nt lying in the group of the 3d (as expected),
• But the size of any atom of the Sd (after lanthanum) is nearly same
that of the atom of the
element lying in the same group of the 4d.

• A few eleme nts of the 1st, 2nd and 3n1 transi tion series along with their
atomic radii are given
below :
<;n,up No. _. 3
--- -
r;
4 I
I
I
I st lr:1n-; illon s eries ~ 1Sc [1 "'1 pm) n TI (1 32 pm) I -:.iV ( I 'l.'/. pm)
·, nd Tr;:i nsitlon series
:{rd Tr:in silion ser ies
39 Y ( l Hll pm)
,, 7 Li ( l H7 pm)
--
l:1111h;i 111ll d
40 Zr ( l bO pm)
72 1-lf{ l SCJ pm)
l 41 Nhl I H, pm)
71T :1 l l II• pm)
I
(r; !J - 7 1)
-- -- - ---·- -- -·--· -··-- -· ~--- ..

• The similarity in size of the atoms of the elements belonging to the same
group of the 2nd and
3rd transi tion series (after lantha num) (e.g., rzr =::
nu, rNb ~ rra etc.) is evidently due to the effect
oflant hanoi d contraction.
decrea ses from
(iii") Effect on the basic strength of hydroxides. As the size of the lanthanoids ions
basic streng th
La3• to Lu3•, the covalent charac ter of the hydroxides increases and hence the
decrea ses.
• Thus, La(OH)3 is most basic where as Lu(OH)3 is least basic.

General Characteristics
soft metals and
1. Silvery appearance and softne ss : All the lanthanoids are silvery white
r. Samar ium
tarnish rapidly in the air. Their hardne ss increases with increas ing atomic numbe
(Sm) is exceptionally hard like steel.
K except samari um
2. Melting points : They have high meltin g points in the range 1000 to 1200
which has a very high melting point of 1623 K.
structu re and are
3. Electrical and Thermal conductivity : All of them have typical metallic
good conduc tors of heat and electricity.
range 6.77 to 9.74 g
4. Density and other properties: They have high densities which lie in the
r except for
cm-3. Density and other proper ties vary smoothly with increasing atomic numbe
Eu and Yb and occasionally for Sm and Tm.
nt metal ions
5. Colour : The lanthanoids are silvery white metals. However, most of the trivale
partly filled (-
are coloured, both in the solid state and in aqueous solution. This is due to the
orbitals which permit f-f transit ion. e.g., La•3 and Lu• are colourless.
3
anoids except La•3
6. Magnetic behav ior: Paramagnetism is shown by the positive ions oflanth
noids is due to
(lanthanum ion, f 0) and Lu•~ (lutetiu m ion, f ). This proper ty of the lantha
14

presen ce of unpair ed electrons in the incomplete 4f subshell.

600 kJ mol-
7. Ionization enthal pies: The first ionization enthalpies oflanth anoids are around
rable with those of calcium. /
1 and the second about 1200 kJ mol- which are compa
1
of 3d transit ion
• The variati ons of the third ionization enthalpies shows that just as in case
series, the loss of the first two electro ns is accompanied by exchange enthalpy.
is low if it leads to
• Further, the loss of third electron is easier, i.e., third ionization enthalpy
ally low
stable empty, half-filled or completely filled configuration, as indicated by thee abnorm
third ionization enthalpies of La, Gd and Lu.
low ionization
8. Electropositive character : They are highly electropositive because of their
enthalpies.
E0 values for the
9. Standard electr ode potentials : Their standa rd reduction potentials, i.e.,
only exception
half reaction, M3• (aq) +3 e·---+ M (s), lie in the range of - 2.2 to - 2.4 V, the
being europium (Eu) for which the E values is - 2.0 V.
0

agents .
10. Reducing agents : They readily lose electrons and are thus good reducing
complexes due to
11. Complex formation: The lanthan oids do not have much tendency to form
xes and their
low charge density because of their large size. The tendency to form comple
stability increases with increasing atomic numbe r.
e, almost like
12. Chemical behav ior : The first few members of the series are quite reactiv
r to that of
calcium. However, with increasing atomic number, their behavior becomes simila
·
aluminium. A few properties are given below :
Halogen
r--- ---- - LnX3
C, 2773 K
r---- ----- Ln3C, Ln2C3 & LnC2
Dilute acids
Liberate H2 gas
Ln Burn in 0 2
(Lanthanold) Ln 20 3
Heated with N2
LnN
Heated with S
Ln 2SJ
I Ln(7H), I + H,
The hydroxide are definite compound
not just hydrated oxides.
They are basic like alkaline earth
metal oxides and hydroxide s.

Uses of Lanthanoids

1. Lanthanoids do not find any use in the pure state.

2. A well known alloy is mischmetall 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.
3. Mixed oxides of lanthanoid s are employed as catalysts in petroleum cracking.
4. Ln oxides are used as phosphors in television screens and similar fluorescing surfaces.

The Actinoids

• The study of actinoids in detail is not done because of following reason.

1. Oxidation state : The ability of actinoids to exists in different oxidation states has made their
chemistry more complex.
2. Radioactivity : Most of these elements are radioactive and the study their chemistry in
laboratory is difficult
3. Half-life: The earlier members of the series have relatively long half-lives, the later ones have
half-lives ranging from a day to 3 minutes (For lawrencium, Z = 103).
4. Less amount: The later members have therefore, been prepared only in nano gram quantities.

(,
Electronic Conftpratton

Name of the Electronic stability

Symbol
element configuration
Actinium Ac [Rn] 6d 1 7s 2
Thorium Th [Rn] 6d 2 7s2 f1l empty stability
Protactinium Pa [Rn] Sfl 6d 1 7s 2
Uranium u [Rn] Sf3 6d 1 7s 2
Neptunium Np [Rn] Sf4 6d 1 7s 2
Plutonium Pu [Rn] Sf6 7s 2
Americium Am [Rn] 5f7 7s 2 f7 half filled stability
Curium Cm (Rn] Sf' 6d 1 7s 2 f7 half filled stability
Berkelium Bk [Rn] Sf 7s 2
Californium Cf [Rn] 5f10 7s2
Einsteinium Es [Rn] Sfl 1 7s 2
Fermium Fm [Rn] Sf12 7s2
Mendelevium Md [Rn] Sf1 3 7s 2
Nobelium No [Rn] Sf14 7s 2 P 4 full filled stability
Lawrencium Lr [Rn] SP 4 6d 1 7s 2 P 4 full filled stability

(i) All the actinoids have common 7s 2 configuration and variable occupancy of Sf and 6d subshell.

(ii) The 14 electrons are being added into Sf, except in thorium (Z = 90) but filling of Sf continues
again after thorium till Sf orbitals are complete at Z = 103 (Lawrencium).

(iii) The irregularities in the electronic configuration of actinoids like those in the lanthanoids, are
related to the stabilities of fO, r and fl 4 configurations.
For example,
fO - Th [Rn] SfO 6d2 7s2

r -Am [Rn] sr 1s2

Cm [Rn] sr 6d1 7s2

f1 4 - No [Rn] Sf1 4 7s2

Lr [Rn] Sf14 6d1 7s2

(iv) Berkelium (Bk, Z = 97) also shows an exceptional configuration of [Rn] Sf9 6dO 7s2 which is
neither half-filled nor completely filled.

(v) Though 4f and Sf orbitals have similar shapes (angular part of the wave function) but Sf is less
deeply buried than 4f. Hence, Sf electrons can participate in bonding to a far greater extent
Oxidation States ofActinoids
.(
Name of the Oxidation states
symbol
element
Actinium Ac +3
Thorium Th (+3), +4
Protactinium Pa +3,+4, +5
1st half Uranium u +3, +4, +5, +6
Neptunium Np +3, +4, +5, +6, +7
Plutonium Pu +3, (+4), +5, +6
Americium Am +3, (+4)
Curium Cm +3, +4
Berkelium Bk +3
Californium Cf +3
Einsteinium Es +3
2nd half Fermium F111 +3
Mende]evlum Mel +3
Nobe1lum No +3
Lawrencium Lr +3

• There is a greater range of oxidation states, which is in part attributed to the fact that the Sf,
6d and 7s levels are of comparable energies and so all take part in bond formation.
• 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.
• 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.

Ionic Radius & Actinoid Contraction

• The general trend in lanthanoids is observable in the actinoids as well.

• 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.
• The contraction is, however, greater from element to element in this series resulting from poor
shielding by 5/electrons

General Characteristics of Actinoids

1. Silvery appearance : Like lanthanoids, actinoids are metals with silvery appearance.
2. Structural variability : As they have much greater irregularities in their metallic radii than
lanthanoids, they show great structural variability.
3. Colour: These metals are silvery white. However, actinoid cations are generally coloured. The
colour of the cation depends upon the number of Sf-electrons.
4. Melting and Boiling points : High melting and boiling point and shows irregular trend.
S. Density : All the actinoids except thorium and amercium have high densities.
6. Ionization enthalpies : The actinoids have lower ionization enthalpies than lanthanoids
because Sf is less penetrating than 4f and hence is more effectively shielded from the nuclear
charge.
8

....
7. electroposi tive.
7 Electroposftive character : All the know n actinoids metals are highly
8. ly param agnet ic, but
Magnetic behavior : Like lanthanoids, the actino id eleme nts are strong
th e value s are highe r for the actino ids than for the lanth anoid s.
9 .
· Reducing agents : All the actinoids are stron g reducing agent
few memb ers have relati vely
lO. Radioactivity : All the actlno id eleme nts are radio active. First
ives ranging from a few days to
long half-lives. However, the remaining mem bers have half-J
few minu tes (e.g., 3 min for Lr).
in the finely divid ed state. A
l l. Chemical behavior : They are highly reacti ve metal s especially
few prope rties are given below :
~!) They react with boiling water to give a mixtu re of oxide and hydri
de.
eratu re.
(u) They combine with most of the non-m etals at mode rate temp
of nitric acid is very small due
(iii) All these metal s are attack ed by hydrochloric acid but the effect
to the formation of a protective oxide layer on their surface.
(iv) Alkalies have no action on them.

Com paris on of Actlnoids and Lanth anoid s

of f-orbitals, t hey show
• Similarities. As both lanthanoids and actinoids involve filling
simila rities in many respe ct as follows :
(i) Both show mainl y an oxida tion state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibits magn etic and spect ral prope rties.
action show n by lanth anoids.
(iv) Actinoids exhibits actinoids contraction like lantha noids contr

• Differences :
Lantha noids Actin oids
S. No. Prope rty
+3 in most cases but +2 and +4 are +3, +4, +S, +6. +7: Np show s +7
1. Oxidation states
.i lso available. oxidntion st;1te.

Bindi ng energy Bindi ng energies of 4f are higher. Binding energy of [Link] lower:
2. - -
Shield ing effect 4f electrons have greate r shielding Sf electrons havl' poor sh ieldin g
3.
cflecl and thus less contraction in effect. so more contractio n in ionic
ionk radii. radii.

Tendency to form Tende ncy to form complexes is less Comp aratively highe r te ndency lo
4.
form complexes.
comp lexes ·· -- ---- - - - -- - ·--- -
Basic d1ara rter Less basic Hclalivl'ly more basic.
5.
6. Radioactivi ty Only promethium is radioactive. All actinoids nre radioacrive.
-- . ------ ~
tanth anoid s /\ctino ids
S. No. Prope rty
7. Colourless Most ol their ions are colourless. A large numb er of ions :ire coloured.
e.g., ll 1• is red colou r:
u·1• is grer n colou r .~
uo~+ is yellow t·nlour:
- ·-- · - _,__ _ - -- - ----~- - -- - - --·- - - - -·-·-
8. P.11-;i nwgnetic They an· paramagnetic and thl"ir They a re abo para111;1gne tic but
d1:'lr..1ct er magn C'l ic µropcrti es can be difficu lt to t•.xpbi n tht"ir 11wg11etic
identifil'd ea~ily. prupt•rties.
-
CJ. Tendenc:y to form They dn not form oxoions. They form oxnions
oxoinn,; cuo:t, Npo;-. uo~+) ---
.. - -- ·----- -
(