f-Block Elements

The elements in which the last electron enters the f orbital of ante-penultimate shell ie
(n ─ 2) f orbital are called f-block element.
Also called inner transition elements because they form a transition series with in the
transition series(d- block elements)
General electronic configuration: (n ─ 2)f 1─ 14 (n ─ 1)d0 ─ 1 ns2.
Classification:
(i)Lanthanoids or Lanthanides(58-71): called so because follow lanthanum of d-
block,include 14 elements,constitute 4f series because last electron enters 4f orbital,were
known as rare earth elements because of their rare occurrence, are all metals
(ii)Actinoids or actinides(90-103): called so because follow actinium of d- block,include
14 elements,constitute 5f series because last electron enters 5f orbital,are all radioactive.
All elements beyond uranium ie. Transuranic elements are man made elements.
4f series:
General electronic configuration: 54[Xe] 4f 1─14 5d0 ─ 1 6s2.

Elements: Symbol: Electronic Ln3+

configuration:
1 2
Lanthanum 57La 54[Xe] 5d 6s 4f0
1 1 2
Cerium 58Ce 54 [Xe] 4f 5d 6s 4f1
3 2
Praseodymium 59Pr 54 [Xe] 4f 6s 4f2
4 2
Neodymium 60Nd 54 [Xe] 4f 6s 4f3
5 2
Promethium 61Pm 54 [Xe] 4f 6s 4f4
6 2
Samarium 62Sm 54 [Xe] 4f 6s 4f5
7 2
Europium 63Eu 54 [Xe] 4f 6s 4f6
7 1 2
Gadolinium 64Gd 54 [Xe] 4f 5d 6s 4f7
9 2
Terbium 65Tb 54 [Xe] 4f 6s 4f8
10 2
Dysprosium 66Dy 54 [Xe] 4f 6s 4f9
11 2
Holmium 67Ho 54 [Xe] 4f 6s 4f10
12 2
Erbium 68Er 54 [Xe] 4f 6s 4f11
13 2
Thulium 69Tm 54 [Xe] 4f 6s 4f12
14 2
Ytterbium 70Yb 54 [Xe] 4f 6s 4f13
14 1 2
Lutetium 71Lu 54 [Xe] 4f 5d 6s 4f14

(Exceptions: Gadolinium 54 [Xe] 4f7 5d1 6s2 ,highly stable half-filled orbitals
Lutetium 54 [Xe] 4f14 5d1 6s2 highly stable completely filled orbitals)
* Promethium: The only man-made radioactive lanthanoid.

Q: Write down the electronic configuration of (i) Pm3+ (ii) Ce4+ (iii) Lu2+ (iv) Th4+

Q: What are inner-transition elements?Decide which of the following are atomic

numbers of the inner-transition elements: 29,59,74,95,102,104.
Ans: 59, 95 , 102
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Q: Write the electronic configuration of Ce3+ ion and calculate its magnetic moment
on the basis of spin only formula.
Ans: n=1 , magnetic moment = 1.73 BM.

Characteristics:
(i)Silvery white soft metals
(ii)Tarnish rapidly in air.
(iii)Hardness increases with increasing atomic number.*Samarium-hard like steel.
(iv) High melting points in the range 1000K-1200 K. *Samarium- 1623 K.
(v)Good conductors of heat and electricity.
(vi)High density
(vii)Most of trivalent metal ions are coloured both in solid state and in aqueous solution
due to partly filled f-orbitals which allow f-f transition.
*La3+ ,Lu3+ are colourless.
*Lanthanoids with x f electrons have same colour as those with (14-x) f electrons.
(viii) All are paramagnetic due to unpaired electrons in f orbitals.
*La3+ ,Lu3+ are diamagnetic.
(ix) 1st ionisation enthalpies around 600 kJ /mol, 2nd ionisation enthalpies around 1200
kJ/mol (comparable to that of Ca) ,3rd ionisation enthalpy is low if it leads to stable
empty,half filled or fully filled configuration as indicated by abnormally low 3rd
ionisation enthalpies of La,Gd and Lu.
(x) highly electropositive due to low ionisation enthalpies.
(xi) Their standard reduction potential values ie Eo values for the reaction
M3+ (aq) + 3 e ─ → M (s)
Lie in the range of ─ 2.2 to ─ 2.4 V.
* Eo value for Eu is ─ 2.0 V.
(xii) They readily lose electrons and are thus good reducing agents.

Oxidation States:
 All lanthanoids show a common oxidation state of +3.
 In addition some lanthanoids also show oxidation states of +2 and +4.They are
generally shown by those elements which by doing so attain the stable f0 , f7 or f14
configurations.
eg. Ce4+ : [Xe] 4f0 Tb4+ : [Xe] 4f7
Eu2+ : [Xe] 4f7 Yb2+ : [Xe] 4f14
*
Pr , Nd , Dy , Yb , Nd , Sm , Tm2+
4+ 4+ 4+ 2+ 2+ 2+

 Generally lanthanoids in +4 oxidation states act as strong oxidising agents and

change their oxidation state from +4 to +3.eg in aqueous solution Ce4+ is good
oxidising agent.
lanthanoids in +2 oxidation states act as strong reducing agents and
change their oxidation state from +2 to +3.eg in aqueous solution Eu2+,Yb2+ and
Sm2+ are good reducing agents.
 Lanthanoids donot show as many different oxidation states as are exhibited by the
transition metals.This is probably due to the reason that d electrons are present in
(n- 1)d subshell and can easily participate in bond formation.On the other hand f
2
 electrons occupy (n- 2) f subshell which penetrate closer to the nucleus and
therefore it is not easy for them to participate in bond formation with other
elements.As a result lanthanoids exhibit only limited oxidation states out of which
+3 is the most common.
Q: Name a member of the lanthanoid series which is well known to exhibit +4
oxidation state.

Q: What are different oxidation states exhibited by Lanthanoids?

Q: Name the elements of lanthanoid series which exhibit +4 oxidation states and
Those which exhibit +2 oxidation states.Try to correlate this type of behaviour
with the electronic configuration of these elements.

Q: What is lanthanoid contraction? What are the consequences of lanthanoid

contraction?
Ans:
The regular decrease in the atomic and ionic radii of elements of the lanthanoid
series with increasing atomic number is called lanthanoid contraction.
Cause:
As we move along the lanthanoid series,the nuclear charge increases. Also new electrons
enter into the (n-2) f subshell but f electrons shield each other from nuclear charge
poorly because of very diffused shapes of f orbitals.This imperfect shielding is unable to
counterbalance the effect of the increased nuclear charge.This results in net decrease in
size though decrease is very small.
Consequences of lanthanoid contraction:
(i) Lanthanoids have similar ionic radii, similar chemical properties, so they are
difficult to separate.However lanthanoid contraction results in slight
difference in properties which help in separation of individual lanthanoid
elements by ion exchange methods.
(ii) Due to lanthanoid contraction, atoms of the elements belonging to same group
of 2nd and 3rd transition series have similar atomic radii.
(iii) As the size of lanthanoid ions decreases from La3+ to Lu3+ ,the covalent
character of the hydroxides increases,M-OH bond length decreases and hence
the basic strength decreases.Thus La(OH)3 is most basic whereas Lu(OH)3 is
least basic.

Chemical Reactions: Lanthanoids are highly electropositive in nature and they have
almost similar reactivity.
halogen
→ LnX3
C , 2773K
→ Ln3C , Ln2C3 , LnC2
Dilute acid
Ln → liberate H2 gas
Burn in O2
→ Ln2O3
 3
heated with N2
→ LnN
heated with S
→ Ln2S3
H O
2
→ Ln(OH)3 + H2
Uses:
(i) In production of alloy steel to improve its strength .
(ii) Mischmetal
Composition:lanthanoid metals ≈ 95%, Iron≈ 5%, traces of S,C,Ca and Al.
Used in making a pyrophoric alloy by mixing 3% mischmetal with Mg ; the alloy thus
obtained emits spark when struck and is used in making bullets,shells and lighter flints.
(iii)Their oxides are used in glass industry for polishing glass and for making coloured
glasses for goggles as they give protection against UV light and as phosphor for
television screens.
Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.

Q: What are alloys? Name an important alloy which contains some of the lanthanoid
metals.Mention its uses.

5f series: General electronic configuration: 86[Rn] 5f 1─14 6d0 ─ 17s2.

Elements: Symbol: Electronic M3+

configuration:
1 2
Actinium 89Ac 86[Rn] 6d 7s 5f0
2 2
Thorium 90Th 86 [Rn] 6d 7s 5f1
2 1 2
Protactinium 91Pa 86 [Rn] 5f 6d 7s 5f2
3 1 2
Uranium 92U 86 [Rn] 5f 6d 7s 5f3
4 1 2
Neptunium 93Np 86 [Rn] 5f 6d 7s 5f4
6 2
Plutonium 94Pu 86 [Rn] 5f 7s 5f5
7 2
Americium 95Am 86 [Rn] 5f 7s 5f6
7 1 2
Curium 96Cm 86 [Rn] 5f 6d 7s 5f7
9 2
Berkelium 97Bk 86 [Rn] 5f 7s 5f8
10 2
Californium 98Cf 86 [Rn] 5f 7s 5f9
11 2
Einsteinium 99Es 86 [Rn] 5f 7s 5f10
12 2
Fermium 100Fm 86 [Rn] 5f 7s 5f11
13 2
Mendelevium 101Md 86 [Rn] 5f 7s 5f12
14 2
Nobelium 102No 86 [Rn] 5f 7s 5f13
14 1 2
Lawrencium 103Lr 86 [Rn] 5f 6d 7s 5f14
*Though 4f and 5f orbitals have similar shapes but 5f is less deeply buried than
4f.Hence 5f electrons can participate in bonding to a far greater extent.

Q: Write the electronic configurations of the elements with atomic numbers

61,91,101 and 109.
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Oxidation State:
 Most common oxidation state is +3.
 Because of very small energy difference b/w 5f,6d and 7s subshells,all the
electrons can participate in bond formation.Therefore actinoids show a large
number of oxidation states unlike lanthanoids.
 The maximum oxidation state first increases up to middle of the series and then
decreases.eg. +4 for Th to +5,+6 and +7 for Pa,U and Np then decreases in the
succeeding elements.
Q: Name the last member of actinoid series.Write the electronic configuration of this
element. Comment on the possible oxidation state of this element.

Q: The chemistry of the actinoid elements is not as smooth as that of the

Lanthanoids. justify this statement by giving examples from the oxidation state
of these elements.

Actinoid Contraction:
The actinoids show actinoid contraction due to poor shielding effect of 5f electrons.As a
result ,the radii of atoms/ions decreases regularly across the series.
The magnitude of actinoid contraction is much more than that of
lanthanoid contraction.This is due to reason that 5f orbitals are more diffused than the
orbitals present in 4f subshell. Consequently,the shielding by 5f electrons is much less
than by 4f electrons in lanthanoids.

Q: Actinoid contraction is greater from element to element than lanthanoid

contraction . Why?

Characteristics:
(i) Silvery in appearance.
(ii) lower ionisation enthalpies than lanthanoids because 5f is less penetrating than 4f
and hence is more effectively shielded from nuclear charge.
(iii)strongly paramagnetic in nature.
(iv)strong reducing agents.
(v)Highly electropositive metals ,more reactive than lanthanoids .A few properties
are:
*React with boiling water to give a mixture of oxide and hydride.
*combine with most of the metals at moderate temperature.
*all metals readily attacked by HCl but slightly affected by nitric acid due to
formation of a protective oxide layer on their surface.
*alkalies have no action on them.

Q:Compare the chemistry of actinoids with that of lanthanoids with special reference to
(i)electronic configuration (ii) oxidation state
(iii) atomic and ionic sizes (iv) chemical reactivity.
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