Unit : 8 – d- & f- Block Elements

The element in which incoming electron enters in (n-1)d orbitals are called d-block elements.

Position in the Periodic Table

The d–block occupies the large middle section flanked by s– and p– blocks in the periodic table. The
very name ‘transition’ given to the elements of d-block is only because of their position between s–
and p– block elements.

d-orbital elements involve three completely filled 3d, 4d, 5d series and one 6d incomplete series.

Electronic Configurations of the d-Block Elements : (n-1)d1–10 ns1–2

The electronic configurations of Zn, Cd and Hg are represented by the general formula (n-1)d10 ns2 .
The orbitals in these elements are completely filled in the ground state as well as in their common
oxidation states. Therefore, they are not regarded as transition elements

Problem : Silver atom has completely filled d-orbitals (4d10) in its ground state.How can you say that
it is a transition element?

General Properties of the Transition Elements (d-Block)

1) Physical Properties :
 The transition metals (with the exception of Zn, Cd and Hg) are very much hard and have
low volatility. Their melting and boiling points are high
 The high melting points of these metals are attributed to the involvement of greater number
of electrons from (n-1)d in addition to the ns electrons in the interatomic metallic bonding.
 They have high enthalpies of atomization.

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 Unit : 8 – d- & f- Block Elements

 The metals of the second and third series have greater enthalpies of atomisation than the
corresponding elements of the first series due to much more frequent metal – metal
bonding in compounds of the heavy transition metals.
 In general, greater the number of valence electrons, stronger is the resultant bonding and
high enthalpy of atomization.

Problem : In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the
lowest, i.e., 126 kJ mol –1. Why?

2) Variation in Atomic and Ionic Sizes of Transition Metals

Progressively decrease in radius with increasing atomic number. This is because the new
electron enters a d-orbital and each time the nuclear charge increases by unity and the
shielding effect of a d-electron is not that effective, hence the ENC increases and the ionic
radius decreases.

Due lanthanoid contraction, the second and the third d series exhibit similar radii (e.g., Zr 160
pm, Hf 159 pm) and have very similar physical and chemical properties

3) Ionisation Enthalpies : Increases regularly due to decrease in atomic size.

4) Oxidation States : Common oxidation states is +2

 Mn shows maximum oxidation state (+7) in KMnO4 (3d series ) and Os (+8) in
OsO4 (5d series ).
 The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals .

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 Unit : 8 – d- & f- Block Elements

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

5) Trends in the M2+/M Standard Electrode Potentials : Std. electrode potential is the sum
of the first and second ionization enthalpy and sublimation enthalpy and hydration enthalpy.

The metals which are having high value of first and second IE are having positive std. electrode
potential. i.e. Cu

The metals which are having high value of hydration enthalpy are having negative std.
electrode potential. i.e. Zn
 The general trend towards less negative E0 values is related to the increase in the sum of
the first and second ionisation enthalpies.

Problem : The E0 (M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this?

(Hint consider its high ΔaH0 and low ΔhydH0)

6) Trends in the M3+/M2+ Standard Electrode Potentials :

 The low value for Sc reflects the stability of Sc 3+ 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 Mn 2+ (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 V 2+(half-filled t2g level)

7) Trends in Stability of Higher Oxidation States :

 The highest oxidation states are shown by metals with fluorine and oxygen.

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 Unit : 8 – d- & f- Block Elements

 The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice
energy as in the case of CoF3, or higher bond enthalpy terms for the higher covalent
compounds, e.g., VF5 and CrF6
 copper (I) compounds are unstable in aqueous solution and undergo disproportionation.

 The ability of oxygen to stabilise the highest oxidation state is demonstrated in the oxides.
 The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine. The
ability of oxygen to form multiple bonds to metals explains its superiority than fluorine.

Problem :
1. How would you account for the irregular variation of ionization enthalpies (first and
second)
in the first series of the transition elements?
2. Explain why Cu+ ion is not stable in aqueous solutions?

8) Chemical Reactivity and E0 Values :

 The metals of the first series with the exception of copper are relatively more reactive and
are oxidised by 1M H+ .
 An examination of the E0 values for the redox couple M3+/M2+ shows that Mn3+and Co3+ ions
are the strongest oxidising agents in aqueous solutions. The ions Ti2+, V2+and Cr2+ are
strong reducing agents and will liberate hydrogen from a dilute acid, e.g.

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 Unit : 8 – d- & f- Block Elements

Problems :
1.Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
2.Which is a stronger reducing agent Cr2+ or Fe2+ and why

9) Magnetic Properties :
 Due to presence of unpaired electrons.
 Each unpaired electron having a magnetic moment associated with its spin angular
momentum and orbital angular momentum .
 For the compounds of the first series of transition metals, the contribution of the orbital
angular momentum is effectively quenched and hence is of no significance .
 For these, the magnetic moment is determined by the number of unpaired electrons and is
calculated by using the ‘spin-only’ formula, i.e.,

 where n is the number of unpaired electrons and µ is the magnetic moment in units of Bohr
magneton (BM).

Problem : Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).

10) Formation of Coloured Ions :

 Transition metals form coloured solution (ions) due to the excitation of electron from t2g
orbital to eg orbital
 Explanation : When an electron from a lower energy d orbital is excited to a higher energy d
orbital, the energy of excitation corresponds to the frequency of light absorbed in the visible
region. The colour observed corresponds to the complementary colour of the light absorbed
.
 The colour of ions depends on nature of ligand .

11) Formation of Complex Compounds :

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 Unit : 8 – d- & f- Block Elements

The transition metals form a large number of complex compounds. This is due to the
comparatively
smaller sizes of the metal ions, their high ionic charges and the availability of d orbitals for
bond formation.

12) Catalytic Properties :

The transition metals and their compounds are known for their catalytic activity. This activity is
due to their ability to adopt multiple oxidation states and to form complexes.
For example, iron(III) catalyses the reaction between iodide and persulphate ions.

13) Formation of Interstitial Compounds :

Interstitial compounds are those in which small atoms occupy the interstitial sites in the crystal
lattice. Interstitial compounds are well known for transition metals because of small
– sized atoms like H, B, C, N etc can easily occupy positions in the voids present in
the crystal lattice of transition metals.

14) Alloy Formation :

An alloy is a blend of metals prepared by mixing the components. Because of similar radii and
other characteristics of transition metals, alloys are readily formed by these metals.
Alloys of transition metals with non transition metals such as brass (copper-zinc) and bronze
(copper-tin), are also of considerable industrial importance.

Some Important Compounds of Transition Elements

(i) Oxides and Oxoanions of Metals :

(a) Potassium dichromate K2Cr2O7 : Preparation –

Dichromates are generally prepared from chromate, which in turn are obtained by the
fusion of chromite ore (FeCr2O4) with sodium or potassium carbonate in free access of air.
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 Unit : 8 – d- & f- Block Elements

Compound Colour Name

Green Chromite Ore

Orange Potassium dichromate

Orange Sodium dichromate

Yellow Sodium chromate

 Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.

 The chromates (yellow) and dichromates (orange)are inter convertible in aqueous solution
depending upon pH of the solution.

 Sodium and potassium dichromates are strong oxidising agents .

 Reaction of dichromate ion and ferrous ions

(b) Potassium permanganate KMnO4 : Preparation –

Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and
an oxidising agent like KNO3. This produces the dark green K2MnO4 which disproportionates
in a neutral or acidic solution to give permanganate.

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 Unit : 8 – d- & f- Block Elements

The manganate and permanganate ions are tetrahedral; the green manganate is paramagnetic
with one unpaired electron but the permanganate is diamagnetic.

 On heating it decomposes and shows disproportionate reaction.

 It act as strong oxidizing agent in acidic medium and weak oxidizing agent in basic medium.
 Examples

 Permanganate titrations in presence of hydrochloric acid are unsatisfactory since

hydrochloric acid is oxidised to chlorine.
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 Unit : 8 – d- & f- Block Elements

THE INNER TRANSITION ELEMENTS ( f-BLOCK)

The f-block consists of the two series, lanthanoids (the fourteen elements following lanthanum) and
actinoids (the fourteen elements following actinium)

The Lanthanoids : The elements in which incoming electron enters in 4f orbital are called
lanthanoids.

(i) Electronic Configurations : 4f1-14 5d0-2 6s2 (Missing Confi. f2, f8 )

(ii) Lanthnoid contraction :

The decrease in atomic and ionic radii with increasing atomic number in lanthanoid is called
lanthanoid contraction.

Effect of Lanthanoid contraction :

(i) The radii of the members of the third transition series is similar to those of the
corresponding members of the second series . i.e Zr(160 pm) and Hf (159 pm),
(ii)Due to similar atomic size , their separation becomes difficult .

(iii) Oxidation States : Most common oxidation state is +3 and some lanthanoid element also
exhibit +2 and +4 oxidation state.
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 Unit : 8 – d- & f- Block Elements

(iv) Reactivity of Lanthanoids

(v) Alloy of lanthanoids (Misch Metal) : consists of a lanthanoid metal (~ 95%) and iron (~
5%) and traces of S, C, Ca and it is used in Mg-based alloy to produce bullets, shell and
lighter flint.

The Actinoids : The elements in which incoming electron enters in inner 5f orbital .

(i) Electronic Configurations : 4f0-14 5d0-1 6s2 (Missing Confi. f1, f5, f8 )

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 Unit : 8 – d- & f- Block Elements

(ii) Ionic Sizes : There is a gradual decrease in the size of atoms or M3+ ions across the
series due to actinoid contraction (like lanthanoid contraction). The contraction is,
however, greater from element to element in this series resulting from poor shielding by
5f electrons.

(iii) Oxidation States : Common oxidation state is +3

* There is a greater range of oxidation states, which is in part attributed to the fact that
the 5f, 6d and 7s levels are of comparable energies.

Comparasion between Lanthanoids and Actinoids

SN Lanthanoids Actinoids
1 4f-orbital is progressively filled 5f-orbital is progressively filled
2 +4 O.S. is most common along Shows more oxidation states +2 ,
with +2 and +4 +3, +4, +5, +6, +7
3 Only Promethium (Pm) is All are radioactive
radioactive
4 Less reactive More reactive
5 Magnetic properties are less Magnetic properties are more
complex complex

Problem : Actinoid contraction is greater from element to element than lanthanoid contraction.
Why?

(i) This is because transition metals have strong metallic bonds as they have a large
number of unpaired electrons.
(ii) Because of their variable oxidation states and ability to provide suitable large surface
area with free valencies on which reactants are adsorbed.
(iii) This is due to poorer shielding by 5f electrons in actinoids than that by 4f electron in
the lanthanoids.
(iv)This is because half filled d-subshell (3d5 ) in Mn 2+ is more stable.
(v) This is because scandium has partially filled d orbitals in the ground state (3d14s2 )

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 Unit : 8 – d- & f- Block Elements

3 Discuss the relative stability in aqueous solutions of +2 oxidation state among the elements
: Cr, Mn, Fe and Co. How would you justify this situation?

4 Compare actinoids and lanthanoids with reference to their :

(i) electronic configurations of atoms
(ii) oxidation states of elements
(iii) general chemical reactivity of elements.

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 Unit : 8 – d- & f- Block Elements

(i) On moving from titanium to copper in general atomic mass increases where as
atomic size decreases, therefore density increases in general.
(ii) The frequent metal-metal bonding in compounds of heavy transition elements is due
to their high enthalpy of atomization.
(iii) This is due to very small energy gap between 5f , 6d and 7s orbitals in the actinoid
series.
6

(i) Due to poor shielding effect of 5f orbitals than 4f orbitals

(ii) Due to having more no. of unpaired electrons

(i) Transition elements form many interstitial compounds as they are capable of entrapping
small atoms like H, C or N in the interstitial sites in their crystal lattice.

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 Unit : 8 – d- & f- Block Elements

(i) This is due to d – d transition as the energy of excitation of d orbital electrons from
lower energy to higher energy level lies in the visible region.
(ii) The variable oxidation states of transition metals are due to the participation of ns
and (n -1)d electrons in bonding as energy difference between ns and (n -1)d
orbitals is small.
(iii) This is due to comparable energies of 5f , 6d and 7s orbitals of actinoids.
8

(i) The atomic radii of transition metals decreases with atomic number in a series as the
nuclear charge increases due to poor shielding effect of d orbitals.
(ii) This is due to its high enthalpy of atomization and low hydration enthalpy.
(iii) This is due to much large third ionisation energy of Mn as Mn 2+ is very stable on
account of stable d 5 configuration.
9 What is meant by the term lanthanoid contraction? What is it due to and what
consequences does it have on the chemistry of elements following lanthanoids in the
periodic table?
Lanthanoid contraction: The steady decrease in the atomic and ionic radii of lanthanoids
with increase in atomic number is known as lanthanoid contraction.

Cause of lanthanoid contraction: As we move along the lanthanoid series, for every
additional proton in the nucleus, the corresponding electron goes into 4 f -subshell, there is
poor shielding of one electron by another in this subshell due to the shapes of these f-
orbitals. The imperfect shielding is not able to counterbalance the effect of the increased
nuclear charge.Thus the net result is decrease in size with increase in atomic number.

Consequences:
(i) 5d series elements have nearly same radii as that of 4d-series.
(ii) The basic strength of hydroxides decreases from La(OH) 3 to Lu(OH) 3 .

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 Unit : 8 – d- & f- Block Elements

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(i) Because the high hydration enthalpy of Cu 2+ easily compensates the second
ionization enthalpy of Cu.
(ii) Because strong ligand cause spin pairing giving rise to diamagnetic octahedral
complex which are very stable and have very large crystalfield stabilization
energy. This splitting energy overcomes the ionization enthalpy.
(iii) This is due to stability of Mn 2+ as it has half filled d5 configuration.
11 (i) The metallic radii of the third (5d) series of transition elements are virtually the same
as those of the corresponding members of the second series.
(ii) There is a greater range of oxidation states among the actinoids than among the
lanthanoids
(i) This due to filling of 4f orbitals which have poor shielding effect or due to lanthanoid
contraction.
(ii) This is due to comparable energies of 5f, 6d and 7s orbital in actinoids.
12 How would you account for the following?
(i) The atomic radii of the metals of the third (5d) series of transition elements are
virtually the same as those of the corresponding members of the second (4d)
series.
(ii) The E° value for the Mn 3+
/ Mn 2+ couple is much more positive than that for Cr 3+
/
2+ 3+
Cr couple or Fe / Fe2+ couple.
(iii) The highest oxidation state of a metal is exhibited in its oxide or fluoride.
(iv) Zinc is not regarded as a transition element.
(v) Transition elements generally form coloured compounds
(i) This is due to lanthanide contraction. Or This is due to filling of 4f orbitals which
have poor shielding effect.
(ii) The E° value for the Mn3+/Mn2+ couple is much positive than Cr3+/Cr2+ couple or
Fe3+/Fe2+ couple because Mn3+ ion receiving an electron gets d-subshell half-filled
which is highly stable. While in case of Fe3+ d-sub shell is already half-filled, so it
does not receive electron easily.
(iii) This is because fluorine and oxygen are highly electronegative elements and have
small size.
(iv)Because the atoms or simple ions of zinc never have partially filled d orbitals.
(v) This is due to d-d transition. When visible (white) light falls on a compound, it
absorbs certain radiations of white light and transmit the remaining ones. The
transmitted light has the complementary colour to that of the absorbed light.

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 Unit : 8 – d- & f- Block Elements

13

(i) This is due to increase in the oxidation state of the metal ion.
(ii) The third ionisation enthalpy of manganese (Z = 25) is exceptionally high because
Mn2+ ion has 3d5 configuration which is highly stable since it is half-filled.
(iii) Cr2+ stronger reducing agent than Fe2+ as its configuration changes from d4 to d3, a
more stable half filled t2g configuration.
14 Explain the following observations:
(i) La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.
(ii) Among the divalent cations in the first series of transition elements, manganese
exhibits the maximum paramagnetism.
+
(iii) Cu ion is not known in aqueous solutions.
(i) La3+ and Lu3+ ions do not show any colour in solution because they do not contain any
unpaired electrons.
(ii) Among the divalent cations in the first series of transition elements, manganese exhibits
the maximum paramagnetism because manganese (Mn2+) ion has maximum number of 5
unpaired electrons.

15 Describe the preparation of

(i) Potassium dichromate from sodium chromate, and
(ii) KMnO4 from K2MnO4

16 How would you account for the following:

(i) Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an
oxidising agent.
(ii) In a transition series of metals, the metal which exhibits the greatest number of
oxidation occurs in the middle of the series.
(iii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+ ions of the 3d series of
elements, the 4dand the 5d series metals generally do not form stable cationic
species.
(iv)The chemistry of actinoids is not as smooth as that of lanthanoids

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 Unit : 8 – d- & f- Block Elements

(iv) This is because due to lanthanoid contraction the expected increase in size does not
occur
(v) The chemistry of actinoids is not as smooth as lanthanoid because they are
radioactive and show greater number of oxidation states due comparable energies
of 5f, 6d and 7s orbitals.
17 How would you account for the following:
(i) Metal-metal bonding is more extensive in the 4d(2nd) and 5d(3rd) series of transition
elements than the 3d series.
(ii) Mn (III) undergoes disproportionation reaction easily.
(iii) Co (II) is easily oxidised in the presence of strong ligands
(iv)With same (d4) configuration Cr (II) is reducing whereas Mn (III) is oxidising.
(i) In general in the same group of d block elements, the 4d and 5d transition element
has larger size than that of 3d elements. Thus, the valence electrons are less
lightly held and hence can form metal-metal bond more frequently.
(ii) Mn is less stable and changes to Mn2+ which is more stable due to half filled d-
3+

orbital configuration. That is why, Mn3+ undergoes disproportionation reaction.

(iii) Co (III) has electric configuration 3d, 4s, i.e., it has three unpaired electron. In the
presence of strong ligands, two unpaired electrons in 3d subshell pair up and
third unpaired electron shift to higher energy subshell from where it can be easily
lost and hence oxidised to Co(III).
(iv)Cr is reducing as its configuration changes from d4 to d3, a more stable half filled
2+

t2g configuration while Mn3+ is oxidising as Mn3+ to Mn2+results a more stable half
filled d5 configuration.
18

19 (i) Lanthanoids form primarily +3 ions, while the actinoids usually have higher oxidation
states in their compounds, +4 or even +6 being typical.
(ii) Among lanthanoids, Ln (III) compounds are predominant. However, occasionally in
solutions or in solid compounds, +2 and +4 ions are also obtained .
(iii) There is a general increase in density from titanium (Z = 22) to copper (Z = 29)
(iv) Actinoids exhibit a much larger number of oxidation states than the lanthanoids.
.
(i) This is due to very small energy gaps between 5f, 6d and 7s subshells in actinoids
(ii) Lanthanoid metals show +2 and +4 oxidation states to attain extra stable f 0 and f 7
configurations.
(iii) The decrease in metallic radius coupled with increase in atomic mass results in a
general increase in density from titanium to copper in the first series of transition
elements.
(iv) This is due to very small energy gaps between 5f, 6d and 7s subshells in
actinoids.
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 Unit : 8 – d- & f- Block Elements

20

21

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