M.E.

S INDIAN SCHOOL, DOHA - QATAR

CHEMISTRY NOTES: 2020- 2021
Section : Boys’/Girls’ Date : 08-10-2020
Class & Div. : XII (All Divisions) Subject: CHEMISTRY
Lesson / Topic: Chapter 8 (The d & f Block Elements)
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Group 3 4 5 6 7 8 9 10 11 12
First Sc Ti V Cr Mn Fe Co Ni Cu Zn
Series 21 22 23 24 25 26 27 28 29 30
( 3d [ Ar ] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar] [Ar]
Series) 3d1 3d2 3d3 4S2 3d5 4S1 3d5 4S2 3d6 4S2 3d7 4S2 3d8 4S2 3d104S1 3d10 4S2
4S2 4S2
Second Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Series 39 40 41 42 43 44 45 46 47 48
( 4d [ Kr] [Kr] [Kr] [Kr] [Kr] [Kr] [Kr] [Kr] [Kr] [Kr]
Series 4d1 4d2 4d3 5S2 4d5 5S1 4d5 5S2 4d6 5S2 4d7 5S2 4d8 5S2 4d105S1 4d10 5S2
5S2 5S2
Third La Hf Ta W RE Os Ir Pt Au Hg
Series 57 72 73 74 75 76 77 78 79 80
( 5d
Series
Fourth Ac Rf Db Sg Bh Hs Mt Ds Rg Uub
Series 89 104 105 106 107 108 109 110 111 112
( 6d
Series

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 d & f block Elements
d block Elements :
 Also called Transition elements
 Includes Group 3 to 12 Elements
 Consists of four series of elements
 First Series - 3d series – From Sc to Zn – Filling of 3d orbital
 Second Series - 4d series – From Y to Cd- filling of 4d orbital
 Third series- 5d series- From La to Hg, omitting Ce to Lu—Filling of 5d orbital
 The fourth 6d series which begins with Ac is still incomplete.
 The two series of the inner transition metals, (4f and 5f) are known as lanthanoids and actinoids
respectively
 General Electronic Configuration :
 A transition element is defined as the one which has incompletely filled (partly filled) d orbitals
in its ground state or in any one of its oxidation states.
Account for the following:
1. Which of the d-block elements may not be regarded as the transition elements? (Or) Zinc,
cadmium and mercury are not considered as true transition elements?
Zn, Cd and Hg have completely filled d 10 configuration in their ground state as well as in
their common oxidation states. Therefore, they are not regarded as transition elements.

2. On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is
not?
Scandium has incompletely filled 3d orbitals in its ground state (3d 1), hence it is regarded
as a transition element. On the other hand, zinc atom has completely filled d orbitals (3d 10) in its
ground state as well as in its oxidised state; hence it is not regarded as a transition element.

3. Silver atom has completely filled d orbitals (4d 10) in its ground state. How can you say that it is
a transition element?
Silver can exhibit +2 O.S where it has incompletely filled d- orbital; (4d 9 ) hence we can
say it as a transition element.

4. Though Cu, Ag and Au have completely filled d orbitals in its ground state yet they are
considered as transition element. Why?
Cu, Ag, Au metals have incompletely filled (partly filled) d orbitals in their common
oxidation state . Eg; Cu2+ - 3d9 , Ag2+ - 4d9 and Au3+ - 5d8

5. The transition elements have many irregularities in their electronic configuration.

In transition elements, the (n-1)d subshell and ns subshell have very small difference in
energy. The incoming electrons may enter into ns or (n-1)d subshell. Hence they show many
irregularities in their electronic configuration.

6. In what way is the electronic configuration of the transition elements different from that of the
non transition elements?
In the non transition elements the valence electrons are present only in the outermost shell
while in the transition elements the valence electrons are present in the outermost as well as d-
orbitals of penultimate shell.
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7. The E.C of Cu is written as [Ar] 3d 104s 1 and not as [Ar] 3d 9 4s 2 . (Or) The E.C of Cr is written
as [Ar] 3d 5 4s 1 and not 3d 4 4s 2 (Or) Cr and Cu exhibit exceptional E.C.
 Because of very little energy difference between (n-1) d and ns orbitals.
 Half and completely filled sets of orbitals are relatively more stable due to symmetry and
larger exchange energy.

PHYSICAL PROPERTIES:

I. MELTING AND BOILING POINTS: ( Fig. 8.1)

 Transition metals have high melting and boiling points.
 Transition metals are hard and low volatility.
 Transition metals have high enthalpies of atomization.
 Exception: Zn, Cd. Hg are soft metals.
Account for the following:
1. Transition Elements have high melting and boiling points. (OR) Transition metals are hard
metals and low volatility.
The high melting points of transition metals is due to the involvement of greater number
of unpaired electrons from (n-1) d in addition to the ns electrons resulting in stronger inter-
atomic interaction and hence stronger metallic bonding.

2. Transition Elements exhibit higher enthalpies of atomization..

The high enthalpies of atomization of transition metals is due to the involvement of
greater number of unpaired electrons from (n-1) d in addition to the ns electrons resulting in
stronger inter-atomic interaction and hence stronger metallic bonding.

3. Chromium group metals (Cr, Mo and W) are hard metals and have low volatility (OR) Cr, Mo
and W have greater enthalpy of atomization.
This is due to the involvement of greater number of unpaired electrons from (n-1) d in
addition to the ns electrons and hence stronger inter-atomic metallic bonding between the atoms
resulting in higher enthalpies of atomization and hence they are very hard and have low
volatility.

4. Zn, Cd and Hg are soft metals, volatile and have low M.P (OR) Hg is a liquid.
Zn, Cd and Hg do not have any unpaired electrons and due to the absence of unpaired
electrons they have weak inter atomic interactions therefore, these are not very hard.

5. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the lowest, i.e.,
126 kJ mol–1
In the formation of metallic bonds, no electrons from 3d-orbitals are involved in case of
zinc, while in all other metals of the 3d series, electrons from the d-orbitals are always involved
in the formation of metallic bonds. Zn has weaker interatomic interactions due to fully filled d-
sub-shell (3d10)

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6. Mn, Tc (technetium) and Re metals have abnormally low melting points.
Because these metals have exactly half-filled stable electronic configuration .Hence the
electrons are held tightly by the nucleus so that the delocalization is less and the metallic bond is
much weaker than the preceding elements.

7. The metals of the second (4d) and third series (5d) have greater enthalpies of atomisation and
melting point than the corresponding elements of the first series.
This is due to the occurrence of much more frequent metal – metal bonding in compounds
of the heavy transition metals.

8. The metals of the second (4d) and third series (5d) have much more frequent metal – metal
bonding in compounds than do the 3d metals
In the same group of d block elements, the 4d and 5d series of transition elements have
larger size than that of 3d elements ( Down the group atomic size increases). Thus the valence
electrons are less tightly held and hence can form metal - metal bond more frequently.

II. ATOMIC AND IONIC SIZE: ( Fig: 8.3 & Table 8.2 )
 Period : The ions of the same charge in a given series show progressive decrease in
radius with increasing atomic number.
 With the increase in atomic number , the atomic radius does not change very much in
transition series.
As the atomic radius increases nuclear charge increases but the addition of
electron in the d subshell increases the screening effect which counter balance the effect
of increased nuclear charge
 Group : The atomic size increase from the first (3d) to the second (4d) series of the
elements but the radii of the third (5d) series are virtually the same as those of the
corresponding members of the second series.
 The decrease in metallic radius coupled with increase in atomic mass results in a general
increase in the density of these elements. Thus, from titanium (Z = 22) to copper (Z =
29) the significant increase in the density may be noted.
Account for the following:
1. The ions of the same charge in a given series (Period) show progressive decrease in radius
with increasing atomic number.
This is because the new electron enters a d orbital each time the nuclear charge increases
by unity. Since the shielding effect of a d electron is not that effective, the net electrostatic
attraction between the nuclear charge and the outermost electron increases and the ionic radius
decreases.

2. The atomic radius shows an increase from the first (3d) to the second (4d) series of the
elements but the radii of the third (5d) series are virtually the same as those of the
corresponding members of the second series.
This phenomenon is associated with the intervention of the 4f orbitals which must be
filled before the 5d series of elements begin. The filling of 4f before 5d orbital results in a regular
decrease in atomic radii called Lanthanoid contraction which essentially compensates for the
expected increase in atomic size with increasing atomic number.
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3. What is meant by lanthanoid contraction? What is the cause of Lanthanoid contraction?

The steady decrease in atomic and ionic sizes of Lanthanide elements (from La to Lu) with
increasing atomic number due to the poor shielding of 4f electrons is called Lanthanoid
contraction.
4. What are the Consequences of lanthanoid contraction?
 Resemblance of second and third transition series:
The pairs of elements Zr-Hf, Nb-Ta, Mo-W, etc., possess almost the same size&
similar properties.
 Difficulty in separation of lanthanoids: A consequence of the lanthanoid contraction,
account for their occurrence together in nature and for the difficulty faced in their
separation in pure state.
Eg: 1. Zr and Hf occur together in nature.
2. Separation of Zr and Hf if difficult from a mixture.
 Basicity differences: As a result of decrease in size, the covalent character of the
hydroxides increases and hence the basic strength decreases.
Eg : La (OH) 3 is most basic while Lu(OH) 3 is the least basic.

III. IONISATION ENTHALPY:

 There is an increase in ionisation enthalpy along each series (Period) of the transition elements
from left to right due to an increase in nuclear charge which accompanies the filling of the
inner d orbitals. However, many small variations occur.
 The first ionisation enthalpy, in general, increases, the magnitude of the increase in the second
and third ionisation enthalpies for the successive elements, in general, is much higher
Special cases : 1. Chromium & Copper 2. Zn. Cd. Hg 3. Mn & Fe
Account for the following :
1. Chromium (Cr) and Copper (Cu) has low first ionization enthalpy( IE)
Cr- Due to the loss of one electron gives stable configuration (3d 5 ) and Cu – due to the
loss of one electron gives stable configuration. (3d 10 ).

2. Zn, Cd and Hg have very high first ionization enthalpy.

Because in Zn, Cd and Hg electron has to be removed from 4s orbital of the stable fully
filled configuration (3 d 10 4s2 ) . Hence large amount of energy is required to remove the
electron.

3. The third ionisation enthalpy of Manganese (Mn) is very high in comparison to iron ( Fe).
The third ionisation enthalpy of Mn is very high because the 3rd electron has to be removed
from the stable half- filled 3d- orbital.
Mn : [Ar]3d5 4s2 Mn2+ [Ar]3d5
Fe : [Ar]3d6 4s2 Fe2+ [Ar]3d6

4. The third ionisation enthalpy for change from Fe2+ to Fe3+ is very small.
Because loss of 3rd electron gives stable configuration of 3d5 in Fe3+. ( Fe3+ [Ar]3d5 ) .

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5. The first I.E of third transition series (5d) are higher than those of first (3d) and second
transition series (4d). (OR) The IE of Hf (6th period) is higher than that of Zr (5th period)
In the atoms of third transition series (5d), there are filled 4f- orbitals. The 4f-orbitals
have very poor shielding effect. As a result the effective nuclear charge on the outer valence
electrons increases as a result size decreases. Hence their I.Es are higher.

6. How would you account for the irregular variation of ionisation enthalpies (first and second)
in the first series of the transition elements?
The irregular variation of ionisation enthalpies is mainly attributed due to the varying
degree of stability of different 3d configurations. For eg. d 0 , d 5, d 10are exceptionally stable.

IV. ELECTRODE POTENTIAL & CHEMICAL REACTIVITY :

 The low value for Sc reflects the stability of Sc3+ ( d0)which has a noble gas configuration.
 The highest value for Zn is due to the removal of an electron from the stable d10 configuration of
Zn2+.
 The comparatively high value for Mn shows that Mn2+(d5 ) is particularly stable, whereas
comparatively low value for Fe shows the extra stability of Fe3+ (d5 ).
 The comparatively low value for V is related to the stability of V2+ (half-filled t2g level, Unit 9)
NOTE : Reducing agent- means undergoes Oxidation- Loses electron
Oxidising agent – means undergoes Reduction- gains electron.

Account for the following :

1. Cr2+ is reducing and Mn3+ is oxidising when both have d 4 configuration.
Cr2+ is reducing as its configuration changes from d 4 to d 3 , the d3 having a half-filled t2g 3
level. On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d 5 )
configuration which has extra stability.

Cr- : [Ar]3d5 4s1 Mn : [Ar]3d5 4s2 Fe : [Ar]3d6 4s2

Cr2+ : [Ar]3d4 Mn3+ : [Ar]3d4 Fe2+ : [Ar]3d6
Cr3+ : [Ar]3d3 ( t2g 3 ) Mn2+ : [Ar]3d5 Fe3+ : [Ar]3d5

2. Which is a stronger reducing agent Cr2+ or Fe2+ and why?

Cr2+ is stronger reducing agent than Fe2+ This can be explained in terms of E° (M3+/M2+)
value . E° (Cr3+/Cr2+) has high negative value (-0.41V) indicating that Cr2+would change into Cr3+
readily ( t2g 3 ) whereas when Fe 2+ d 6 changes to Fe3+ d 5.
Fe2+ changes from d6 to d5 – stable half filled d5 configuration
Cr2+ Changes from d 4 to d 3 - stable half filled t2g 3configuration
Half filled t2g 3 configuration is more stable than d5 configuration.

3. Why is the E° value for the (Mn3+/Mn2+) couple much more positive than that for (Cr3+/Cr2+) or
(Fe3+/Fe2+) Explain.
Much larger third ionisation energy of Mn (where the required change is d 5 to d 4 ) is
mainly responsible for this. This also explains why the +3 state of Mn is of little importance.

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4. The E° (M2+/M) value for copper is positive (+0. 34V). What is possibly the reason for this?
The positive value of E° (M2+/M) for Cu is due to its high enthalpy of atomization and high
value of enthalpies of ionisation (∆iH°1+ ∆iH°2), that the sum of enthalpies of sublimation and IE is
not balanced by its low hydration enthalpy. Therefore, high energy is required to transform Cu(s) to
Cu2+ (aq).

5. Cu+ ion is not stable in aqueous solutions.(Or)Copper(I) has d10 configuration, while copper(II)
has d9 configuration, still copper(II) is more stable in aqueous solution than copper(I).
Copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.

6. The d1 configuration is very unstable in ions.

The ions in d1 configuration have greater tendency to acquire more stable d0 configuration
by losing the one d-electron and act as reducing agent.

GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS:

 Transition metals show variable oxidation states.
 Transition metal ions are paramagnetic in nature.
 Transition metals generally form coloured ions.
 Transition metals form complexes.
 Transition metals and its compounds act as catalyst.
 Transition metals form alloys.
 Transition metals form interstitial compounds.
 Transition metals form alloys.

I. OXIDATION STATES :
1. Transition elements show a great variety of oxidation states in its compounds.
Due to the participation of inner (n-1) d- electrons in addition to outer ns-
electrons in bond formation since the energies of (n-1) d- and ns- subshells are almost equal.

2. Name the element of the first row transition series (3d) which exhibits the largest no of
Oxidation states? Why?
Manganese, it exhibits all the oxidation states from +2 to +7 due to the maximum
number of unpaired electrons.

3. What is the highest oxidation state shown by transition metal in the 3d series?
Manganese (+7)

4. What is the highest oxidation state shown by any transition metal ?

+8 (Osmium (Os) and (Ru) ruthenium)
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5. Name the element of the first row transition series (3d) which exhibits +1 oxidation state most
frequently and why?
Copper . Because Cu +1 has stable [Ar] 3d10 configuration.
6. Name a transition element which does not exhibit variable Oxidation state.
Scandium (+3)
7. A transition metal exhibits higher oxidation state in oxides and fluorides.
Because fluorine and oxygen are small in size, the most electronegative elements
and best oxidizing element, hence they can oxidise the metal to its highest oxidation states.

8. The highest oxidation state is exhibited in oxoanions of a metal.

Because oxygen is small in size, electronegative element and best oxidizing element
hence it can oxidise the metal to its highest oxidation state. But the ability of oxygen to stabilise
these high oxidation states exceeds that of fluorine due to the ability of oxygen to form
multiple bonds to metals. Eg : The highest Mn fluoride is MnF4 whereas the highest oxide
is Mn2O7.

9. The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.

In the lower oxidation state of the metal, some of the valence electrons of the metal
atom are not involved in bonding. Hence, it can donate electrons and behave as a base. In the
higher oxidation state, valence electrons are involved in bonding and are not available for
donation. Instead, effective nuclear charge is also high. Hence, it can accept electrons and
behave as an acid.

10. Low oxidation states for transition metals are found when a complex compound has ligands
capable of π-acceptor character in addition to the σ-bonding.
For example in metal carbonyls like Ni(CO)4 and Fe(CO)5, the oxidation state of nickel and
iron is zero.

11. Why Mn2+ compounds are more stable than Fe2+ towards oxidation to their +3 oxidation state.
Mn2+ Due to the stable half filled d5 sub-shell it is not easily oxidised to Mn3+. Fe 2+ (3d6
) only after the loss of one electron it will get stable half filled sub-shell. Hence, Fe2+ is easily
oxidised to +3 oxidation state.

12. Classifies the following oxides in the increasing order of acidic strength.
Mn2O7, MnO2, Mn3O4, Mn2O3 , MnO
The increasing order of acidic strength of the oxides is MnO (+2)< Mn3O4 ( +8/3) <
Mn2O3 ( +3) < MnO2 ( +4) < Mn2O7 ( +7).
NOTE :
 Higher the oxidation state of the metal , higher the acidic strength of the oxides.
 As the oxidation number of the metal increases , ionic character decreases.

13. Name the oxometal anions of the first series of the transition metals in which the metal exhibits
the oxidation state equal to its group number.
 Dichromate ion Cr2O7 2-, Oxidation state of Cr is + 6. and its group number 6.
 Permanganate ion , MnO4-Oxidation state of Mn is + 7 and its group number is 7.
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14. How is the variability in oxidation states of transition metals different from that of the non-
transition metals? Illustrate with examples.
 In transition elements, the oxidation states differ by one unit (Fe2+and Fe3+; Cu+ and
Cu2+). In nontransition elements, the oxidation states differ by 2 unit, for example, +2 and
+4 ( Group 16) or +3 and +5 ( Group 15), etc.
 In the p–block ( non transition element) the lower oxidation states are favoured by the
heavier members (due to inert pair effect). Eg: TlCl is more stable than TlCl3 . The
opposite is true in the groups of d-block. For example, in group 6, Mo(VI) and W(VI) are
found to be more stable than Cr(VI).

15. How would you account for the increasing oxidising power in the series? VO2+ < Cr2O7 2- <
MnO4 - ?
This is due to the increasing stability of the lower species to which they are reduced.

16. Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily
oxidised.
Co (III) has greater tendency to form coordination complexes than Co (II). Hence in the
presence of ligands, Co (II) changes to Co (III). ie the CFSE more than compensates the 3rd
ionisation enthalpy.

17. What is meant by ‘disproportionation’ of an oxidation state? Give two examples.

When a particular oxidation state becomes less stable relative to other oxidation states,
one lower, one higher, it is said to undergo disproportionation. For example, manganese (VI)
becomes unstable relative to manganese (VII) and manganese (IV) in acidic solution.

II. MAGNETIC PROPERTIES:

1. Many of the transition metals and their compounds show paramagnetic behavior.
Paramagnetism arises due to the presence of unpaired electrons in the (n-1) d
orbitals
NOTE:
 Greater the number of unpaired elecrons, greater is the paramagnetic character and
larger is the magnetic moment.
 Magnetic moment can be calculated by the spin only formula BM.

2. Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic number is 25.
With atomic number 25, the divalent ion in aqueous solution will have d 5 configuration
(five unpaired electrons). The magnetic moment = 5.92BM ( n= 5)

3. Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27).
M 2+ (aq) ion: [Ar] 3d7 -3unpaired electrons. =3.87BM. ( n=3)

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NOTE:
 Diamagnetic substances are repelled by the applied field and all the electrons are paired.
 Paramagnetic substances are weakly attractedby the magnetic field and have unpaired electrons.
 Ferromagnetic substances are strongly attracted by applied field.It is an extreme form of
paramagnetism.

III. FORMATION OF COLOURED IONS:

1. Most of the compounds of transition metals are coloured in the solid form or solution form.
This is due to the presence of unpaired electron in the (n-1) d subshell. Hence they
can under go d-d transition by absorbing light of suitable frequency from the visible region
and emitting complementary colour.

2. Why Zn 2+ salts are white while Ni2+ salts are blue?

Zn 2+ has completely filled 3d10 orbital while Ni2+ has incompletely filled 3d8 orbitals
which can undergo d-d transition
.
3. Scandium forms no coloured ions, yet it is regarded as a transition element. Explain why?
Scandium in the ground state has one electron in the 3d subshell. Hence, it is
regarded as a transition element. However, in its common oxidation state of +3, it has no
electrons in 3d subshell( 3d0 ). Hence no d-d transition and does not form coloured ions.

IV. FORMATION OF COMPLEX COMPOUNDS:

Transition metals form a large number of complex compounds.
 This is due to the comparatively smaller sizes of the metal ions.
 Due to their high ionic charges.
 Due to the availability of vacant d orbitals for bond formation with ligands.

V. CATALYTIC PROPERTIES:
Transition metals and their compounds are known for their catalytic activity. (Or) Why
does Vanadium pentoxide act as a catalyst?
 Due to the ability of transition metal to adopt multiple oxidation states
 Ability to form complexes as they have incompletely filled d- orbitals
 Surface of the metals where reaction can occur.
Eg : Vanadium(V) oxide (in Contact Process), finely divided iron (in Haber’s Process),
and nickel (in Catalytic Hydrogenation).

VI. FORMATION OF INTERSTITIAL COMPOUNDS:

1. Transition elements form interstitial compounds.
Due to the presences of voids of suitable size in which small atoms like H, C or N
are trapped inside the crystal lattices of metals. These voids are present because of defects
in their structure and existence of variable oxidation state.

2. What are Interstitial Compounds?

Interstitial compounds are those which are formed when small atoms like H, C or N are
trapped inside the crystal lattices of metals.
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3. List the characteristics of interstitial compounds.
 Interstitial Compounds have high melting points, higher than those of pure metals.
 They are very hard, some borides approach diamond in hardness.
 They retain metallic conductivity.
 They are chemically inert

VII. ALLOY FORMATION:

1. Transition elements form alloys with other transition metals easily.
The transition metals are quite similar in radii and one metal can substitute the
atoms of other metal in its crystal lattice and due to some other characteristics of transition
metals, alloys are readily formed by these metals.

2. What are alloys? Give examples.

An alloy is a blend of metals prepared by mixing the components. Alloys may be
homogeneous solid solutions in which the atoms of one metal are distributed randomly among
the atoms of the other.
 Eg: Brass (copper-zinc) and Bronze (copper-tin).
 Ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are used for
the production of a variety of steels and stainless steel.

THE INNER TRANSITION ELEMENTS ( f BLOCK ELEMENTS)

1. What are inner transition elements? How are they classified? Write their general electronic
configuration.
 Inner transition elements are the elements in which the last electron enters the f- orbital
and are called f-block elements .
 The f-block consists of the two series, lanthanoids (the fourteen elements following
lanthanum) where filling of 4f orbital takes place.
 Actinoids (the fourteen elements following actinium) where filling of 5f orbital takes
place.

2. Electronic configuration is (n-2) f1-14 (n-1) d0-1 nS2

3. Atomic and Ionic size :Lanthanoid Contraction and its consequences. ( Refer d block)

4. Oxidation State:
 Common oxidation state +3
 Occasionally +2 and +4 in solution and solid compounds.
 The irregularity arises mainly from the extra stability of empty, half-filled or filled f
subshell.
 Formation of Ce(IV) is favoured by its noble gas configuration, but it is a strong oxidant
reverting to the common +3 state. and hence Ce(IV) is a good analytical reagent.
 Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts for the
formation of this ion. However, Eu2+ is a strong reducing agent changing to the common
+3 state.
 Yb2+ which has f 14 configuration is a reductant.
 Tb(IV) has half-filled f-orbitals and is an oxidant.
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5. General Characteristics:
 Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous
solutions. Colour of these ions may be attributed to the presence of unpaired f electrons (
f-f transition).
 Neither La3+ nor Lu3+ ion shows any colour (f0 and f14)but the rest do so. However,
absorption bands are narrow, probably because of the excitation within f level.
 The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and
Lu3+) are all paramagnetic. The paramagnetism rises to maximum in neodymium.

6. Uses of Lanthanoids:
 A well known alloy is mischmetall which consists of a lanthanoid metal (~ 95%) and
iron (~ 5%) and traces of S, C, Ca and Al is used in Mg-based alloy to produce bullets,
shell and lighter flint.
 Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
 Some individual Ln oxides are used as phosphors in television screens and similar
fluorescing surfaces.
 The best single use of the lanthanoids is for the production of alloy steels for plates and
pipes.

ANSWER THE FOLLOWING :

1. Ce (III) can easily be oxidised to Ce (IV). Explain why? (Or) Ce forms a tetrapositive ion, Ce4+
in solutions.
Ce(III) has 4f1 . It can be easily oxidized because it can readily lose an electron to
acquire the stable 4f0 configuration and form Ce(IV).

2. Use Hund’s rule to derive the electronic configuration of Ce3+ ion, and calculate its magnetic
moment on the basis of ‘spin-only’ formula.
Ce= [Xe] 4f1 5d1 6s2 ( n=1 ), µ = √1(1+2) =√3 =1.72BM

3. Actinoid contraction is greater from element to element than lanthanoid contraction.

In actinoids, 5f orbitals are filled. These 5f orbitals have a poorer shielding effect
than 4f orbitals (in lanthanoids). Hence the actinoid contraction is greater from element to
element due to poor shielding of 5f electrons than by 4f electrons.

4. Actinoids shows a wide range of oxidation states than lanthanoids.

Due to the comaparable energies of 5f, 6d and 7s subshells , all can take part in bond
formation.

5. The chemistry of the actinoid elements is not so smooth as that of the Lanthanoids.
Actinoids shows a large number of oxidation states and actinoids are radioactive .

6. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
Cerium (Z = 58)

F 061, Rev 01, dtd 10th March 2020

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 d & f block Elements

F 061, Rev 01, dtd 10th March 2020

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