NOTES (2023-2024)

Subject: CHEMISTRY
Name of the lesson: d and f Block Elements
Grade: XII
INTRODUCTION
The d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitals
are progressively filled in each of the periods.
The f-block consists of elements in which 4 f and 5 f orbitals are progressively filled.
The names transition metals and inner transition metals are often used to refer to the elements of
d-and f-blocks respectively.

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ELECTRONIC CONFIGURATIONS OF THE d-BLOCK ELEMENTS
In general the electronic configuration of outer orbitals of these elements
is (n-1)d1–10ns1–2.

PRACTICE QUESTIONS - 1
1. On what ground can you say that scandium (Z = 21) is a transition element but
zinc (Z = 30), Cadmium (Cd = 48) and Mercury (Z = 80) are not?
Ans: On the basis of incompletely filled 3d-orbitals in case of scandium atom in its ground state
(3d1), it is regarded as a transition element. On the other hand, zinc, Cadmium and Mercury have

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 completely filled d-orbitals (3d10, 4d10, 5d10) in its ground state as well as in its oxidised state, hence
it is not regarded as a transition element.

2. Silver atom has completely filled d orbitals (4d10) in its ground state. How can
you say that it is a transition element?
Ans: Ag has a completely filled 4d orbital (4d10 5s1) in its ground state. Now, silver displays two
oxidation states (+1 and +2). In the +1 oxidation state, an electron is removed from the s-orboital.
However, in the +2 oxidation state, an electron is removed from the d-orbital. Thus, the d-orbital
now becomes incomplete (4d9). Hence, it is a transition element.
PHYSICAL PROPERTIES:
Nearly all the transition elements display typical metallic properties such as high tensile strength,
ductility, malleability, high thermal and electrical conductivity and metallic lustre.
With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic structures at
normal temperatures.
Transition metals have high melting point and boiling point. This is due to the strong metallic
bonding.
PRACTICE QUESTIONS - 2
1. The transition metals (with the exception of Zn, Cd and Hg) are very hard and
have low volatility.
OR
• The transition metals (with the exception of Zn, Cd and Hg) have high melting
and boiling points. Why?
Ans: It is due to the involvement of greater number of electrons from (n-1)d in addition to the ns
electrons in the interatomic metallic bonding.
2. The transition metals such as Zn, Cd and Hg are not hard and have high volatility.
Why?
OR
• The transition metals such as Zn, Cd and Hg have low melting and boiling
points. Why?
Ans: It is due to the absence of interatomic metallic bonding because of completely filled orbitals.
ENTHALPY OF ATOMIZATION:
Transition elements have very high enthalpy of atomization due to the strong metallic bonds they
form.
The exceptionally low value in the middle of each series is due to the stability of their electronic
configurations.

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PRACTICE QUESTIONS - 3
1. Why do the transition elements exhibit higher enthalpies of atomisation?
Ans: Because of large number of unpaired electrons in their atoms they have stronger interatomic
interaction and hence stronger bonding between atoms resulting in higher enthalpies of
atomisation.
2. 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. Why?
The extent of metallic bonding an element undergoes decides the enthalpy of atomization. In all
transition metals (except Zn, electronic configuration: 3d10 4s2), there are some unpaired electrons
that account for their stronger metallic bonding. Due to the absence of these unpaired electrons,
the inter-atomic electronic bonding is the weakest in Zn and as a result, it has the least enthalpy of
atomization.
ATOMIC AND IONIC SIZES
The variation of atomic size within a series is quite small.

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PRACTICE QUESTIONS - 4
1. The radii of the third (5d) series are virtually the same as those of the
corresponding members of the second series (4d). Why?
OR
• The atomic radii of Zr and Hf are nearly same. Why?
This is because of lanthanoid contraction. Lanthanoid contraction is caused due to imperfect
shielding of f electrons. The net result of the lanthanoid contraction is that the second and the third
d series exhibit similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar properties.
IONIZATION ENTHALPY:
There is an increase in ionization enthalpy along each series of the transition elements from left to
right due to an increase in nuclear charge.
The successive enthalpies of these elements do not increase as steeply as in the case of non-
transition elements. The trend in change of first ionization enthalpy in a series is irregular.
Ionization enthalpy will decrease when the resulting ion formed is either d5 or d10 as in the case of
formation of Fe3+ ion.
PRACTICE QUESTIONS - 5
1. Why is the third ionization enthalpy of Zinc very high?
Ans:
Zn=1s2 2s2 2p6 3s2 3p6 4s2 3d10
Zn+=1s2 2s2 2p6 3s2 3p6 4s1 3d10
Zn2+=1s2 2s2 2p6 3s2 3p6 3d10
So it is difficult to remove an electron from Zn2+ compared to Zn. Because Zn2+ has stable fully
filled d orbital.
That's why Zn has third ionization energy greater than first ionization energy.
2. How would you account for the irregular variation of ionisation enthalpies (first
and second) in the first series of the transition elements?

Ans: Ionization enthalpies are found to increase in the given series due to a continuous filling of the
inner−d orbitals. The irregular variation of ionization enthalpies can be attributed to the extra stability of
configuration such as d0,d5,d10. Since these states are exceptionally stable, their ionization enthalpy are very
high.

OXIDATION STATES:
One of the notable features of a transition elements is the great variety of oxidation states these
may show in their compounds. The variability of oxidation states, arises out of incomplete filling of
d orbitals in such a way that their oxidation states differ from each other by unity.

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PRACTICE QUESTIONS - 6
1. Name a transition element which does not exhibit variable oxidation states.

Ans: Scandium (Z=21) does not exhibit variable oxidation states and yet it is regarded as a transition
element because scandium has partially filled d-orbitals in the ground state (3d14s2).

2. Which of the 3d series of the transition metals exhibits the largest number of
oxidation states and why?
Ans: Mn (Z = 25) = 3d5 4s2 Mn has the maximum number of unpaired electrons present in the d-
subshell (5 electrons). Hence, Mn exhibits the largest number of oxidation states, ranging from +2
to +7.
OXIDATION TRENDS IN THE M2+/M STANDARD ELECTRODE POTENTIALS:
The general trend towards less negative Eo values across the series is related to the general
increase in the sum of the first and second ionisation enthalpies.
The positive value of Cu is due to the high energy to transform Cu(s) to Cu2+ is not balanced by its
hydration enthalpy.
PRACTICE QUESTIONS - 7
1. The value of Eo for Mn, Ni and Zn are more negative than expected from the
trend.
Ans: Negative reduction potential refers to the stability of a species in its oxidized form, more
negative reduction potential signifies less tendency to get reduced and thus more stable will be the
oxidized species.

Electronic configuration of Mn=[Ar]3d54s2

Electronic configuration of Mn2+=[Ar]3d54s0

Electronic configuration of Zn=[Ar]3d104s2

Electronic configuration of Zn2+=[Ar]3d104s0

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Mn and Zn readily lose two electrons to attain half-filled and fully filled stable configurations
respectively, thus they readily get oxidized and have more negative E0 values.

Electronic configuration of Ni=[Ar]3d84s2

Electronic configuration Ni2+=[Ar]3d8

Ni2+has high hydration enthalpy due to which it is quite stable. That’s why Ni has a tendency of
getting oxidized to Ni2+, hence has more negative E0 value than expected.

2. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Ans: Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-
filled t2g level.
On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which
has extra stability. That is why Cr2+ is reducing and Mn3+ is oxidising when both
have d4 configuration.
3. The Eo (M2+/M) value for copper is positive (+0.34V). What is possible reason for
this?

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 4. Why is the Eo value for the Mn3+/Mn2+ couple much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+? Explain

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

Ans: Cr2+ is a better reducing agent. As it attains a d3 configuration on loosing an electron while
Fe2+ attains d5 configuration. In an aqueous medium d3 (half filled t2g orbital) is more stable than
d5.
6. Explain why Cu+ ion is not stable in aqueous solutions?

Ans: In aqueous medium, Cu+2 is more stable than Cu+. This is because although energy is required to
remove one electron from Cu+ to Cu2+, high hydration energy of Cu2+ compensates for it.
Therefore, Cu+ ion in an aqueous solution is unstable.

7. Why is the highest oxidation state of a metal exhibited in its oxide or

fluoride only?

Ans: The highest oxidation state of a metal exhibited in its oxide or fluoride only since fluorine and oxygen
are the most electronegative elements. The highest oxidation state shown by any transition element is +8.

MAGNETIC PROPERTIES:
Most of the transition metal ions are paramagnetic. This is because of the presence of unpaired
electrons. The magnetic moment is determined by the number of unpaired electrons and is
calculated by using the ‘spin-only’ formula.

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 where n is the number of unpaired electrons and µ is the magnetic moment in units of Bohr
magneton (BM).
PRACTICE QUESTIONS - 8
1. Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.

Ans: he atomic number is 25. The metal is manganese with valence shell ,electronic configuration 3d54s2.
The divalent ion Mn2+ has valence shell electronic configuration 3d54s0. It contains five unpaired electrons.
n=5
It's spin only magnetic moment is

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

FORMATION OF COLOURED IONS

Transition metal ions are mostly coloured. 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 in the visible region. The
colour observed corresponds to the complementary colour of the light absorbed.

The ions with d0 and d10 configuration will not exhibit colour because transition of
electrons among d-orbitals is not possible.

PRACTICE QUESTIONS – 9
1. Why is that Zn2+ and Sc3+ are colourless in nature?

Ans:

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 2. Predict which of the following will be coloured in aqueous solution? Ti 3+, V3+ ,
Cu+ , Sc3+, Mn2+, Fe3+ and Co2+. Give reasons for each.

Ans:

FORMATION OF COMPLEX COMPOUNDS:

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.

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. These metals and ions are also
good adsorbents for reactants.

FORMATION OF 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. Transition metals from interstitial compounds because the void spaces in their
crystals are large enough to accommodate small molecules. The properties of metals are altered
by formation of interstitial compounds.

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FORMATION OF ALLOYS
Because of similar radii and other characteristics of transition metals, alloys are readily formed by
these metals. The alloys so formed are hard and have often high melting points and also have great
industrial importance.

SOME IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

1. 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.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr2O7 . 2 H2O can be crystallised.
2 Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
Potassium dichromate is prepared by treating the solution of sodium dichromate with
potassium chloride.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
Structure

Properties:
(i) The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution. The oxidation state of chromium in chromate and dichromate is
the same.
2 CrO42– + 2 H+ → Cr2O72– + H2O
Cr2O7 2– + 2 OH- → 2 CrO42– + H2O
(ii) K2Cr2O7 is a very good oxidising agent in acidic medium.

Cr2O72– + 14 H+ + 6 e– → 2 Cr3+ + 7 H2O

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 Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur,
tin(II) to tin(IV) and iron(II) salts to iron(III). The half-reactions are noted below:
6 I– → 3 I2 + 6 e–
3 Sn2+ → 3 Sn4+ + 6 e–
6 Fe2+ → 6 Fe3+ + 6 e–
3 H2S → 6 H+ + 3 S + 6 e–
Eg: Cr2O72– + 14 H+ + 6 Fe2+ → 2 Cr3+ + 6 Fe3+ + 7 H2O
(Refer Note book for more examples)

2. POTASSIUM PERMANGANATE. KMNO4

Preparation:
Potassium permanganate is prepared by fusion of MnO2 (Pyrolusite) with an alkali
metal hydroxide and an oxidising agent like KNO3. This produces the dark green K2MnO4 (
Potassium Manganate) which disproportionates in a neutral or acidic solution to give permanganate.
2 MnO2 + 4 KOH + O2 → 2 K2MnO4 + 2 H2O
3 MnO42– + 4 H+ → 2 MnO4– + MnO2 + 2 H2O
Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the
electrolytic oxidation of manganate (Vl).
In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.
2 Mn2+ + 5 S2O82– + 8 H2O → 2 MnO4– + 10 SO42– + 16 H+
Potassium permanganate forms dark purple (almost black) crystals which
are isostructural with those of KClO4.
Structure:

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Properties
KMnO4 is a very good oixidising agent in acidic and neutral or alkaline medium.
A few important oxidising reactions of KMnO4 are given below:
In acid solutions:
(a) Iodine is liberated from potassium iodide :
10 I– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5 Fe2+ + MnO4– + 8 H+ → Mn2+ + 4 H2O + 5 Fe3+
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5 C2O42– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 10 CO2
(d) Hydrogen sulphide is oxidised, sulphur being precipitated:
5 S2– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 5 S
(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:
5 SO32– + 2 MnO4– + 6 H+ → 2 Mn2+ + 3 H2O + 5 SO42–
(f) Nitrite is oxidised to nitrate:
5 NO2– + 2 MnO4– + 6 H+ → 2 Mn2+ + 5 NO3– + 3 H2O
In neutral or faintly alkaline solutions:
(a) A notable reaction is the oxidation of iodide to iodate:
2 MnO4– + H2O + I– → 2 MnO2 + 2 OH– + IO3–
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8 MnO4– + 3 S2O32– + H2O → 8 MnO2 + 6 SO42– + 2 OH–
(c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate
or zinc oxide catalyses the oxidation:
2 MnO4– + 3 Mn2+ + 2 H2O → 5 MnO2 + 4 H+

(Refer Notebook for more examples)

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THE INNER TRANSITION ELEMENTS ( f-BLOCK)
LANTHANOIDS
The outermost electron is filled in the f-orbital of the antepenultimate shell. The general electronic
configuration of lanthanides is [Xe] 4f1-14 5d0,1 6s2.

ATOMIC AND IONIC SIZES

The overall decrease in atomic and ionic radii from lanthanum to lutetium is called lanthanoid
contraction. This phenomenon is caused due to the imperfect shielding 4 f electrons.
Consequences of Lanthanide contraction
The consequences of lanthanide contraction
(i) The radii of the members of the third transition series becomes similar to corresponding
members of the second series. The almost identical radii of Zr (160 pm) and Hf (159 pm),
(ii) The occurrence of Lanthanoids together in nature and for the difficulty faced in their
separation.
OXIDATION STATES:
The most common oxidation state is +3 oxidation state. Occasionally +2 and +4 ions in solution or
in solid compounds are also obtained. The stability of +2 and +4 oxidation states can be attributed
to the stable electronic configurations of these ions ( f0, f7 or f14).
Eu2+ is formed by losing the two s electrons and its f7 configuration accounts for the formation of
this ion. However, Eu2+ is a strong reducing agent changing to the common +3 state. Similarly Yb2+
which has f14 configuration is a reductant.
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Q. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation
state.
Ans: Cerium (Z = 58)
General properties:

MISCHMETALL
It is an alloy of Lanthanoids 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.
ACTINOIDS
The general electronic configuration of actinoides is [Rn] 5f1-14 6d0,1 7s2.
The elements after Uranium are called trans-uranic elements and are artificial and radioactive.

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ATOMIC AND IONIC SIZES:
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 (like lanthanoid contraction). The contraction
is, however, greater from element to element in this series resulting from poor shielding by 5f
electrons.
OXIDATION STATES:
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. The actinoids resemble the
lanthanoids in having more compounds in +3 state than in the +4 state.

PRACTICE QUESTIONS - 10
1. Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
Ans: The 5f orbitals in Actinoids have a very poorer shielding effect than 4f orbitals in
lanthanoids. 2. Thus, the effective nuclear charge experienced by electron in valence shells in case
of actinoids is much more than that experienced by lanthanoids.
2. Why do actinoids show more variety for oxidation state than lanthanoids.
Ans: Actinides exhibit larger oxidation states than lanthanides, because of the very small energy gap
between 5f, 6d and 7s subshells. Thus, the outermost electrons get easily excited to the higher energy
levels, giving variable oxidation states.
TEXTBOOK EXERCISE

8.1 8.16
8.2 8.17
8.5 8.18
8.6 8.21
8.7 8.22
8.8 8.23
8.11 8.24
8.12 8.25
8.14 8.26
8.15 8.27

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