D and F BLOCK ELEMENTS

CLASS-12

The d-block of the Periodic Table contains the elements of the groups 3-12 in
which the d·orbitals are progressively filled. There are mainly three series of
the elements, 3d-series (Sc to Zn) 4d-series (Y to Cd) and 5d-series (La to Hg
omitting Ce to Lu). The fourth 6d-series which begins with Ac is still
incomplete.

Transition Elements
Elements having partially filled d-orbitals in ground state or in excited state,
are known as transition elements. They have been placed in the centre of the
Periodic Table between s-block and p-block elements.

Iron is the most abundant and widely used transition metal.

General Electronic Configuration of Transition Elements

Transition elements have the electronic configuration (n – 1)d1 – 10 nso – 2, Zn,
Cd, Hg, the end members of first three series have general electronic
configuration (n – 1)d10ns2. These elements do not show properties of
transition elements to any extent and are called non-typical transition
elements.
Electronic Configuration of Transition Elements

General Physical Properties of Transition Elements

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(i) Atomic and ionic size Ions of the same charge in a given series exhibit
regular decrease in radius with increasing atomic number, because the new
electron enters in a d – orbital and nuclear charge increases by unity.
In last of the series, a small increase in size is observed due to electron-
electron repulsion.

(Atomic and ionic radii increase from 3d-series to 4d-series but the radii of the
third (Sd) series elements are virtually the same as those of the corresponding
member of the second series. It can be explained on the basis of lanthanoid
contraction [poor shielding of 4f ].

Due to lanthanide contraction Zr and Hf Have almost similar radii.

(ii) Ionisation enthalpies In a series as we move from left to right, ionization

enthalpy increases due to increase in nuclear charge but not in regular trend.
The irregular trend in the first ionisation enthalpy of the 3d metals, though of
little chemical significance, can be accounted by considering that the removal
of one electron alters the relative energies of 4s and 3d-orbitals.

(iii) Oxidation states Transition metals show variable oxidation state due to
two incomplete outermost shells. Only stable oxidation states of the first row
transition metals are
Sc(+3) , Ti(+4). V(+5), Cr(+3, +6), Mn(+2, +7), Fe(+2. +3). Co(+2, +3). Ni(+2),
Cu(+2), Zn(+2).

The transition elements in their lower oxidation states (+2 and +3) usually
forms ionic compounds. In higher oxidation state compounds are normally
covalent.

Only Os and Ru show +8 oxidation states in fluorides and oxides. Ni and Fe in

Ni(CO)4 and Fe(CO)5 show zero oxidation state.

(iv) Enthalpy of atomisation Transition elements exhibit higher enthalpies of

atomization. Because of the presence of a large number of unpaired electrons
in their atoms, they have stronger interatomic interactions and hence, stronger
bond.

(v) Trends in the M2+ / M standard electrode potentials

EoM2+ / M is governed by three factors. Enthalpy of sublimation, enthalpy of
ionisation and enthalpy of hydration.

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The irregular trend in 3d series is due to irregular variation in ionisation

enthalpy and heat of sublimation.

Except copper 3d – elements are good reducing agents.

[If sum of the first and second ionisation enthalpies is greater than hydration
enthalpy standard potential (EoM2+ / M) will be positive and reactivity will be
lower and vice-versa.]

(vi) Melting and boiling point Due to strong metallic bond, they have high m.p.
and b.p. The m.p. of these elements becomes maximum and then decreases
with the increase in atomic number.
Manganese and technetium show abnormal values in the trend. Tungsten has
the highest m.p. (3410oC).
Mercury is liquid at room temperature (m.p. – 38.9°C) due to absence of
unpaired electrons, and weak metallic bonding.

(vii) Density d-block elements have high density because of their small atomic
size and strong metallic bonding.

Osmium has slightly lower density (22.52 g cm-3) as compared to iridium (22.61
g cm-2). Thus, iridium has the highest density among transition metals.

(viii) Atomic volume Atomic volume decreases along the period due to
decrease in atomic size.

(ix) Reactivity d-block elements are less reactive due to high ionisation
energies. Some are almost inert and known as noble metals, e.g., Au; Pt, Os, Ir,
etc

(xii) Complex formation They are well known to form a large number of
complex compounds mainly due to
(a) small atomic size and high nuclear charge

(b) presence of partly filled or vacant d-orbitals, e.g.,K4[Fe(CN)6]

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(xiii) Coloured ions Colour exhibited by transition metal ions is due to the
presence of unpaired electrons in d-orbitals and is due to the d-d transitions of
electrons, when invisible light is incident on the ion.
Colour of a complex depends on the metal, its oxidation state and its ligands,
e.g., [Cu(H2O)4]2+ is pale blue while [Cu(NH3)4]2+ is dark blue. CuSO4· 5H2O is
blue in colour and anhydrous CuSO4 is colourless.
Charge transfer also give intense colour e.g., MnO–4 ion does not contain any
unpaired d-electron. Its purple colour is due to charge transfer from O to MD,
thus O-2 change to O– and Mn(VII) to Mn(Vl). Charge transfer is possible only
when the energy levels on the two different atoms involved are fairly close.
(xiv)

Magnetic properties
(a) Paramagnetic nature is due to the presence of unpaired electrons in d-
orbitals. Paramagnetic character increases with increase in the number of
unpaired electrons and highest for Mn(II) [among 3d-series].
(b) Diamagnetic substances are repelled by applied magnetic field and have no
unpaired electron.

(c) In ferromagnetism, permanent magnetic character is acquired by substance

e.g., Fe.

Magnetic moment is given by

μ = √n (n + 2) BM,
Where, n = number of unpaired electrons and BM = Bohr magneton (unit of
magnetic moment).

(xv) Catalytic properties The transition metals anti their compounds behave
like catalyst due to
(a) the presence of partly filled d-orbitals resulting in variable oxidation states.

(b) formation of intermediate complex with reactants by lowering the energy

of activation.

(c) their rough surface area which provides active sites for adsorption of
reactant molecules.

Iron in the preparation of NH3 (Haber’s process), finely divided nickel for
hydrogenation, Pt in the preparation of nitric acid (Ostwald’s process)

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Some important catalysts having transition metals are

1. Ziegler Natta catalyst : TiCI4 + (C2H5)3 AI

2. Lindlar’s catalyst : Pd / BaSO4
3. Wilkinson’s catalyst : [Ph3P3RhCI
4. Adam’s catalyst : Pt / PtO

5. Brown’s catalyst or P-2 catalyst: Nickel boride

(xiv) Formation of alloys d-block elements have a strong tendency to form

alloys, because their atomic sizes are very similar and in the crystal lattice one
metal can be readily replaced by another. Alloys so formed have high m.p.. The
metals Mo, W, Cr, Ni, and V are used for the production of stainless steel.
Amalgam is an alloy formed by mercury with other metals, Iron and platinum
do not form any alloy with mercury.

List of Alloys

(xv) Interstitial compounds The vacant space present in a crystal lattice is

known as interstitial site or void. The non-metal atoms (e.g., H, N, C, etc.) due
to their small size when occupy such place, the resulting compound is known
as interstitial compound. Such compounds are hard and rigid, e.g., cast iron
and steel.
(xvi) Non-stoichiometric compounds The compounds not navm the elements
in the exact ratio as in the ideal crystal are known non-stoichiometric

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compounds e.g., in Fe0.94O1 the Fe : O is approx 0.94 : 1 and not exactly 1 : 1. It

is due to the variability of Oxidation state in the transition metal. These
elements form such compound by trapping H, B, C and N etc.
(xvii) Spinel These are the mixed oxides in which oxygen atoms constitute a fcc
lattice e.g., ZnFe2O4 It is a normal spinel in which the trivalent ions occupy the
octahedral holes and divalent ions occupy the tetrahedral holes.
In inverse spinel, the trivalent ion occupy the tetrahedral holes and divalent
ion occupy the octahedral holes. e.g., FeFe2O4 or Fe3O4.
Some important reagents having transition metals

1. Baeyer’s reagent Dilute alkaline KMnO4 used to test the presence of

unsaturation.
2. Tollen’s reagent Ammoniacal solution of AgNO3, i.e., [Ag(NH3)2]OH. used to
test the aldehyde group.
3. Nessler’s reagent Alkaline solution of K2HgI43 (g) and NH: .
4. Benedict’s solution CuSO4 solution + sodium citrate + Na2CO3, used to test
the aldehyde group.
5.Lucas reagent HCl (cone.) + anhydrous ZnCl2, used to distinguish between 1°,
2° and 3° alcohols.
Applications of transition elements
1. A mixture of TiO2 and BaSO4 is called titanox and a mixture of ZnS + BaSO4 is
called lithopone.
2. TiCI2 and TiO2 are used in smoke screens. TiO2 is also used as white pigment
of paints.
3. Tantalum is used in surgical venables and analytical weights.

4. Chromium is used in stainless steel and chrome plating.

5. Mo is used in X-rays tubes. Pt is used in resistance thermometers.

6. Cd is used for making joints in jewellery.

7. Ce is used as a scavenger of oxygen and sulphur in many metals-

8. Alkaline solution of K2HgI4 is called Nessler’s reagent and is used to test the
presence of ammonium ion (NH+4).
1. Potassium Dichromate (K2 Cr2 O7)
Ore Ferrochrome or chromite (FeO· Cr2O3) or (FeCr2O4)
Preparation

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Sodium dichromate is more soluble than potassium dichromate.

Chromates and dichromates are interconvertible in aqueous solution

depending upon pH of the solutions.

Properties Sodium and potassium dichromates are strong oxidising agents,

thus, acidified K2Cr27 will oxidise iodides to iodine, sulphides to sulphur, tin (ll)
to tin (IV) and iron (ll) salts to iron (III).

Uses
1. K2Cr27 is used as oxidising agent in volumetric analysis.
2. It is used in mordant dyes, leather industry, photography (for hardening of
film).

3. It is used in chromyl chloride test.

4. It is used in cleaning glassware.

2. Potassium Permanganate (KMnO 4)

Ore Pyrolusite (MnO2)
Preparation
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Commercial preparation

Properties KMnO4 acts as strong oxidising agent.

1. In the presence of dilute H2SO4, KMnO4 is reduced to manganous salt.

Acidic KMnO4 solution oxidises oxalates to CO2, iron(II) to iron (lll), nitrites to
nitrates and iodides to iodine. The half-reactions of reductants are

To acidify KMnO4, only H2SO4 is used and not HCI or HNO3 because HCI reacts
with KMnO4 and produce Cl2 while HNO3, itself acts as oxidising agent.
2. In alkaline medium, KMnO4 is reduced to insoluble MnO2.

Alkaline or neutral KMnO4 solution oxidises I– to IO–3, S2O2-3 to SO2-4, Mn2+ to

MnO2, etc.
Aqueous KMnO4, reacts with NH$ to liberate N2 gas.
2KMnO4 + 2NH3 → 2KOH + 2MnO2 + N2 + 2H2O
Uses
KMnO4 is used
(i) in laboratory preparation of CI2.
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(ii) as an oxidising agent and disinfectant.

(iii) in making Baeyer’s reagent.

Structures

3. Copper Sulphate (CUSO4 ·5H2O)

It is also known as blue vitriol.

Method of preparation It is obtained by the action of dil H2SO4 on copper

scrap in the presence of air.

Properties
1. On heating it turns white due to loss of water of crystallisation.

At 1000 K, CuSO4 decomposes into CuO and So3

2. It gives blue solution with NH4OH and white ppt of Cu2I2 with KI.
Uses It 1S used in electroplating, as mordant in dyeing, in making bordeaux
mixture [(Ca(OH) 2 + CuSO4)], etc.
4. Silver Nitrate (AgNO3)
It is also called Lunar caustic.

Method of preparation It is prepared by heating silver with dilute nitric acid

Properties
1. It is colourless, crystalline compound which blackens when comes in contact
of organic substances (skin, cloth, etc.)

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2. With potassium dichromate, it gives red ppt of Ag2CrO4.

3. On strong heating, it decomposes to metallic silver.

4. Ammoniacal solution of silver nitrate is known as Tollen’s reagent.

Uses It is used as laboratory reagent, in silvering of mirror, in the preparation

of inks and hair dyes, etc.
Inner-Transition Elements
The elements in which the filling of atomic orbitals by electrons take place in {-
subshells, two levels inside the outer subshell, are known as inner-transition
elements. They are also known as f-block elements

Classification of f-block Elements

They have been classified into two series.

(a) 4f-series (first inner-transition series) The last electron enters in 4f-orbital.
The elements belonging to this series are also known as lanthanoids.
(b) 5f-series (second inner-transition series) The last electron enters in 5f-
orbital. The elements belonging to this series are also known as actinides.
Lanthanides
The fifteen elements from lanthanum (at. no. 57) to lutetium (at. no. 71) are
known as lanthanides or rare earths. Their properties are as follows :

1. Electronic configuration
The general electronic configuration of these elements is [Xe]4f0 – 14 5d0-1 6s2.
The lanthanum, electronic configuration [Xe]4f0 5d1 6s2 and lutetium,
electronic configuration [Xe]4f14 5d1 6s2, have no partially filled 4f-orbital in
their ground state, are considered as lanthanides due to their properties close
to these elements.
2. Oxidation state
The most common and most stable oxidation state of lanthanides is +3 but
some elements also exhibit +2 and +4 oxidation states in which they leave
behind stable ions, e.g.,

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An aqueous solution of Ce4+ is a good oxidising agent. The Eu2+ and Yb2+ can
exist in aqueous solution and are good reducing agents. But there are
exceptions also e.g.,

3. Magnetic properties
Magnetic properties have spin and orbit contributions. Hence, magnetic
moments are given by the formula

μ = √4S(S + 1)+ L (L + 1)
Where, L = orbital quantum number, S = spin quantum number

All lanthanide ions with the exception of La3+, Lu3+ and Ce4+, are paramagnetic
in nature.
4. Lanthanoid contraction
Steady decrease in the atomic and ionic (Ln3+) radii as the atomic Dumber of
the lanthanide elements increases is called lanthanide contraction. This is
because the additional electron goes to 4f-subshell and 4f-orbitals being large
and diffuse, have poor shielding effect. The effective nuclear charge increases
which causes the contraction in the size of electron charge cloud. This
contraction in size is quite regular and is known as lanthanoid contraction.
The f- f transitions are possible due to absorption of light from the visible
region.

Consequences of lanthanoid contraction

(i) Covalent character of cations increase.
(ii) The electronegativity of trivalent ions increases slightly.
(iii) There is decrease in basic strength of oxides and hydroxides from La to Lu.
(iv) There is small increase in standard electrode potential values.
(v) Sizes of Zr and Hf; Nb and Ta are similar, so they are called chemical twins.

5. Colour
The species containing unpaired electrons are coloured and so on in the case
of lanthanide ions.

6. Melting and boiling pOints

Lanthanides have high melting and boiling points but there is no regular trend.

7. Density
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Lanthanides have densities varying . from 6.67 to 9.7 g cm-3, but there IS no
regular trend for these values.
8. Electronegativity
For lanthanides the electronegativity values are almost same as that of $-block
elements. Lanthanides form ionic compounds.

9. Ionisation energies
The ionisation energy values of lanthanoids are not very high due to their large
size and comparable with those of alkaline earth metals.

10. Complex compound

Due to their large ionic SIze, they have little tendency to form complexes.

11. Reactivity
Due to their low values of ionisation energies, the lanthanides are very
reactive.

12. Alloys
They form alloy especially with iron e.g., misch metal rare earths 94 _ 95%, iron
~ 5% and S, C, Ca and AI in traces. Mg mixed with 3% misch metal is used for
making jet engine parts.

Actinides
The fifteen elements from actinium (at. no. 89) to lawrencium (at. no. 103) are
known as actinides and constitute the 5f series. From neptunium to onwards
the elements are man-made (artificially prepared) and also known as
transuranic elements.

1. Electronic configuration
The last electron in such elements enters in the 5f atomic orbital.

Their general electronic configuration is

[Rn]5 f0 – 14 6d0 – 1 7s2

There is not much difference between the energies of 5f and 6d, so it is
difficult to predict whether the electron has entered in 5f or 6d.

2. Oxidation state
The common oxidation state is +3 but other oxidation states are also exhibited
by actinides upto the maximum being +7.

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3. Magnetic properties
The magnetic moments of actinide ions are smaller than theoretical values. It is
hard to interpret due to large spin orbit coupling.

4. Actinide contraction
It is similar to lanthanide contraction due to poor shielding or 5f – electrons

5. Melting and boiling points

They have high values for melting and boiling points but there is no regular
trend.

6. Density
The value of density vary from 7.0 gcm-3 to 20 gcm-3. Again there is no regular
trend in density.
7. Reducing character
They are strong reducing agents as they have high E° values approximately 2.0
V.

8. Reactivity
Actinide are very reactive in nature and combine with oxygen and halogens like
lanthanoids.

9. Coloured ions
Actinide ions are coloured due to the presence of unpaired electrons and f-f
transitions.

10. Complex formation

They have higher tendency to form complex compounds.

PREVIOUS YEAR QUESTIONS (CBSE)

Why is zinc not regarded as a transition element?
Answer:
It is because neither Zn nor Zn+2

ions have incompletely filled d-orbitals.

Question 2:
Copper atom has completely filled d-orbitals in its ground state but it is a
transition element. Why?

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Answer:
It is because Cu+2

has 3d9, incompletely filled d-orbitals, therefore, it is a transition metal.

Question 3:
Zn+2 salts are white while Cu+2 salts are coloured. Why?
Answer:
Zn+2 salts are white because it does not have unpaired electron, whereas
Cu+2 salts are coloured because it has unpaired electron and undergoes d-d
transition by absorbing light from visible region and radiate blue colour.

Short Answer Type Questions [I] [2 Marks]

Question 4:
Why do transition elements show variable oxidation states? How is the
variability in oxidation states of d-block different from that of the p-block
elements?
Answer:
It is due to similar energy of (n – 1 )d and ns orbitals, electrons from both can
be lost. In p-block, lower oxidation state is more stable due to inert pair effect,
whereas in ehblock elements higher oxidation states are more stable. In d-
block, oxidation states differ by one, whereas in p-block, it differs by two.

Question 5:
(i) Why do actinoids show wide range of oxidation states?
(ii) Why is actinoid contraction greater than lanthanoid contraction?
Answer:
(i) It is because 5f, 6d and 7s have comparable energy.
(ii) 5f orbitals have poor shielding effect than 4f orbitals, therefore, effective
nuclear charge is more in actinoids than lanthanoids.

Question 6:
What are the transition elements? Write two characteristics of the transition
elements.
Answer:
Those elements which either themselves or their ions have incompletely filled
Characteristics:

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(i) They show variable oxidation state.

(ii) They form coloured ions.

Question 7:
Write one similarity and one difference between the chemistry of lanthanoids
and that of actinoids.
Answer:
Similarity:
Lanthanoids show lanthanoid contraction like actinoids contraction.
Dissimilarity:
Lanthanoids show mostly +3 oxidation state. Few show +2 and +4, whereas
Actinoids show +3, +4, +5, +6 and +7 oxidation states.

Question 8:
Why dp transition elements show variable oxidation states? In 3d series (Sc to
Zn), which element shows the maximum number of oxidation states and why?
Answer:
Transition elements show variable oxidation states because electrons from
both s and d orbitals take part in bond formation. In 3d series, ‘Mn’ shows
maximum number of oxidation states because it has maximum number of
electrons in s as well as in d orbitals which can take part in bond formation.

Short Answer Type Questions [II] [3 Marks]

Question 9:
(i) E° value for the Mn+3/Mn+2 couple is positive (+1.5 V) whereas that of
Cr+3/Cr+2 is negative (-0.4 V). Why? ‘
(ii) Transition metals form coloured compounds. Why?
(iii) Complete the following equation:

Answer:
(i) Mn+2 is more stable than Mn+3 due to half filled d-orbitals (3d5), whereas
Cr+3 is more stable than Cr+2 due to half filled orbitals.
(ii) It is due to presence of unpaired electrons which undergo d-d transition by
absorbing light from visible region and radiate complementary colour.
(iii) 2MnO4– + 16 H+ + 5C204– ———-> 2Mn+2 + 8H20 + 10CO2

Question 10:
(i) MnO is basic whereas Mn207 is acidic in nature. Why?

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(ii) Transition metals form alloys. Why?

(iii) Complete the following equation:
2MnO4 + 4KOH + O2 ———>
Answer:
(i) In MnO, Mn has +2 oxidation state, whereas in Mn2O7, Mn has + 7 oxidation
state. Higher the oxidation state, more will be acidic nature, e.g. Mn207. Lower
the oxidation state, more will be basic nature, e.g. MnO.
(ii) It is due to similar atomic size, they can replace one another in metallic
bond.
(iii) 2MnO4+ 4KOH + 02 ———> 2K2Mn04+ 2H20

Question 11:
(a) How would you account for the following:
(i) Actinoid contraction is greater than lanthanoid contraction.
(ii) Transition metals form coloured compounds.
(b) Complete the following equation:
2 MnO4 + 6H+ + 5NO2 – ———->
Answer:
(a) (i) Refer Ans. to Q.5 (ii).
(ii) Refer Ans. to Q.9 (ii).
(b) 2 MnO4+ 6H+ + 5NO2 – ———-> 2Mn2+ + 3H20 + 5N03

Question 12:
(a) Account for the following:
(i) Cu+ is unstable in an aqueous solution.
(ii) Transition metals form complex compounds
(b) Complete the following equation:
Cr202,- + 8H+ + 3NO2 – ———>
Answer:
(a) (i) It is because hydration energy of Cu2+ overcomes 2nd ionisation
enthalpy, that is why Cu+ changes to Cu2+ and Cu.
2Cu+ —–> Cu2+ + Cu
(ii) It is due to their small size, high charge and availability of vacant d-orbitals

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Question 13:
(a) How would you account for the following:
(i) Highest fluoride of Mn is MnF4 whereas the highest oxide is Mn2O2
(ii) Transition metals and their compounds show catalytic properties.
(b) Complete the following equation:
3MnO4– + 4H+ ———>
Answer:
(a) (i) Oxygen can form double bond, therefore, it can form Mn207, whereas ‘F’
cannot form double bonds, so, it can form MnF4.
(ii) Transition metals show variable oxidation states, therefore, they and their
compounds act as catalyst.
(b) 3MnO4– + 4H+ ——–> Mn02 + 2Mn04– + 2H20

Long Answer Type Questions [5 Marks]

Question 14:
(a) A blackish brown solid ‘A’ when forced with alkali metal hydroxide in
presence of air, produces a dark green coloured compound ‘B’, which on
electrolytic oxidation in alkaline medium gives a dark purple coloured
compound ‘C’. Identify A, B, C and write the reactions involved. What happens
when an acid solution of green coloured compound (B) is allowed to stand for
some time.
(b) (i) Calculate the spin magnetic moment of M2+(aq) ion. Atomic number (Z)
= 27.
(ii) Chromium is typical hard metal while mercury in liquid, explain.
Answer:

(ii) Cr is typically hard metal due to presence of large number of unpaired

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electrons, metal-metal interaction is strong whereas mercury does not have

unpaired electrons and has large size, therefore, forms weak metallic bond.

Question 15:
Account for the following:
(a) (i) EU2+ is strong reducing agent
(ii) Transition metals form coloured compounds
(iii) Zn has lowest enthalpy of atomisation.
(b) Complete the following equations:
(i) KMn04-(heat) ——-> (ii) Cr2072- + 14H+ + 6Fe2+ ———–>
Answer:
(a) (i) It is because Eu3+ is more stable.
(ii) Refer Ans. to Q.9 (ii).
(iii) It is due to weak metallic bonds due to completely filled d-orbitals.
(b) (i) 2KMn04———> K2Mn04+ MnO2+ O2
(ii) Cr2072 – + 14H+ + 6Fe2+ ———> 2Cr3+ + 7H20 + 6Fe3+

Question 16:
Account for the following:
(a) (i) Transition elements form interstitial compounds.
(ii) Mns+(3d4) is strongly oxidising, whereas Cr2+(3d4) is strongly reducing.
(iii) Transition metals have high melting points.
(b) What is misch metal? Write its one use.
Answer:
(a) (i) Small size atoms B, C, H can occupy voids present in transition metals.
(ii) Mn3+ gains one electron to form Mn2+ since 3dD is more stable, whereas
Cr2+ loses one electron for Cr3+(i3p which is more stable, so, it acts as
reducing agent.
(iii) It is due to involvement of unpaired ((-electrons to form strong metallic
bond.
(b) It contains 95% lanthanoid metal, 5% iron and traces of S, C, Ca and AI.
Use: Its magnesium based alloy is used to produce bullets, shells, flints.

2014

Very Short Answer Type Questions [1 Mark]

Question 17:
Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
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Answer:
Refer Ans. to Q. 5 (ii).

Short Answer Type Questions [I] [2 Marks]

Question 18:

Answer:

Question 19:

Answer:

Question 20:

Answer:

Question 21:
Describe the general trends in the following properties of first series 3d of
transition elements:
(i) number of oxidation states exhibited (ii) formation of oxometal ions.
Answer:
(i) The tendency to show number of oxidation states increases from Sc to Mn
and then decreases because number of unpaired electrons increases till Mn,
then decreases.
(ii) Tendency to form oxometal ions increases from Sc to Cr and then decreases

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due to increase in unpaired electrons and ability to form multiple bonds with
oxygen.

Short Answer Type Questions [II] [3 Marks]

Question 22:
(a) What are the different oxidation states exhibited by the lanthanoids?
(b) Write two characteristics of the transition elements.
(c) Which of the 3d-block elements may not be regarded as the transition
elements and why?
Answer:
(a) Lanthanoids, mostly show +3 oxidation state but some of them show +2
and +4 oxidation states also due to the stability of electronic configuration (4f°,
4f7 and 4f14), e.g. Eu shows +2, whereas Ce shows +4 oxidation state.
(b) (i) They show variable oxidation states.
(ii) They form coloured compounds.
(c) Zn may not be regarded as transition metal because neither ‘Zn’ nor Zn2+
ions have incompletely filled d-orbital.

Question 23:
Assign suitable reasons for the following:
(a) The Mn2+ compounds are more stable than Fe2+ towards oxidation to their
+3 state.
(b) In the 3d series from Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization
of Zn is the lowest.
(c) Sc3+ is colourless in aqueous solution, whereas Ti3+ is coloured.
Answer:
(a) Mn2+ has 3d5 (stable electronic configuration), therefore, it does not get
oxidised to Mn3+, whereas Fe2+ has 3d6 which readily changes to Fe3+ (3d5),
which has stable electronic configuration.
(b) Zinc does not have unpaired electrons and larger in size, therefore, it has
weak metallic bonds. That is why it has least enthalpy of atomisation.
(c) Sc3+ is colourless as it does not have unpaired electron and cannot undergo
d-d transition, whereas Ti3+ is coloured due to presence of unpaired electrons
and undergoes d-d transition by absorbing light from visible region and radiate
complementary colour.

Long Answer Type Questions [5 Marks]

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Question 24:
(a) How do you prepare:
(i)K2Mn04 from Mn02?
(ii) Na2Cr207 from Na2Cr04?
(b) Account for the following:
(i) Mn2+ is more stable than Fe2+ towards oxidation to +3 state.
(ii) The enthalpy of atomization is lowest for Zn in 3 d series of the transition
elements.
(iii) Actinoid elements show wide range of oxidation states.
Answer:
(a) (i) 2Mn02 + 4KOH + 02——–> 2K2Mn04 + 2H20
(ii) 2Na2Cr04 + H2S04(conc.) ——-> Na2Cr207 + Na2S04 + H20
(b) (i) Refer Ans. to Q.23 (a).
(ii) Refer Ans. to Q.23 (b).
(iii) Refer Ans. to 0.5 (i).

Question 25:
(i) Name the element of 3d transition series which shows maximum number of
oxidation states. Why does it show so?
(ii) Which transition metal of 3d series has positive E°(M2+/M) value and why?
(iii) Out of Cr3+ and Mn3+, which is a stronger oxidizing agent and why?
(iv) Name a member of the lanthanoid series which is well known to exhibit + 2
oxidation state.
(v) Complete the following equation:
MnO4– + 8H+ + 5e- ———->
Answer:
(i) Mn because it has five unpaired electrons and 2 electrons in s-orbital which
can take part in bond formation, therefore, it shows maximum number of
oxidation states.
(ii) E°CU9+/CU has +ve value due to high ionisation enthalpies and sublimation
energies and lower hydration energy.
(iii) Mn3+ is stronger oxidising agent because it can gain electrons to become
Mn2+ which is more stable due to 3d5 (half filled d-orbitals), whereas Cr3+ is
stable due to f3 (half filled orbitals).
(iv) Europium shows +2 oxidation state. Ytterbium (Yb) also shows +2 oxidation
state.
(v) Mn04 + 8H+ + 5e- ———> Mn2+ + 4H20.

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Question 26:
(a) Complete the following equations:
(i) Cr2072- + 20H- ———->
(ii) Mn04- + 4H+ + 3e- ———> ‘
(b) Account for the following:
(i) Zn is not considered as a transition element.
(ii) Transition metals form a large number of complexes.
(iii) The E° value for the Mn3+/Mn2 + couple is much more positive than that
for Cr3+/Cr2+ couple.
Answer:
(a) (i) Cr2072- + 20H- ——–> 2CrO4– + H2O
(ii) MnO- + 4H+ + 3e- ——-> Mn02 + 2H20
(b) (i) Refer Ans. to Q.l.
(ii) It is due to small size, higher charge and presence of vacant d-orbitals of
suitable energy.
(iii) Refer Ans. to Q.9 (i).

Question 27:
(i) With reference to structural variability and chemical reactivity, write the
Differen ces between lanthanoids and actinoids.
(ii) Name a member of the lanthanoid series which is well known to exhibit +4
oxidation state.
(iii) Complete the following equation:
Mn04– + 8H+ + 5e- ———–>
(iv) Out of Mn3+ and Cr3+, which is more paramagnetic and why?
(Atomic nos.: Mn = 25, Cr = 24)
Answer:

(ii) Ce shows +4 oxidation state.

(iii) MnO- + 8H4 + 5e- ———> Mn2+ + 4H20
(iv) Mn3+ (3d4) has 4.unpaired electrons, therefore, it is more paramagnetic
than Cr3+) which has three unpaired electrons.

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2013

Short Answer Type Questions [I] [2 Marks]

Question 28:
(a) Which metal in the first transition series (3d series) exhibits +1 oxidation
state most frequently and why?
(b) Which of the following cations are coloured in aqueous solutions and why?
Sc3+, V3+, Ti4+, Mn2+
(At. Nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
Answer:
(a) Copper exhibits +1 oxidation state frequently due to stable electronic
configuration.
(b) V3+ and Mn2+ are coloured, due to the presence of unpaired electrons,
they can undergo d-d transitions. Others are colourless due to the absence of
unpaired electrons and cannot undergo d-d transitions.

Short Answer Type Questions [II] [3 Marks]

Question 29:
How would you account for the following?
(i) Transition metals exhibit variable oxidation states.
(ii) Zr (Z = 40) and Hf (Z = 72) have almost identical radii.
(iii) Transition metals and their compounds act as catalyst.
Answer:
It is because electrons from (n – 1 )d and ns take part in bond formation.
(ii) It is due to lanthanoid contraction which is due to poor shielding effect of f-
electrons, due to which effective nuclear charge increases, therefore, Zr and Hf
have almost identical radii.
(iii) It is because they show variable oxidation states and form unstable
intermediates which readily change into products.

Question 30:

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Answer:

Long Answer Type Questions [5 Marks]

Question 31:

Answer:

Question 32:
(a) Why do transition elements show variable oxidation states?
(i) Name the element showing maximum number of oxidation states among
the first series of transition metals from Sc (Z = 21) to Zn (Z = 30).
(ii) Name the element which shows only +3 oxidation state.
(b) What is lanthanoid contraction? Name an important alloy which contains
some of the lanthanoid metals.
Answer:
(a) Refer Ans. to Q.29 (i).
(i) ‘Mn’ shows maximum number of oxidation states; +2, +3, +4, +6, +7.
(ii) Sc shows only +3 oxidation state.
(b) The decrease in atomic and ionic size with increase in atomic number is
called lanthanoid contraction. Misch metal is an important alloy which contains
some of the lanthanoid metals.
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Question 33:
Assign reasons for the following:
(i) In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of Zn is
the lowest.
(ii) Zr and Hf have almost identical radii.
(iii)Transition metals show variable oxidation states.
(iv) The value for copper is positive (+ 0.34 V).
(v) Cr2+ is a very good reducing agent.
Answer:
(i) It is due to weak metallic bond due to absence of unpaired electrons.
(ii) It is due to lanthanoid contraction.
(iii) Refer Ans. to Q.29 (i).
(iv) It is because of high ionisation enthalpy of Cu which is not compensated by
hydration energy.
(v) It is because Cr2+ loses an electron to form Cr3+ which is more stable as i2g
orbitals are half-filled, i.e. more stable.

Question 34:
Describe the preparation of KMn04 from pyrolusite ore (MnO4). How does the
acidified permanganate solution react with the following:
(i) Fe2+ ions
(ii) Oxalic acid (C2H204)
Write the ionic equations for the reactions involved.
Answer:
Potassium permanganate is prepared by fusion of Mn02 with alkali metal
hydroxide (KOH) in presence of 02 or oxidising agent like KNO3. It produces
dark green K2Mn04 which undergoes oxidation as well as reduction in neutral

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or acidic solution to give permanganate.

2012

Short Answer Type Questions [I] [2 Marks]

Question 35:

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Answer:

Short Answer Type Questions [II] [3 Marks]

Question 36:

How would you account for the following?

(i) Many of the transition elements are known to form interstitial compounds,
(ii) The metallic radii of the third (5d) series of transition metals are virtually
the same as those of the corresponding group members of the second (4d)
series.
(iii) Lanthanoids form primarily +3 ions, while the actinoids usually have higher
oxidation states in their compounds, +4 or even +6 being typical.
Answer:
(i) Small size atoms, such as B, C and H can occupy voids present in transition
metals.
(ii) It is due to lanthanoid contraction.
(iii) It is because lanthanoid lose 2 electrons from 6s orbitals and one from 5d –
or 4/ orbitals and are stable in +3 oxidation state. Actinoids can lose electrons
from 7s, 6d and 5/ orbitals easily due to comparable energies and show higher
oxidation states +4 and +6.

Question 37:
How would you account for the following?
(i) With the same d-orbital configuration (d4) Cr2+ is a reducing agent while
Mn3+ is an oxidising agent. .
(ii) The actinoids exhibit a large number of oxidation states than the
corresponding members in the lanthanoid series.

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(iii) Most of the transition metal ions exhibit characteristic colours in aqueous
solutions
Answer:
(i) Refer Ans. to Q.16 (a) (ii).
(ii) It is because 5f, 6d and Is have comparable energy.
(iii) Refer Ans. to Q.9 (ii).

Question 38:
Explain the following observations giving an appropriate reason for each:
(i) The enthalpies of atomization of transition elements are quite high.
(ii) There occurs much more frequent metal-metal bonding in compounds of
heavy transition metals (i.e. 3rd series).
(iii) Mn2+ is much more resistant than Fe2+ towards oxidation.
Answer:
(i) It is because of strong metallic bonds due to large number of unpaired
electrons in d-orbitals.
(ii) It is due to presence of unpaired electrons which participate in metal-metal
bonding in 5d series (3rd series).
(iii) Refer Ans. to Q.23 (a).

Question 39:
How would you account for the following:
(i) Among lanthanoids, Ln(III) compounds are predominant. However,
occasionally in solutions or in solid compounds, +2 and +4 ions are also
obtained.
(ii) The E°M2+/M for copper is positive (0.34V). Copper is the only metal in the
first series of transition elements showing this behaviour.
(iii) The metallic radii of the third (5d) series of transition metals are nearly the
same as those of the corresponding members of the second series.
Answer:
(i) It is because after losing 2 electrons and 4 electrons, they acquire stable
configuration, i.e. f°,f7,f14.
(ii) E°CU2+/CU *ias +ve value due to high ionisation enthalpies and sublimation
energies and lower hydration energy.
(iii) It is due to lanthanoid contraction.

Question 40:
Explain the following observations:
(i) Many of the transition elements are known to form interstitial compounds.

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(ii) There is a general increase in density from titanium (Z = 22) to copper (Z =

29).
(iii) The members of the actinoid series exhibit a larger number of oxidation
states than the corresponding members of the lanthanoid series.
Answer:
(i) Refer Ans. to Q.16 (a) (i).
(ii) It is due to increase in atomic mass and decrease in atomic size, therefore,
density increases from Ti(22) to Cu(29).
(iii) It is because 5f, 6d and 7s have comparable energy.

Question 41:
Explain each of the following observations:
(i) With the same d-orbital configuration (d4), Cr2+ is a reducing agent while
Mn3+ is an oxidising agent.
(ii) Actinoids exhibit a much larger number of oxidation states than the
lanthanoids.
(iii) There is hardly any increase in atomic size with increasing atomic numbers
in a series of transition metals.
Answer:
(i) Refer Ans. to Q.16 (a) (ii).
(ii) It is due to 5f electrons which are more effectively shielded than 4f
electrons therefore, outer electrons are less firmly held and available for
bonding in actinoids and they show a wide range of oxidation states.
(iii) It is due to lanthanoid contraction, effective nuclear charge does not
decrease, therefore, atomic size does not increase appreciably in the series of
transition metals

Long Answer Type Questions [5 Marks]

Question 42:
(a) Complete and balance the following chemical equations:
(i) Cr2072- + I- + H+ ——–>
(ii) Mn04– + SO2– + H+ ———>
(b) Explain the following observations:
(i) Transition elements and their compounds are known to act as catalysts.
(ii) The higher oxidation states are usually exhibited by the members in the
middle of a series of transition elements.
(iii) The metal-metal bonding is more frequently found with the second and
third series of transition elements.
Answer:
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(b) (i) Refer Ans. to Q.29 (iii).

(ii) It is due to large number of unpaired electrons in the middle of series of
transition metals.
(iii) It is due to poor shield effect ofd, and f-orbitals, more unpaired electrons
can take part in metal-metal bonds.

Question 43:
(a) Calculate the number of unpaired electrons in the following gaseous state
ions:
Mn2+, Cr3+, V3+ and Fe2+
which one of these in the most stable in aqueous solutions?
(At. nos. V = 23, Cr = 24, Mn = 25, Fe = 26)
(b) Explain the following observations:
(i) The transition metal ions are usually coloured in aqueous solutions.
(ii) Cu(I) is not stable in an aqueous solution.
(iii) The highest oxidation state of a transition metal is exhibited in its oxide or
fluoride.
Answer:

(b) (i) Refer Ans. to Q.9 (ii).

(ii) It is because Cu2+ is more stable because hydration energy overcomes 2nd
ionisation energy.
(iii) It is because oxygen and fluorine are strong oxidising agents, highly
electronegative, small size and can provide energy for formation of transition
metal ion in higher oxidation state.

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