d & f

Chapter–8
The d- and
f- Block Elements
1. d-Block Elements: The d-block elements are those elements in which the last electron enters the d–subshell
of penultimate shell. The general electronic configuration of these elements is (n – 1) d 1–10 ns1–2, where n
is outermost shell. The d-block consisting of groups 3–12 occupies the large middle section of the periodic
table.
2. Transition Elements: The elements of d-block are known as transition elements as they possess properties
that are transitional between the s and p block elements. A transition element is defined as an element which
has incompletely filled d-orbitals in its ground state or any one of its oxidation states. There are four series
of transition elements spread between group 3 and 12.
First transition series or 3d-series: Scandium (21Sc) to Zinc (30Zn)
Second transition series or 4d-series: Yttrium (39Y) to Cadmium (48Cd)
Third transition series or 5d-series: Lanthanum (57La) and Hafnium (72Hf) to Mercury (80Hg)
(Omitting 58Ce to 71Lu)
Fourth transition series or 6d-series: Begins with Actinium (89Ac) is still incomplete.
Zinc, cadmium and mercury of group 12 have full d 10 configuration in their ground state as well as in their
common oxidation states and hence, are not regarded as transition metals. However, being the end elements
of the three transition series, their chemistry is studied along with the chemistry of the transition elements.
3. General Characteristics of Transition Elements
(a) Atomic radii: The atomic radii of transition elements are smaller than those of s-block elements
and larger than those of p-block elements in a period. In a transition series, as the atomic number
increases, the atomic radii first decreases till the middle, becomes almost constant and then increases
towards the end of the period. The decrease in atomic radii in the beginning is due to the increase in
the effective nuclear charge with the increase in atomic number. However, with the increase in the
number of electrons in (n – 1) d–subshell, the screening effect of these d-electrons on the outermost
ns-electrons also increases. This increased screening effect counterbalances the effect of increased
nuclear charge, therefore, the atomic radii remain almost constant in the middle of the series. Increase
in atomic radii towards the end may be attributed to the electron–electron repulsion. The pairing of
electrons in the d-orbitals of the penultimate shell occurs only after the d–subshell is half filled. The
repulsive interactions between the paired electrons in d-orbitals (of the penultimate shell) become
very dominant towards the end of the series and causes the expansion of the electron cloud and thus,
resulting in increased atomic size.
The atomic radii usually increase down the group. But the atomic radii of the elements of second
and third transition series belonging to a particular group are almost equal. This is due to lanthanoid
contraction.
(b) Ionic radii: The ionic radii of the transitional elements follow the same order as their atomic radii. In
general, the ionic radii decrease with increase in oxidation state.
(c) Ionisation enthalpies: The first ionisation enthalpies of transition elements are higher than those of
s-block elements but lower than p-block elements. In a particular transition series, ionisation enthalpy
increases gradually with increase in atomic number, though some irregularities are observed.
The d- and f- Block Elements 303

Reason: The increase in ionisation enthalpy is due to increase in nuclear charge with increase in
atomic number which tends to attract the electron cloud with greater force.
The addition of d-electron in penultimate shell with increase in atomic number provides a screening
effect and shield the outer s-electrons from inward nuclear pull. Thus, the effect of increased nuclear
charge and increased magnitude of screening effect tend to oppose each other. Consequently, the
increase in ionisation enthalpy along the series of transition element is very small. The irregular
variations of first and second ionisation enthalpies in the first transition series is mainly due to varying
degree of stability of different 3d-configuration. For example, Cr has low first ionisation enthalpy
because loss of one electron gives stable 3d5 configuration and Zn has very high first ionisation
enthalpy because the electron has to be removed from 4s-orbital of the stable 3d104s2 configuration.
The first ionisation enthalpies of 5d-transition elements are higher than those of 3d and 4d elements.
This is due to greater effective nuclear charge acting on the outer valence electrons in these elements
because of the ineffective shielding of the nucleus by 4f-electrons.
(d) Metallic character: All the transition elements are metallic in nature. They show gradual decrease in
electropositive character in moving from left to right in a series. The metallic bond in transition metals
are very strong. This is due to greater effective nuclear charge, low ionisation energies and large
number of vacant orbitals in their outermost shell. Nearly, all the transition metals are hard, possess
high density and high enthalpy of atomisation. This is due to presence of strong metallic bonds.
(e) Melting and boiling points: Except zinc, cadmium and mercury all the other transition elements
generally have high melting and boiling points. This is due to strong metallic bonds and presence of
partially filled d-orbitals in them. Because of these half-filled orbitals some covalent bonds also exist
between atoms of transition elements. As zinc, mercury and cadmium have fully filled d-orbitals,
therefore, there is no covalent bonding amongst the atoms of these elements. This accounts for their
low melting and boiling points.
In moving along series from left to right, the melting and boiling points of transition elements first
increase to a maximum and then decrease towards the end of the period. As the number of unpaired
electrons increases, the tendency to form metallic and covalent bonds also increases. In first transition
series after chromium, the number of unpaired electrons decreases, hence the melting point also
decreases. Manganese possesses anomalous melting and boiling points because it has stable 3d 54s2
configuration, i.e., electrons are held tightly by nucleus so that the delocalisation is less and the metallic
bond is much weaker than that of preceding element.
(f) Oxidation states: All transition elements except first and last member of the series exhibit variable
oxidation states as (n – 1)d and ns orbitals have comparable energies so that both can enter into
chemical bond formation. The maximum oxidation state shown by first series increases from Sc to Mn
and then decreases. The common oxidation state of first series is +3 (except Sc). The highest oxidation
state of transition elements is 8 (Os and Ru).
The compounds of transition elements in lower states +2 and +3 are mostly ionic and of higher
oxidation states are covalent, e.g., ZnCl2 and CdCl2 are ionic whereas Cr2O72– and MnO4– are covalent
in nature, higher oxidation state of transition elements are shown in oxides and oxoacids (e.g., MnO4–).
Transition metals with fluorine and oxygen exhibit higher oxidation state due to higher electronegative
nature of fluorine and oxygen. Transition metals also exhibit +1 and 0 oxidation states. For example:
Cu2Cl2, AgCl, Hg2Cl2 (OS of metal is +1)
Ni(CO)4 , Fe(CO)5 (OS of metal is 0)
When the metal exhibit more than one OS, their relative stabilities can be known from their standard
electrode potential, e.g.,
Cu2+(aq) + 2e– Cu(s) E ored = 0.34 volt
+ –
Cu (aq) + e Cu(s) E ored = 0.52 volt
Lower standard reduction potential indicates Cu2+ is more stable than Cu+ in aqueous medium.
(g) Standard electrode potential: Electrode potential is the electric potential developed on a metal
electrode when it is in equilibrium with a solution of its own ions, taking electrons from the electrode.
There is irregular variation in electrode potential due to irregular variation in ionisation enthalpy,
sublimation energy and energy of hydration. The E° value decreases from left to right across the
304 Xam idea Chemistry–XII

series; Mn, Ni and Zn have higher values than expected because of their half-filled or completely filled
3d-orbitals in case of Mn2+ and Zn2+ respectively and the highest negative enthalpy of hydration, Ni2+.
(h) Magnetic properties: Substances containing unpaired electrons are said to be paramagnetic. A
diamagnetic substance is one in which all the electrons are paired. Except the ions of d 0 (Sc3+, Ti4+)
and d10 (Cu+, Zn2+) configurations, all other simple ions of transition elements contain unpaired
electrons in their (n – 1) d subshell and are, therefore, paramagnetic. The magnetic moments (µ) of
the elements of first transition series can be calculated with the unpaired electrons (n) by the spin only
formula.
µ n(n 2) BM (Bohr Magneton)
(i) Complex formation: The tendency to form complex ions is due to
(i) the high charge on the transition metal ions,
(ii) the availability of d-orbitals for accommodating electrons donated by the ligand atoms.
(j) Catalytic property: Most of the transition metals and their compounds possess catalytic properties.
The catalytic activity of transition metal ions is attributed to the following two reasons:
(i) Variable oxidation states due to which they can form a variety of unstable intermediate products.
(ii) Large surface area so that the reactants are adsorbed on the surface and come close to each other
facilitating the reaction process.
(k) Colour: Most of the transition metal ions in solution as well as in solid states are coloured. This is due
to the partial absorption of visible light. The absorbed light promotes the electron from one orbital to
another orbital of the same d-subshell. Since the electronic transition occurs within the d-orbitals of
the transition metal ions, they are called d–d transitions. It is because of these d–d transitions occurring
in a transition metal ion by absorption of visible light that they appear coloured.
(l) Alloy formation: The transition metals have similar radii and other characteristics. Therefore, these
metals can mutually substitute their position in their crystal lattices and form alloys. The alloys so
formed are hard and often have high melting point. Various types of steel, brass, bronze are examples
of this type of alloy.
(m) 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 small-
sized atoms of H, B, C, N, etc., can easily occupy positions in the voids present in the crystal lattices
of transition metals.
4. Some Important Compounds of Transition Elements: Though the transition elements are sufficiently
electropositive, yet they are not very reactive because of
(i) their high enthalpies of sublimation, and
(ii) their high ionisation enthalpies.
Oxides: Transition metals form oxides of the general composition MO, M2O3, MO2, M2O5 and MO6.
Oxides in the lower oxidation states are generally basic in nature and those in the higher oxidation states
are amphoteric or acidic in nature. For example,
+2 +3 +8/3 +4 +7
MnO Mn2O3 Mn3O4 MnO2 Mn2O7
Basic Amphoteric Amphoteric Amphoteric Acidic
(a) Potassium Dichromate, K2Cr2O7: It is prepared from the chromite ore. Different reactions involved
in the preparation of potassium dichromate from chromite ore are:
Roasted
4FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
Chromite ore Sodium chromate
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Sodium dichromate
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
Potassium dichromate
K2Cr2O7 is separated by fractional crystallisation.
Properties: When potassium dichromate is heated with any ionic chloride (e.g., NaCl, BaCl2, etc.)
and concentrated H2SO4, red vapours of chromyl chloride are obtained.

K 2 Cr2 O 7 4KCl 6 H 2 SO 4
2CrO2 Cl2 6KHSO 4 3H 2 O
Chromyl chloride
Potassium dichromate is a powerful oxidising agent. In acidic medium, its oxidation action can be
represented as follows:
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O+ 3[O]
Cr2O72– +
+ 14H + 6e –
2Cr3+ + 7H2O (Eo = +1.31 V)
(i) It oxidises ferrous to ferric.
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Fe2+ Fe3+ + e– ] × 6
Cr2O72– + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O
(ii) It oxidises stannous to stannic.

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Sn2+ Sn4+ + 2e– ] × 3
Cr2O72– + 3Sn2+ + 14H+ 2Cr3+ + 3Sn4+ + 7H2O
(iii) It oxidises sulphur dioxide to sulphuric acid.

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
SO2 + 2H2O SO42– + 4H+ + 2e– ] × 3
Cr2O72– + 3SO2 + 2H+ 2Cr3+ + 3SO42– + H2O
(iv) It oxidises hydrogen sulphide to sulphur.

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
H2S 2H+ + S + 2e– ] × 3
Cr2O72– + 3H2S + 8H+ 2Cr3+ + 3S + 7H2O
(v) It oxidises iodides to iodine.

Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
2I – I2 + 2e– ] × 3
Cr2O72– + 6I – + 14H+ 2Cr3+ + 3I2 + 7H2O
Structures of chromate and dichromate ions:
O 2–
m 2–
O 9p O O
17
126°
Cr O Cr Cr O
163
O pm O
O O O
Chromate ion Dichromate ion
The chromate and dichromate ions are interconvertible in aqueous solution depending upon the pH of
the solution.
2CrO 24– + 2H + Cr2 O72– + H 2 O
Dichromate ion
^orange red h
Cr2 O72– + 2OH – 2CrO 24– + H 2 O

Chromate ion
^ yellow h
Potassium dichromate is used as primary standard in volumetric analysis.

(b) Potassium permanganate, KMnO4: It is prepared by fusion of pyrolusite, MnO2, with KOH in
the presence of an oxidising agent like KNO3. This produces the dark green potassium manganate,
K2MnO4 which disproportionates in a neutral or acidic solution to give purple permanganate.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
Potassium manganate
3MnO42– + 4H+ 2MnO4– + MnO2 + 2H2O
Or, 3K2MnO4 + 4H+ 2KMnO4 + MnO2 + 2H2O + 4K+
Potassium
permanganate
Commercially, it is prepared by alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (VI).
Fused with KOH
MnO 2 oxidised with air or KNO3
MnO 2– 4
Manganate ion
Electrolytic Oxidation
MnO 24– in alkaline solution
MnO 4–
Permanganate ion
In the laboratory, KMnO4 is prepared by oxidation of manganese (II) ion salt by peroxodisulphate.
2Mn 2+ + 5S 2 O82– + 8H 2 O 2MnO 4– + 10SO 24– + 16H +
Peroxodisulphate Permanganate
Properties:
Potassium permanganate is a dark purple crystalline solid.
On heating, it decomposes at 513 K and O2 is evolved.
2KMnO 4
Heat
K 2 MnO 4 + MnO 2 + O 2
Potassium manganate
Potassium permanganate acts as a powerful oxidising agent in acidic, alkaline and neutral media. Few
important oxidation reactions of KMnO4 are given below:
1. In acidic medium potassium permanganate oxidises:
(i) Iodide to iodine
MnO4– + 8H+ + 5e– Mn2+ + 4H2O] × 2
2I– I2 + 2e– ] × 5
2MnO4– + 10I – + 16H+ 2Mn2+ + 5I2 + 8H2O
(ii) Ferrous to ferric

MnO4– + 8H+ + 5e– Mn2+ + 4H2O
Fe2+ Fe3+ + e– ] × 5
MnO4– + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
(iii) Oxalate to carbon dioxide

MnO4– + 8H+ + 5e– Mn2+ + 4H2O] × 2
C2O42– 2CO2 + 2e– ] × 5
2MnO4– + 5 C2O42– + 16H+ 2Mn2+ + 10CO2 + 8H2O
(iv) Hydrogen sulphide to sulphur

MnO4– + 8H+ + 5e– Mn2+ + 4H2O] × 2
S2– S + 2e– ] × 5
2MnO4– + 5S2– + 16H+ 2Mn2+ + 5S + 8H2O

(v) Sulphite to sulphate
MnO4– + 8H+ + 5e– Mn2+ + 4H2O ] × 2
SO32– + H2O SO42– + 2H+ + 2e– ] × 5
5SO32– + 2MnO4– + 6H+ 2Mn2+ + 5SO42– + 3H2O
(vi) Nitrite to nitrate

MnO4– + 8H+ + 5e– Mn2+ + 4H2O ] × 2
NO2– + H2O NO3– + 2H+ + 2e– ] × 5
2MnO4– + 5NO2– + 6H+ 2Mn2+ + 5NO3– + 3H2O
2. In neutral or faintly alkaline solutions potassium permanganate oxidises:

(i) Iodide to iodate
2MnO4– + I – + H2O IO3– + 2MnO2 + 2OH–
(ii) Thiosulphate to sulphate
8MnO4– + 3S 2 O32– + H2O 8MnO2 + 6SO 2–
4
+ 2OH –
(iii) Manganous salt to MnO2 in presence of zinc sulphate or zinc oxide
2MnO4– + 3Mn 2+ + 2H2O 5MnO2 + 4H+
The MnO42– and MnO4– are tetrahedral; the green MnO42– is paramagnetic with one unpaired electron
but the purple MnO4– is diamagnetic.
O– O
Mn Mn
O O– O O–
O O
Tetrahedral manganate ion Tetrahedral permanganate ion
(green) (purple)
Inner Transition Elements (f-Block Elements)

The inner transition elements consist of lanthanoids and actinoids. They are characterised by filling of the ‘f ’
orbitals.
5. Lanthanoids
The series involving the filling of 4f-orbitals following lanthanum La (Z = 57) is called the lanthanoid
series. There are 14 elements in this series, starting with cerium Ce (Z =58) to lutetium Lu (Z = 71). The
lanthanoids
°° are highly dense metals.
°° have high melting points.
°° form alloys easily with other metals.
°° are soft, malleable and ductile with low tensile strength.
(i) Oxidation state: The most characteristic oxidation state of lanthanoid elements is +3. Some of the
elements also exhibit +2 and +4 oxidation states.
(ii) Colour: Some of the trivalent ions of lanthanoids are coloured. This is due to the absorption in visible
region of the spectrum, resulting in f-f transitions because they have partly filled orbitals.
(iii) Magnetic properties: Among lanthanoids, La3+ and Lu3+, which have 4f 0 or 4f 14 electronic
configurations are diamagnetic and all the other trivalent lanthanoid ions are paramagnetic because of
the presence of unpaired electrons.
(iv) Reactivity: All lanthanoids are highly electropositive metals and have an almost similar chemical
reactivity.

(v) Lanthanoid contraction: In lanthanoids, with increasing atomic number, the atomic and ionic
radii decreases from one element to the other, but the decrease is very small. It is because, for every
additional proton in the nucleus, the corresponding electron goes into a 4f-subshell, which is too
diffused to screen the nucleus as effectively as the more localised inner shell. Hence, the attraction of
the nucleus for the outermost electrons increases steadily with the atomic number.
(vi) Uses of lanthanoids: The pure metals have no specific use. So they are used as alloys or compounds.
°° As alloys lanthanoids are used in making a misch metal which consists of lanthanoid metals (~95%)
and iron (~5%) and traces of sulphur, carbon, calcium and aluminium. Magnesium mixed with 3%
misch metal is used for making jet engine parts.
°° Steel mixed with La, Ce, Pr and Nd is used in the manufacture of flame throwing tanks.
°° Lanthanoid oxides are used for polishing glass. Neodymium and praseodymium oxides are used for
making coloured glasses for goggles.
°° Cerium salts are used in dyeing cotton and also as catalysts.
°° Lanthanoid compounds are used as a catalyst for hydrogenation, dehydrogenation and petroleum
cracking.
°° Pyrophoric alloys are used for making tracer bullets and shells.
6. Actinoids: The elements following actinium, Ac (Z = 89), up to lawrencium (Z = 103), are called actinoids.
The actinoids
°° are highly dense metals with a high melting point and form alloys with other metals, specially iron.
°° are silvery white metals, which are highly reactive.
°° get tarnished when exposed to alkalis and are less reactive towards acids.
(i) Actinoid contraction: The atomic and ionic size decreases with an increase in atomic number.
Electrons are added to the 5f-subshell, as a result the nuclear charge increases causing the shells to
shrink inwards.
(ii) Electronic configuration: The actinoids involve the filling of 5f-subshells. Actinium has the electronic
configuration 6d1 7s2. From thorium (Z = 90) onwards, 5f-orbitals get progressively filled up. Because
of equal energy of 5f and 6d subshells, there are some uncertainities regarding the filling of 5f and 6d
subshells. Most of their properties are comparable to that of lanthanoids.
(iii) Oxidation state: Generally +3 oxidation state is preferred in actinoids. The elements in the first of
actinoid series frequently exhibit higher states. For example, the maximum oxidation increases from
+4 in Th to +5, +6 and +7 in Pa, U and Np, respectively, but decreases in succeeding elements.
(iv) Colour: The actinoid ions are coloured.
(v) Magnetic properties: Many of the actinoid ions are paramagnetic.
(vi) Reactivity: They are also highly electropositive and form salts as well as complexes. Many of these
elements are radioactive.
(vii) Uses of actinoids:
OO Thorium is used in the treatment of cancer and in incandescent gas mantles.
OO Uranium is used in the glass industry, textile industry, in medicines and as nuclear fuel.
OO Plutonium is used in atomic reactors and in atomic bombs.
7. Differences between Lanthanoids and Actinoids
S.No. Lanthanoids Actinoids
(i) 4f-orbital is progressively filled. 5f-orbital is progressively filled.
(ii) +3 oxidation state is most common along with +2 and +4. They show +3, +4, +5, +6, +7 oxidation states.
(iii) Only promethium (Pm) is radioactive. All are radioactive.
(iv) They are less reactive than actinoids. They are more reactive.
(v) Magnetic properties are less complex. Magnetic properties are more complex.

NCERT Textbook Questions
NCERT Intext Questions

Q. 1. Silver atom has completely filled d-orbitals (4d10) in its ground state. How can you say that it is a
transition element?
Ans. Silver (Z = 47) can exhibit +2 oxidation state wherein it will have incompletely filled d-orbitals (4d), hence
a transition element.
Q. 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?
Ans. 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. That is why, the enthalpy of atomisation of zinc is the lowest in the series.
Q. 3. Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?
Ans. Manganese (Z = 25), as it has the maximum number of unpaired electrons in d-subshell. Thus, it shows
oxidation states from +2 to +7 (+2, +3, +4, +5, +6 and +7) which is the maximum number.
Q. 4. The Eo (M2+/M) value for copper is positive (+0.34 V). What is possible reason for this?
(Hint: Consider its high D a H 6 and low Dhyd H 6)
Ans. Eo (M2+/M) for any metal is related to the sum of the enthalpy change taking place in the following steps:
M(s) + Da H M(g), (Da H = Enthalpy of atomisation)
M(g) + Di H M2+(g), (Di H = Ionisation enthalpy)
2+
M (g) + aq M2+(aq) + DhydH, (Dhyd H = Hydration enthalpy)
Copper has high enthalpy of ionisation and relatively low enthalpy of hydration. So, E(oCu2+ /Cu) is positive.
The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.
Q. 5. How would you account for the irregular variation of ionisation enthalpies (first and second) in first
series of the transition elements?
Ans. Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d
configuration (e.g., d 0 , d 5 , d 10 are exceptionally stable).
Q. 6. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Ans. Due to small size and high electronegativity, oxygen or fluorine can oxidise a metal to its highest oxidation
state. As a result of this they can oxidise a metal to its highest oxidation state.
Q. 7. Which is a stronger reducing agent— Cr2+ or Fe2+ and why? [HOTS]
Ans. Cr is a stronger reducing agent than Fe because after the loss of one electron Cr becomes Cr3+ which
2+ 2+ 2+
has more stable t 32g (half-filled) configuration in a medium like water.

Q. 8. Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27).
OR
Calculate the spin-only magnetic moment of Co2+(Z=27) by writing the electronic configuration of Co
and Co2+. [CBSE 2020 (56/1/1)]
Ans. Electronic configuration of M atom with Z = 27 is [Ar] 3d 7 4s 2 .
\ Electronic configuration of M2+ = [Ar] 3d 7, i.e.,
Hence, it has three unpaired electrons.
\ Spin only magnetic moment (µ) =
n(n + 2) BM
= 3(3 + 2) BM = 15BM = 3.87 BM
Q. 9. Explain why Cu+ ion is not stable in aqueous solutions? [HOTS]
Ans. In aqueous solution Cu+ undergoes disproportionation to form a more stable Cu2+ ion.
2Cu+ (aq) Cu2+(aq) + Cu(s)
The higher stability of Cu in aqueous solution may be attributed to its greater negative ∆hyd.Ho than that
2+
of Cu+. It compensates the second ionisation enthalpy of Cu involved in the formation of Cu2+ ions.

Q. 10. Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Ans. This is because the 5f electrons themselves provide poor shielding from element to element in the series.
NCERT Textbook Exercises

Q. 1. Write down the electronic configuration of
(i) Cr3+ (ii) Cu+ (iii) Co2+ (iv) Mn2+ (v) Pm3+
(vi) Ce4+ (vii) Lu2+ (viii) Th4+
3+ 3
Ans. (i) Cr = [Ar] 3d (ii) Cu+ = [Ar] 3d 10
(iii) Co2+ = [Ar] 3d 7 (iv) Mn2+ = [Ar] 3d 5
(v) Pm3+ = [Xe] 4f 4 (vi) Ce4+ = [Xe]
(vii) Lu2+ = [Xe] 4f 14 5d 1 (viii) Th4+ = [Rn]
Q. 2. Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their +3 state?
Ans. Electronic configuration of Mn2+ is 3d 5 which is half-filled and hence stable. So, 3rd ionisation enthalpy is
very high, i.e., 3rd electron cannot be easily lost. In case of Fe2+, electronic configuration is 3d 6. Thus, it
can lose one electron easily to give the stable configuration 3d 5.
Q. 3. Explain briefly how +2 state becomes more and more stable in the first half of the first row transition
elements with increasing atomic number.
Ans. As the atomic number increases from 21 to 25, the number of electrons in the 3d-orbital also increases from
1 to 5. +2 oxidation state is attained by the loss of the two 4s electrons by these metals. Sc does not exhibit
+2 oxidation state. As the number of d- electrons in +2 state increases from Ti to Mn, the stability of +2
state increases (d-orbital gradually becoming half filled). Mn(+2) has d 5 electrons which is highly stable.
Q. 4. To what extent do the electronic configurations decide the stability of oxidation states in the first
series of the transition elements? Illustrate your answer with example.
Ans. The stability of oxidation states in the first series of the transition elements are related to their electronic
configurations.
The first five elements of the first transition series up to Mn in which the 3d-subshell is not more than
half-filled, the minimum oxidation state is given by the number of electrons in the outer s-subshell and the
maximum oxidation state is given by the sum of the outer s and d-electrons. For example, Sc does not
show +2 oxidation state. Its electronic configuration is 3d 1 4s2. It loses all the three electrons to form
Sc3+. +3 oxidation state is very stable as by losing all three electrons, it attains the stable configuration of
Argon. For Mn, +2 oxidation state is very stable, as after losing two 4s electrons, the d-orbitals become
half-filled.
Q. 5. What may be the stable oxidation state of the transition element with the following d-electron
configuration in the ground state of their atoms?
3d 3 , 3d 5 , 3d 8 and 3d 4
Ans. Stable oxidation states:
3d 3 (vanadium): +2, +3, +4, +5 3d 5 (chromium): +3, +4, +6
3d 5 (manganese): +2, +4, +6, +7 3d 8 (nickel): +2, +4
3d 4: There is no d 4 configuration in the ground state.
Q. 6. Name the oxo-metal anions of the first series of the transition metals in which the metal exhibits the
oxidation state equal to its group number.
Ans. Cr2O72– and CrO42– (group no. = oxidation state of Cr = 6)
MnO4– (group no. = oxidation state of Mn = 7)
Vanadate: VO3– (group no. = oxidation state of V = 5)
Q. 7. What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
Ans. Refer to Basic Concepts Point 5 (v).
The consequences of lanthanoid contraction are as follows:
(i) The properties of second and third transition series are similar.

(ii) Basic strength decreases from La(OH)3 to Lu(OH)3.
(iii) Lanthanide contraction makes separation of lanthanoids possible.
Q. 8. What are the characteristics of the transition elements and why are they called transition elements?
Which of the d-block elements may not be regarded as the transition elements?
Ans. Characteristics of the transition elements: Refer to Basic Concepts Point 3.
The d-block elements are called transition elements because these elements represent change (or
transition) in properties from the most electropositive s-block elements to the least electropositive
p-block elements.
The electronic configuration of Zn, Cd and Hg are represented by the general formula (n – 1) d 10 ns 2. 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.
Q. 9. In what way is the electronic configuration of transition elements different from that of the non-
transition elements?
Ans. Transition elements contain incompletely filled d-subshell, i.e., their electronic configuration is
(n – 1) d 1 – 10 ns1 – 2 whereas non-transition elements have no d-subshell or their subshell is completely
filled and have ns1 – 2 or ns2 np1 – 6 in their outermost shell.
Q. 10. What are the different oxidation states exhibited by lanthanoids?
Ans. +2, +3 and +4 (+3 being most common).
Q. 11. Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
Ans. (i) Refer to Basic Concepts Point 3(h).
(ii) The transition elements exhibit high enthalpy of atomisation because they have large number of
unpaired electrons in their atoms. Due to this they have stronger interatomic interaction.
(iii) Refer to Basic Concepts Point 3(k).
(iv) 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. Vanadium oxide (in
Contact Process), finely divided iron (in Haber’s Process), and nickel (in catalytic hydrogenation)
are some examples to mention. Catalysts at a solid surface involve the formation of bonds between
reactant molecules and atoms of the surface of the catalyst (first row transition metals utilise 3d and
4s electrons for bonding). This has the effect of increasing the concentration of the reactants at the
catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is
lowering). Also, since the transition metal ions can change their oxidation states, they become more
effective as catalysts. For example, iron(III) catalyses the reaction between iodide and persulphate ions.
2I – + S2O82– I2 + 2SO42–
An explanation of this catalytic action is given as under:
2Fe3+ + 2I – 2Fe2+ + I2
2Fe2+ + S2O82– 2Fe3+ + 2SO42–
Q. 12. What are interstitial compounds? Why are such compounds well known for transition metals?
Ans. 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 small-sized atoms of H, B, C, N, etc.,
can easily occupy positions in the voids present in the crystal lattices of transition metals.
Q. 13. How is the variability in oxidation states of transition metals different from that of the non transition
metals? Illustrate with examples.
Ans. The oxidation states of transition elements differ from each other by unity e.g., Fe2+ and Fe3+, Cu+ and Cu2+
(due to incomplete filling of d-orbitals) whereas oxidation states of non-transition elements normally differ
by two units e.g., Pb2+ and Pb4+, Sn2+ and Sn4+, etc.

Q. 14. Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate?
Ans. For preparation of potassium dichromate from iron chromite ore refer to Basic Concepts Point 4(a).
In aqueous solution, dichromate and chromate ions exist in equilibrium. On increasing the pH, i.e., on
making the solution alkaline, dichromate ions (orange coloured) are converted into chromate ions and thus,
the solution turns yellow.
Q. 15. Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction
with (i) iodide (ii) iron (II) solution (iii) H2S.
Ans. (i) Cr2O72– + 14H+ + 6I – 2Cr3+ + 7H2O + 3I2
(ii) Cr2O72– + 14H+ + 6Fe2+ 2Cr3+ + 7H2O + 6Fe3+
(iii) Cr2O72– + 8H+ + 3H2S 2Cr3+ + 7H2O + 3S
Q. 16. Describe the preparation of potassium permanganate. How does the acidified permanganate react
with (i) iron (II) ions (ii) SO2 (iii) oxalic acid? Write the ionic equations for the reaction.
Ans. For preparation, refer to Basic Concepts Point 4(b).
(i) MnO4– + 8H+ + 5Fe2+ Mn2+ + 4H2O + 5Fe3+
(ii) 2MnO4– + 2H2O + 5SO2 2Mn2+ + 4H+ + 5SO42–
–
COO
(iii) 2MnO4– + 16H+ + 5 | 2Mn2+ + 8H2O + 10CO2
–
COO
Q. 17. For M2+/M and M3+/M2+ systems, Eo values for some metals are as follows:
Cr2+/Cr = – 0.9 V Cr3+/Cr2+ = – 0.4 V
Mn2+/Mn = – 1.2 V Mn3+/Mn2+ = +1.5 V
Fe2+/Fe = – 0.4 V Fe3+/Fe2+= +0.8 V [CBSE Sample Paper 2016]
Use this data to comment upon
(i) the stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+.
(ii) the ease with which iron can be oxidised as compared to the similar process for either Cr or Mn
metals.
Ans. (i) Higher the reduction potential of a species, greater is the ease with which it undergo reduction. Among
these pairs, Mn3+/Mn2+ has largest positive reduction potential. Hence Mn3+ can be easily reduced to
Mn2+ i.e., Mn3+ is least stable. Cr3+/Cr2+ has a negative Eo value, therefore, Cr3+ is most stable. Fe3+/Fe2+
has a positive value but small. Hence, Fe3+ is more stable than Mn3+ but less stable than Cr3+.
(ii) Lower the reduction potential or higher the oxidation potential of a species, greater is the ease with
which it undergo oxidation. Among these pairs, Mn2+/Mn has the most negative reduction potential
or most positive oxidation potential. Therefore, it will be most easily oxidised. Thus, the decreasing
order of their ease of oxidation is Mn > Cr > Fe.
Q. 18. Predict which of the following will be coloured in aqueous solution?
Ti 3+, V 3+, Cu +, Sc 3+, Mn 2+, Fe 3+, Cq 2+ . Give reasons for each.
Ans. An ion is coloured when it has one or more unpaired electrons. Thus, Ti3+, V3+, Mn2+, Fe3+ and Co2+ are
coloured, due to the presence of unpaired electrons and d-d transitions. Cu+ and Sc3+ are colourless.
Q. 19. Compare the stability of +2 oxidation state for the elements of the first transition series.
Ans. Refer to Ans. 3. of NCERT Textbook Exercises.
Q. 20. Compare the chemistry of actinoids with that of lanthanoids with special reference to
(i) electronic configuration (ii) oxidation states
(iii) atomic and ionic sizes (iv) chemical reactivity.
OR
Give three points of difference between lanthanoids and actinoids. [CBSE 2020 (56/1/1)]
Ans. (i) Electronic configuration: The general electronic configuration of lanthanoids is [Xe]54 4f 1–14 5d 0 –1 6s2
whereas that of actinoids is [Rn]86 5f 1 – 14 6d 0 – 1 7s2. Thus, lanthanoids belong to 4f-series whereas
actinoids belong to 5f-series.

(ii) Oxidation states: Lanthanoids show limited oxidation states (+2, +3, +4), out of which, +3 is most
common. This is because of a large energy gap between 4f, 5d and 6s subshells. On the other hand,
actinoids show a large number of oxidation states because of small energy gap between 5f, 6d and 7s
subshells.
(iii) Atomic and ionic sizes: Both show decrease in size of their atoms or ions in +3 oxidation state. In
lanthanoids, the decrease is called lanthanoid contraction whereas in actinoids, it is called actinoid
contraction. However, the contraction is greater from element to element in actinoids due to poorer
shielding by 5f-electrons.
(iv) Chemical reactivity:
Lanthanoids: In general, the earlier members of the series are quite reactive (similar to calcium) but
with increasing atomic number, they behave more like aluminium.
Values for Eo for the half-reaction:
Ln3 +(aq) + 3e– Ln(s) Ln2O3
H2
bu
are in the range of –2.2 to –2.4 V except
rn
s
s
id
for Eu for which the value is –2.0 V. This
in
ac
O2
ith
is ofcourse, a small variation.
w
The metals combine with hydrogen when heated with S with halogens
gently heated in the gas. The carbides, Ln2S3 Ln LnX3
Ln3C, Ln2C3 and LnC2 are formed when
2
N
the metals are heated with carbon. They
ith
wi
w
th
liberate hydrogen from dilute acids and
2773 K
ed
with C
H2
at
O
he
burn in halogens to form halides. They
form oxides and hydroxides—M2O3 and
M(OH)3. The hydroxides are definite LnN Ln(OH)3 + H2
compounds, not just hydrated oxides, Ln3C, LnC2, Ln2C3
basic like alkaline earth metal oxides and Chemical reactions of the lanthanoids
hydroxides.
Actinoids: The actinoids are highly reactive metals, especially when finely divided. The action of
boiling water on them, for example, gives a mixture of oxide and hydride and combination with most
non-metals takes place at moderate temperatures. Hydrochloric acid attacks all metals but most are
slightly affected by nitric acid owing to the formation of protective oxide layers; alkalis have no action.
Actinoids are more reactive than lanthanoids due to bigger atomic size and lower ionisation energy.
Q. 21. How would you account for the following:
(i) Of the d 4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily
oxidised.
(iii) The d1 configuration is very unstable in ions.
Ans. (i) E° value for Cr3+/Cr2+ is negative (–0.41 V) whereas E° value for Mn3+/Mn2+ is positive (+1.57 V).
Thus, Cr2+ ions can easily undergo oxidation to give Cr3+ ions and, therefore, act as strong reducing
agent. On the other hand, Mn3+ can easily undergo reduction to give Mn2+ and hence act as oxidising
agent.
(ii) This is because in presence of complexing reagents the CFSE value compensates more than the third
ionisation energy of cobalt.
(iii) The ions with d 1 configuration have the tendency to lose the only electron present in d-subshell to acquire
stable d 0 configuration. Therefore, they are unstable and undergo oxidation or disproportionation.
Q. 22. What is meant by ‘disproportionation’? Give two examples of disproportionation reaction in aqueous
solution.
Ans. Disproportionation reactions are those reactions in which the same substance undergoes oxidation as well
as reduction. In disproportionation reaction, oxidation number of an element increases as well as decreases
to form two different products. For example,

VI VII IV
3MnO42– + 4H +
2MnO4– + MnO2 + 2H2O
V VI III
3CrO43– + 8H +
2CrO42– + Cr3+ + 4H2O
Q. 23. Which metal in the first transition series exhibits +1 oxidation state most frequently and why?
Ans. Cu has the electronic configuration 3d10 4s1. It can easily lose 4s1 electron to give the stable 3d10
configuration. Hence, it shows +1 oxidation state.
Q. 24. Calculate the number of unpaired electrons in the following gaseous ions:
(i) Mn3+, (ii) Cr3+, (iii) V3+ and (iv) Ti3+.
Which one of these is the most stable in aqueous solution?
Ans. (i) Mn3+ = 3d 4 = 4 unpaired electrons (ii) Cr3+ = 3d 3 = 3 electrons
3+ 2
(iii) V = 3d = 2 electrons (iv) Ti3+ = 3d 1 = 1 electron.
Cr3+ is the most stable in aqueous solution because it has half-filled t2g level (i.e., t32g).
Q. 25. Give example and suggest reasons for the following features of the transition metal chemistry:
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxo-anions of a metal.
Ans. (i) The lowest oxide of transition metal is basic because the metal atom has low oxidation state. This
means that it can donate valence electrons which are not involved in bonding to act like a base.
Whereas the highest oxide is acidic due to the highest oxidation state as the valence electrons are
involved in bonding and are unavailable. For example, MnO is basic whereas Mn2O7 is acidic.
(ii) A transition metal exhibits higher oxidation states in oxides and fluorides because oxygen and fluorine
are highly electronegative elements, small in size (and strongest oxidising agents). For example, osmium
shows an oxidation states of +6 in OsF6 and vanadium shows an oxidation state of +5 in V2O5.
(iii) Oxometal anions have the highest oxidation state, e.g., Cr in Cr2 O72– has an oxidation state of +6
whereas Mn in MnO 4– has an oxidation state of +7. This is again due to the combination of the metal
with oxygen, which is highly electronegative and oxidising element.
Q. 26. Indicate the steps in the preparation of
(i) K2Cr2O7 from chromite ore.
(ii) KMnO4 from pyrolusite ore.
Ans. (i) Refer to Basic Concepts Point 4(a).
(ii) Refer to Basic Concepts Point 4(b).
Q. 27. What are alloys? Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
Ans. An alloy is a homogeneous mixture of two or more metals, or metals and non-metals. An important alloy
containing lanthanoid metals is misch metal which contains 95% lanthanoid metals and 5% iron alongwith
traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets, shells and lighter flints.
Q. 28. What are inner-transition elements? Decide which of the following atomic numbers are the numbers
of the inner-transition elements: 29, 59, 74, 95, 102, 104.
Ans. The f-block elements, i.e., in which the last electron enters into f-subshell are called inner-transition
elements. These include lanthanoids (58–71) and actinoids (90–103). Thus, elements with atomic numbers
59, 95 and 102 are inner-transition elements.
Q. 29. The chemistry of the actinoid elements is not so smooth as that of the lanthanoids. Justify this
statement by giving some examples from the oxidation state of these elements.
Ans. Lanthanoids show a limited number of oxidation state, viz., +2, +3 and +4 (out of which +3 is the most
common). This is because of a large energy gap between 4f, 5d and 6s subshells. The dominant oxidation
state of actinoids is also +3 but they show a number of other oxidation states also, e.g., uranium (Z = 92)
and plutonium (Z = 94) show +3, +4, +5 and +6, neptunium (Z = 94) shows +3, +4, +5 and +7, etc. This is
due to small energy difference between 5f, 6d and 7s subshells of the actinoids.

Q. 30. Which is the last element of the series of the actinoids? Write the electronic configuration of this
element. Comment on the possible oxidation state of this element.
Ans. Last actinoid = Lawrencium (Z = 103)
Electronic configuration = [Rn]86 5f 14 6d 1 7s2
Possible oxidation state = +3
Q. 31. Use Hund’s rule to derive the electronic configuration of Ce3+ ion and calculate its magnetic moment
on the basis of spin only formula.
Ans. 58Ce = [Xe]54 4f 1 5d1 6s 2
Ce3+ = [Xe]54 4f 1, i.e., there is only one unpaired electron, i.e., n = 1.
Hence, µ = n (n 2) 1(1 2) = 3 = 1.73 BM
Q. 32. Name the members of the lanthanoid series which exhibit +4 oxidation states and those which exhibit
+2 oxidation states. Try to correlate this type of behaviour with the electronic configuration of these
elements.
Ans. + 4 = 58Ce, 59Pr, 60Nd, 65Tb, 66Dy
+ 2 = 60Nd, 62Sm, 63Eu, 69Tm, 70Yb
+2 oxidation state is exhibited when the lanthanoid has the configuration 5d 0 6s 2 so that 2 electrons are
easily lost. +4 oxidation state is exhibited when the configuration left is close to 4f 0 (e.g., 4f 0 , 4f 1, 4f 2) or
close to 4f 7 (e.g., 4f 7 or 4f 8 )
Q. 33. Compare the chemistry of the actinoids with that of landthanoids with reference to:
(i) electronic configuration (ii) oxidation states and
(iii) chemical reactivity
Ans.
S.No. Characteristics Lanthanoids Actinoids
(i) Electronic configuration [Xe] 4f 1 – 14 5d 0 – 1 6s2 [Rn] 5f 1 – 14 6d 0 – 1 7s2
(ii) Oxidation states Besides +3 O.S lanthanoids show Besides +3 O.S actinoids show higher O.S
+2 and +4 O.S only in a few cases. of +4, +5, +6, +7 also because of smaller
energy gap between 5f, 6d and 7s subshell.
(iii) General chemical These are less reactive metals. These are highly reactive metals.
reactivity of elements
Lesser tendency towards complex Greater tendency towards complex
formation. formation.
Do not form oxocation. Form oxocation.
Compounds are less basic. Compounds are more basic.
Q. 34. Write the electronic configurations of the elements with atomic numbers 61, 91, 101 and 109.
Ans. Z = 61 (Promethium, Pm), E.C. = [Xe] 4f 5 5d 0 6s2
Z = 91 (Protactium, Pa), E.C. = [Rn] 5f 2 6d 1 7s2
Z = 101 (Mendelevium, Md), E.C. = [Rn] 5f 13 6d 0 7s2
Z = 109 (Meitnerium, Mt), E.C. = [Rn] 5f 14 6d 7 7s2
Q. 35. Compare the general characteristics of the first series of transition metals with those of the second
and third series metals in the respective vertical columns on the basis of following points:
(i) electronic configurations, (ii) oxidation states,
(iii) ionisation enthalpies, and (iv) atomic sizes.
Ans. (i) Electronic configurations: The elements in the same vertical column generally have similar electronic
configurations. Although, the first series shows only two exceptions, i.e., Cr = [Ar] 3d 5 4s1 and
Cu = [Ar] 3d10 4s1 but the second series shows more exceptions, e.g., Mo(42) = [Kr] 4d5 5s1,
Ru(44) = [Kr] 4d7 5s1, Rh(45) = [Kr] 4d8 5s1, Pd(46) = [Kr] 4d10 5s 0, Ag(47) = [Kr] 4d10 5s1. Similarly,
in the third series, W(74) = [Xe] 4f 14 5d 4 6s 2, Pt(78) = [Xe] 4f 14 5d 9 6s1 and Au(79) = [Xe] 4f 14
5d10 6s1. Hence, in the same vertical column, in a number of cases, the electronic configuration of the
three series are not similar.

(ii) Oxidation states: The elements in the same vertical column generally show similar oxidation states.
The number of oxidation states shown by the elements in the middle of each series is maximum and
minimum at the extreme ends.
(iii) Ionisation enthalpies: The first ionisation enthalpies in each series generally increase gradually as
we move from left to right though some exceptions are observed in each series. The first ionisation
enthalpies of some elements in the second (4d) series are higher while some of them have lower value
than the elements of 3d- series in the same vertical column. However, the first ionisation enthalpies
of third (5d) series are higher than those of 3d and 4d- series. This is because of weak shielding of
nucleus of 4f-electrons in the 5d-series.
(iv) Atomic sizes: Generally, ions of the same charge or atoms in a given series show progressively
decrease in radius with increasing atomic number though the decrease is quite small. But the size of
the atoms of the 4d-series is larger than the corresponding elements of the 3d-series whereas those of
corresponding elements of the 5d-series are nearly the same as those of 4d-series due to lanthanoid
contraction.
Q. 36. Write down the number of 3d electrons in each of the following ions:
Ti2+, V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+.
Indicate how would you expect the five 3d-orbitals to be occupied for these hydrated ions (octahedral).
Ans. Ions Electronic No. of 3d 3d-orbitals occupied
Configurations electrons
e g
2+ 2 2
(i ) Ti [Ar]3d 2 t 2g t 2g
eg
2+ 3 3
(ii) V [Ar]3d 3 t 2g t 2g
eg
3+ 3 3
(iii) Cr [Ar]3d 3 t 2g t 2g
eg
2+ 5 3 2
(iv) Mn [Ar]3d 5 t 2g e g t 2g
eg
2+ 6 4 2
(v ) Fe [Ar]3d 6 t 2g e g t 2g
eg
3+ 5 3 2
(vi) Fe [Ar]3d 5 t 2g e g t 2g
eg
2+ 7 5 2
(vii) Co [Ar]3d 7 t 2g e g t 2g
eg
2+ 8 6 2
(viii) Ni [Ar]3d 8 t 2g e g t 2g
eg
2+ 9 6 3
(ix) Cu [Ar]3d 9 t 2g e g t 2g
Q. 37. Comment on the statement that elements of the first transition series possess many properties
different from those of heavier transition elements. [HOTS]
Ans. The given statement is true. Some evidences in support of this statement are:
(i) Atomic radii of the heavier transition elements (4d and 5d- series) are larger than those of the
corresponding elements of the first transition series though those of 4d and 5d- series are very close
to each other.
(ii) Ionisation enthalpies of 5d- series are higher than the corresponding elements of 3d and 4d- series.
(iii) Enthalpies of atomisation of 4d and 5d- series are higher than the corresponding elements of the first series.
(iv) Melting and boiling points of heavier transition elements are greater than those of the first transition
series due to stronger intermetallic bonding.

Q. 38. What can be inferred from the magnetic moment values of the following complex species?
Example Magnetic Moment (BM)
K4[Mn(CN)6] 2.2
[Fe(H2O)6]2+ 5.3
K2[MnCl4] 5.9
Ans. Magnetic moment (µ) = n (n + 2) BM
For n = 1, µ = 1 (1 2) 3 1.73; For n = 2, µ = 2(2 + 2) 8 2.83

For n = 3, µ = 3 (3 2) 15 3.87; For n = 4, µ = 4(4 + 2) 24 4.90
For n = 5, µ = 5 (5 2) 35 5.92

K4[Mn(CN)6]
Here, Mn is in +2 oxidation state, i.e., as Mn2+, µ = 2.2 BM shows that it has only one unpaired electron.
Hence, when CN – ligands approach Mn2+ ion, the electrons in 3d-subshell pair up.
Hence, CN – is a strong ligand. The hybridisation involved is d 2sp3 forming inner orbital octahedral complex.
3d 4s 4p
25Mn
3d 4s 4p
2+
Mn
3d 4s 4p
[Mn(CN)6] 4– XX = Electron pair from
XX XX XX XX XX XX –
CN ions
2 3
d sp hybrid
2+
[Fe(H2O)6]
Here, Fe is in +2 oxidation state, i.e., as Fe2+. µ = 5.3 BM shows that there are four unpaired electrons. This
means that the electrons in 3d-subshell do not pair up when the ligand H2O molecules approach. Hence,
H2O is a weak ligand. To accommodate the electrons donated by six H2O molecules, the hybridisation will
be sp 3d 2. Hence, it will be an outer orbital octahedral complex.
3d 4s 4p 4d
26Fe
3d 4s 4p 4d
2+
Fe
3d 4s 4p 4d
XX = Electron pair
[Fe(H2O)6]2+ XX XX XX XX XX XX from H2O
3 2
sp d hybrid
K2[MnCl4]
Here, Mn is in +2 state, i.e., as Mn2+. µ = 5.9 BM shows that there are five unpaired electrons. Hence, the
hybridisation involved will be sp 3 and the complex will be tetrahedral.
3d 4s 4p
2+
Mn
4s 4p
2– –
[MnCl4] XX XX XX XX XX = Electron pair from Cl ions
sp3 hybrid

Multiple Choice Questions [1 mark]
Choose and write the correct option(s) in the following questions.
1. Electronic configuration of a transition element X in +3 oxidation state is [Ar]3d 5. What is its atomic
number? [NCERT Exemplar]
(a) 25 (b) 26 (c) 27 (d) 24
2. Metallic radii of some transition elements are given below. Which of these elements will have highest
density?
Element Fe Co Ni Cu
Metallic radii/pm 126 125 125 128 [NCERT Exemplar]
(a) Fe (b) Ni (c) Co (d) Cu
3. Which of the following statements is not correct? [NCERT Exemplar]
(a) Copper liberates hydrogen from acids.
(b) In its higher oxidation states, manganese forms stable compounds with oxygen and fluorine.
(c) Mn3+ and Co3+ are oxidising agents in aqueous solution.
(d) Ti2+ and Cr2+ are reducing agents in aqueous solution.
4. Which of the following is amphoteric oxide?
Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4 [NCERT Exemplar]
(a) V2O5, Cr2O3 (b) Mn2O7, CrO3
(c) CrO, V2O5 (d) V2O5, V2O4
5. Which one of the following does not correctly represent the correct order of the property indicated
against it ?
(a) Ti < V < Cr < Mn, increasing number of oxidation states
(b) Ti < V < Mn < Cr, increasing second ionisation enthalpy
(c) Ti < V < Cr < Mn, increasing melting point
(d) Ti3+ < V3+ < Cr3+ < Mn3+, increasing magnetic moment
6. The magnetic moment is associated with its spin angular momentum and orbital angular momentum.
Spin only magnetic moment value of Cr3+ ion is ____________. [NCERT Exemplar]
(a) 2.87 B.M. (b) 3.87 B.M. (c) 3.47 B.M. (d) 3.57 B.M.
7. Transition elements show magnetic moment due to spin and orbital motion of electrons. Which of the
following metallic ions have almost same spin only magnetic moment? [NCERT Exemplar]
2+ 2+ 2+ 3+
(a) Co (b) Cr (c) Mn (d) Cr
8. The electronic configuration of Cu(II) is 3d 9 whereas that of Cu(I) is 3d10. Which of he following is
correct? [NCERT Exemplar]
(a) Cu(II) is more stable
(b) Cu(II) is less stable
(c) Cu(I) and Cu(II) are equally stable
(d) Stability of Cu(I) and Cu(II) depends on nature of copper salts
9. Generally transition elements form coloured salts due to the presence of unpaired electrons. Which
of the following compounds will be coloured in solid state? [NCERT Exemplar]
(a) Ag2SO4 (b) CuF2 (c) ZnF2 (d) Cu2Cl2
10. Which of the following statement about transition element is not correct?
(a) They show variable oxidation states.
(b) They exhibit diamagnetic and paramagnetic properties.
(c) All ions are coloured.
(d) They exhibit catalytic property.

11. On addition of small amount of KMnO4 to concentrated H2SO4, a green oily compound is obtained
which is highly explosive in nature. Identify the compound from the following. [NCERT Exemplar]
(a) Mn2O7 (b) MnO2 (c) MnSO4 (d) Mn2O3
12. Generally transition elements and their salts are coloured due to the presence of unpaired electrons
in metal ions. Which of the following compounds are coloured? [NCERT Exemplar]
(a) KMnO4 (b) Ce(SO4)2 (c) TiCl4 (d) Cu2Cl2
13. When KMnO4 solution is added to oxalic acid solution, the decolourisation is slow in the beginning
but becomes instantaneous after some time because [NCERT Exemplar]
(a) CO2 is formed as the product. (b) Reaction is exothermic.
(c) MnO 4– catalyses the reaction. (d) Mn2+ acts as autocatalyst.
14. Which of the following reactions are disproportionation reactions? [NCERT Exemplar]
(i) Cu + Cu 2+ + Cu
(ii) 3MnO 4 + 4H +
2–
2MnO 4– + MnO 2 + 2H 2 O
(iii) 2KMnO 4 K 2 MnO 4 + MnO 2 + O 2
2+
–
(iv) 2MnO 4 + 3Mn + 2H 2 O 5MnO 2 + 4H +

(a) (i), (ii) (b) (i), (ii), (iii) (c) (ii), (iii), (iv) (d) (i), (iv)
15. KMnO4 acts an oxidising agent in acidic medium. The number of moles of KMnO4 that will be
needed to react with one mole of sulphide ions in acidic solution is [NCERT Exemplar]
2 3 4 1

(a) (b) (c) (d)
5 5 5 5
16. KMnO4 acts as an oxidising agent in alkaline medium. When alkaline KMnO4 is treated with KI,
iodide ion is oxidised to ____________. [NCERT Exemplar]
– – –
(a) I2 (b) IO (c) IO3 (d) IO 4
17. Which of the following oxidation state is common for all lanthanoids? [NCERT Exemplar]
(a) +2 (b) +3 (c) +4 (d) +5
18. Gadolinium belongs to 4f series. It’s atomic number is 64. Which of the following is the correct
electronic configuration of gadolinium? [NCERT Exemplar]
(a) [Xe] 4f 7 5d 1 6s2 (b) [Xe] 4f 6 5d 2 6s2
(c) [Xe] 4f 8 6d 2 (d) [Xe] 4f 9 5s1
19. Identify the incorrect statement among the following:
(a) Lanthanoid contraction is the accumulation of successive shrinkages.
(b) There is a decrease in the radii of the atoms or ions as one proceeds from La to Lu.
(c) As a result of lanthanoid contraction, the properties of 4d series of the transition elements have no
similarities with the 5d series of elements.
(d) Shielding power of 4f electrons is quite weak.
20. Actinoids exhibit greater number of oxidation states than lanthanoids. The main reason being
(a) more energy difference between 5f and 6d than between 4f and 5f orbitals
(b) 4f orbitals are more diffused than the 5f orbitals
(c) lesser energy difference between 5f and 6d than between 4f and 5d orbitals
(d) more reactive nature of the actinoids than the lanthanoids.
Answers
1. (b) 2. (d) 3. (a) 4. (a) 5. (c) 6. (b) 7. (a, d) 8. (a) 9. (b) 10. (c)
11. (a) 12. (a, b) 13. (d) 14. (a) 15. (a) 16. (c) 17. (b) 18. (a) 19. (c) 20. (c)

Assertion-Reason Questions
In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement.
1. Assertion (A) : In transition elements ns orbital is filled up first and (n – 1)d afterwards, during ionization
ns electrons are lost prior to (n–1)d electrons.
Reason (R) : The effective nuclear charge felt by (n – 1)d electrons is higher as compared to that by
ns electrons.
2. Assertion (A) : Zn, Cd and Hg cannot be regarded as transition elements.
Reason (R) : These elements do not belong to the d-block of the periodic table.
3. Assertion (A) : Transition metals are strong reducing agents.
Reason (R) : Transition metals form numerous alloys with other metals.
4. Assertion (A) : Amongst Cu2+ and Cu+ ions, the more stable ions is Cu2+.
Reason (R) : For determination of stability of an ion its electrode potential is more important factor
than its electronic configuration.
5. Assertion (A) : Transition metals form complexes.
Reason (R) : Transition metals have unpaired electrons.
6. Assertion (A) : A solution of ferric chloride on standing gives a brown precipitate.
Reason (R) : FeCl3 possesses covalent bonds and chlorine bridge structure.
7. Assertion (A) : Members of 4d and 5d series of transition elements have nearly same atomic radii.
Reason (R) : Atomic and ionic radii for transition elements are smaller than their corresponding
s-block elements.
8. Assertion (A) : The most common oxidation state exhibited by actinoids is +2.
Reason (R) : All actinoids possess two electrons in 7s subshell.
9. Assertion (A) : Ce4+ is used as an oxidising agent in volumetric analysis.
Reason (R) : Ce4+ has the tendency of attaining +3 oxidation state.
10. Assertion (A) : The degree of complex formation in actinides decreases in the order
M 4+ > MO 22+ > M3+ > MO 2+
Reason
(R) : Actinides form complexes with p-bonding ligands such as alkyl phosphines and thioethers.
Answers
1. (a) 2. (c) 3. (d) 4. (b) 5. (b) 6. (b) 7. (b) 8. (d) 9. (a) 10. (b)
Passage-based/Case-based Questions
Read the given passages and answer the questions that follow.
PASSAGE–1
The d-block elements are those elements in which the last electron enters the d-subshell of the penultimate shell.
The general electronic configuration of these elements is (n – 1) d1–10 ns1–2, where n is outermost shell. The d-block
consisting of groups 3–12 occupies the large middle section of the periodic table. The elements of d-block are also

known as transition elements as they possess properties that are transitional between the s and p block elements. A
transition element is defined as an element which has incompletely filled d-orbitals in its ground state or any one
of its oxidation states. There are four series of transition elements spread between group 3 and 12. First transition
series or 3d-series: Scandium (21Sc) to Zinc (30Zn), Second transition series or 4d-series: Yttrium (39Y) to Cadmium
(48Cd), Third transition series or 5d-series: Lanthanum (57La) and Hafnium (72Hf) to Mercury (80Hg) (Omitting 58Ce
to 71Lu), Fourth transition series or 6d-series: Begins with Actinium (89Ac) is still incomplete.
1. In what way is the electronic configuration of transition elements different from that of the non-
transition elements?
Ans. Transition elements contain incompletely filled d-subshell, i.e., their electronic configuration is (n –1) d1–10 ns1–2
whereas non-transition elements have no d-subshell or their subshell is completely filled and have ns1–2 or
ns2 np1–6 in their outermost shell.
2. Why is zinc not regarded as a transition clement? [CBSE Guwahati 2015]
Ans. As zinc atom has completely filled d-orbitals (3d 10) in its ground state as well as in oxidised state, therefore,
it is not regarded as a transition element.
3. Why does a transition series contain 10 elements?
Ans. There are five d-orbitals in an energy level and each orbital can contain two electrons. As we move from one
element to the next, an electron is added and for complete filling of the five d-orbitals, 10 electrons are required.
4. Name the element which shows outer electronic configuration 3d 3 4s2.
Ans. Vanadium
5. What are interstitial compounds?
Ans. Interstitial compounds are those in which small atoms occupy the interstitial sites in the crystal lattice.
PASSAGE–2
Potassium permanganate, (KMnO4) is prepared by fusion of pyrolusite, MnO2 with KOH in the presence of an
oxidising agent like KNO3. This produces the dark green potassium manganate, K2MnO4 which disproportionates
in a neutral or acidic solution to give purple permanganate ion. Potassium permanganate is an important oxidising
agent in acidic, alkaline as well as neutral medium.
1. What is the state of hybridisation of Mn in MnO4– ?
Ans. sp3
2. Write an application of potassium permanganate.
Ans. It is used for the estimation of hydrogen peroxide.
3. What are the products formed after heating potassium permanganate?
Ans. K2MnO4, O2 and MnO2 will be formed after heating of potassium permanganate.
4. How many electrons are involved in oxidation by KMnO4 in an acidic medium?
Ans. Five electrons are involved in oxidation by KMnO4 in an acidic medium.
5. Draw the structure of permanganate ion. Is it paramagnetic or diamagnetic?
O
Ans. Mn
O O–
O
Tetrahedral permanganate ion
(purple)
It is diamagnetic.
Very Short Answer Questions [1 mark]
Q. 1. Copper atom has completely filled d-orbitals in its ground state but it is a transition element. Why?
[CBSE Chennai 2015]
Ans. Copper exhibits +2 oxidation state wherein it has incompletely filled d orbitals (3d 4s 0) hence, a transition
9
element.

Q. 2. Give reason:
Zn is soft whereas Cr is hard. [CBSE South 2016]
Ans. Cr (3d 5 4s 1) has five unpaired electrons in its d-orbitals whereas Zn (3d 10 4s 2) has no unpaired electrons in
its d-orbitals. As a result of this weak metallic bonds exist in Zn whereas strong metallic bonds exist in Cr.
Hence, Zn is soft whereas Cr is hard.
Q. 3. Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain. [NCERT Exemplar]
Ans. It is due to regular increase in ionisation enthalpy.
Q. 4. Arrange the following in increasing order of acidic character: [HOTS]
CrO3, CrO, Cr2O3
Ans. CrO < Cr2O3 < CrO3. Higher the oxidation state, more will be acidic character.
Q. 5. Why does copper not replace hydrogen from acids? [NCERT Exemplar]
Ans. Cu shows Eo positive value.
Q. 6. Which divalent metal ion has maximum paramagnetic character among the first transition metals?
Why?
Ans. Mn2+ has the maximum paramagnetic character because of the maximum number of unpaired electrons, viz., 5.
Q. 7. Although Cr3+ and Co2+ ions have same number of unpaired electrons but the magnetic moment of
Cr3+ is 3.87 BM and that of Co2+ is 4.87 BM. Why? [NCERT Exemplar] [HOTS]
Ans. Due to symmetrical electronic configuration there is no orbital contribution in Cr3+ ion. However,
appreciable orbital contribution takes place in Co2+ ion.
Q. 8. Out of Cu2Cl2 and CuCl2, which is more stable and why? [NCERT Exemplar] [HOTS]
Ans. CuCl2 is more stable than Cu2Cl2. The stability of Cu2+(aq) is more than Cu+(aq) due to the much more
negative ∆hyd.Ho of Cu2+(aq) than Cu+(aq).
Q. 9. Zn2+ salts are white while Cu2+ salts are coloured. Why? [CBSE Patna 2015]
Ans. Cu2+ (3d 9 4s 0) has one unpaired electron in d-subshell which absorbs radiation in visible region resulting
in d-d transition and hence Cu2+ salts are coloured. Zn2+ (3d 10 4s 0) has completely filled d-orbitals. No
radiation is absorbed for d-d transition and hence Zn2+ salts are colourless.
Q. 10. Write any one use of pyrophoric alloys.
Ans. Pyrophoric alloys emit sparks when struck. Hence, they are used in making flints for lighters.
Short Answer Questions–I [2 marks]

Q. 1. Use the data to answer the following and also justify giving reason: [CBSE 2019 (56/4/1)]
Cr Mn Fe Co
o
EM 2+
/M
–0.91 –1.18 –0.44 –0.28
o
EM 3+
/M2+
–0.41 –1.57 –0.77 +1.97
(i) Which is a stronger reducing agent in aqueous medium, Cr2+ or Fe2+ and why?
(ii) Which is the most stable ion in +2 oxidation and why?
Ans. (i) Cr2+, due to lower standard reduction potential (Eo)/Higher standard oxidation potential.
(ii) Mn2+, due to highest negative standard reduction potential.
Q. 2. In the following ions:
Mn3+, V3+, Cr3+, Ti4+
(Atomic no. : Mn = 25, V = 23, Cr = 24, Ti = 22)
(i) Which ion is most stable in an aqueous solution?
(ii) Which ion is the strongest oxidizing agent?
(iii) Which ion is colourless?
(iv) Which ion has the highest number of unpaired electrons? [CBSE (F) 2017]
Ans. (i) Cr3+ because of half filled t2g level.

(ii) Mn3+, as the change from Mn3+ to Mn2+ results in stable half filled (d 5) configuration.
(iii) Ti4+, as Ti4+ has empty d-orbitals therefore d-d transition cannot occur in Ti4+.
(iv) Mn3+ (3d 44s0). It has 4 unpaired electrons.
Q. 3. Give reasons for the following:
(i) Eo values of Mn, Ni and Zn are more negative than expected.
(ii) [Ti(H2O)]3+ is coloured while [Sc(H2O)6]3+ is colourless. [HOTS]
OR
Ti3+ is coloured whereas Sc3+ is colourless in aqueous solution. [CBSE 2020 (56/5/1)]
o 2+ 2+
Ans. (i) Negative E values for Mn and Zn are related to stabilities of half-filled and fully filled configurations,
respectively. But for Ni2+, Eo value is related to the highest negative enthalpy of hydration.
(ii) This is due to d-d transition of electron in [Ti(H2O)6]3+ complex. Ti3+ has one electron in d-orbital
(3d1) which absorbs energy corresponding to blue-green region and jumps from t2g to eg set of
d-orbitals (t 12g e 0g t 02g e 1g ). But Sc3+ has no electron in the d-orbital.
Q. 4. How would you account for the following:
(i) Mn (III) undergoes disproportionation reaction easily.
(ii) Co (II) is easily oxidised in the presence of strong ligands. [CBSE (F) 2011]
Ans. (i) Mn3+ is less stable and changes to Mn2+ which is more stable due to half filled d-orbital configuration.
That is why, Mn3+ undergoes disproportionation reaction.
(ii) Co (II) has electronic configuration 3d 7 4s0, i.e., it has three unpaired electrons. In the presence of
strong ligands, two unpaired electrons in 3d-subshell pair-up and third unpaired electron shifts to
higher energy subshell from where it can be easily lost and hence oxidised to Co(III).
Q. 5. When FeCr2O4 is fused with Na2CO3 in the presence of air it gives a yellow solution of compound (A).
Compound (A) on acidification gives compound (B). Compound (B) on reaction with KCl forms an
orange coloured (C). An acidified solution of compound (C) oxidises Na2SO3 to (D). Identify (A), (B),
and (D.) [CBSE 2019 (56/2/1)]
Ans. A = Na 2 CrO 4 , B = Na 2 Cr2 O 7 , C = K2 Cr2 O 7 , D = Na 2 SO 4
Sodium chromate Sodium dichromate Potassium dichromate Sodium sulphate
Q. 6. Complete the following chemical reaction equations:
(i) MnO4– (aq) + C2O42– (aq) + H+ (aq)
(ii) Cr2O72– (aq) + Fe2+ (aq) + H+ (aq)
Ans. (i) [MnO4– + 8H+ + 5e– Mn2+ + 4H2O] × 2
[C2O42– 2CO2 + 2e– ] × 5
MnO4– + 5C2O42– + 16H+ 2Mn2+ + 10CO2 + 8H2O
(ii) Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Fe2+ Fe3+ + e– ] × 6
Cr2O72– + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O
Q. 7. Complete the following chemical equations:
(i) 8MnO4– + 3S2O32– + H2O
(ii) Cr2O72– + 3Sn2+ + 14H+ [CBSE Delhi 2016]
Ans. (i) 8MnO4– + 2H2O + 3e– MnO2 + 4OH– ] × 8
S2O32– + 10OH– 2SO42– + 5H2O + 8e– ] × 3
8MnO4– + 3S2O32– + H2O 8MnO2 + 6SO42– + 2OH–
(ii) Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O

Sn2+ Sn4+ + 2e– ] × 3
Cr2O72– + 3Sn2+ + 14H+
2Cr3+ + 3Sn4+ + 7H2O

Q. 8. Complete and balance the following equations: [CBSE 2019 (56/5/2)]
(i) MnO 4– + I – + H +
(ii) Na 2 Cr2 O7 + KCl
+ +
Ans. (i) 2MnO 4– + 10I – + 16H 2Mn 2 + 8H 2 O + 5I 2
(ii) Na 2 Cr2 O 7 + 2KCl K 2 Cr2 O 7 + 2NaCl
Q. 9. Transition metals can act as catalysts because these can change their oxidation state. How does
Fe(III) catalyse the reaction between iodide and persulphate ions? [NCERT Exemplar]
Ans. Reaction between iodide and persulphate ions is:
Fe (III)
2I – + S2O82– I2 + 2SO42–
Role of Fe(III) ions:
2Fe3+ + 2I – 2Fe2+ + I2
2Fe2+ + S2O82– 2Fe3+ + 2SO42–
Q. 10. Explain each of the following observations:
(i) Mn2+ is much more resistant than Fe2+ towards oxidation. [CBSE Delhi 2012]
(ii) Among lanthanoids, Ln(III) compounds are predominant. However, occasionally in solutions
or in solid compounds, +2 and +4 ions are also obtained. [CBSE (AI) 2012]
Ans. (i) Mn3+(d 4) is less stable than Mn2+ (d 5, half filled) while Fe3+ (d 5, half filled) is more stable than
Fe2+ (d 4). That is why Mn2+ is more resistance than Fe2+ towards oxidation.
(ii) Lanthanoid metals show +2 and +4 oxidation states to attain extra stable f 0 and f 7 configurations.
Q. 11. Explain each of the following observations:
(i) Actinoids exhibit a much larger number of oxidation states than the lanthanoids.
[CBSE 2019 (56/2/1)]
(ii) There is hardly any increase in atomic size with increasing atomic numbers in a series of
transition metals. [CBSE (F) 2012]
Ans. (i) This is due to small energy gap between 5f, 6d and 7s subshells in actinoids.
(ii) This is because with increase in atomic number in a series, the increased nuclear charge is partly
cancelled by the increased shielding effect of electrons in the d-orbitals of penultimate shell.
Short Answer Questions–II [3 marks]

Q. 1.
Cr Mn Fe Co Ni Cu
E oMn2+/Mn
– 0.91 – 1.18 – 0.44 – 0.28 – 0.25 +0.34
From the given data of Eo values, answer the following questions:

(i) Why is E o(Cu2+/Cu) value exceptionally positive?
(ii) Why is E o(Mn2+/Mn) value highly negative as compared to other elements?
(iii) Which is a stronger reducing agent Cr2+ or Fe2+ ? Give reason. [CBSE Patna 2015] [HOTS]
Ans. (i) Copper has high enthalpy of atomisation and low enthalpy of hydration. Since the high energy
to transform Cu(s) to Cu2+(aq) is not balanced by hydration enthalpy, therefore, E oCu2+/Cu value is
exceptionally positive.
(ii) This is due to extra stability of half-filled 3d-orbitals of Mn2+(3d 5).
(iii) Refer to NCERT Intext Questions, Q. 7.

Q. 2. The elements of 3d transition series are given as:
Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn [CBSE East 2016]
Answer the following:
o
(i) Copper has exceptionally positive E M 2+
/M
value. Why?
(ii) Which element is a strong reducing agent in +2 oxidation state and why?
(iii) Zn2+ salts are colourless. Why?
(i) Because the sum of sublimation enthalpy and hydration enthalpy to convert Cu(s) to Cu2+(aq) is so
Ans.
high that it is not balanced by its hydration enthalpy.
(ii) Cr is strongest reducing agent in +2 oxidation state. Cr2+ has configuration 3d 4. After losing one
electron it forms Cr3+ which has stable half filled t2g level.
(iii) Zn2+(3d 10) has completely filled d-orbitals. As a result of this, d-d transition cannot occur and hence,
Zn2+ salts are colourless.
Q. 3. (i) For M2+/M and M3+/M2+ systems, Eo values for some metals are as follows:
Cr2+/Cr = – 0.9 V Cr3+/Cr2+ = – 0.4 V
Mn2+/Mn = – 1.2 V Mn3+/Mn2+ = +1.5 V
Fe2+/Fe = – 0.4 V Fe3+/Fe2+ = +0.8 V
Use this data to comment upon
(a) the stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+.
(b) the ease with which iron can be oxidised as compared to the similar process for either Cr or
Mn metals.
(ii) What can be inferred from the magnetic moment of the complex K4[Mn(CN)6], Magnetic
moment: 2.2 BM? [CBSE Sample Paper 2016]
Ans. (i) (a) Higher the reduction potential of a species, greater is the ease with which it undergo reduction.
Among these pairs, Mn3+/Mn2+ has largest positive reduction potential. Hence Mn3+ can be easily
reduced to Mn2+ i.e., Mn3+ is least stable. Cr3+/Cr2+ has a negative E° value, therefore, Cr3+ is
most stable. Fe3+/Fe2+ has a positive value but small. Hence, Fe3+ is more stable than Mn3+ but
less stable than Cr3+.

(b) Lower the reduction potential or higher the oxidation potential of a species, greater is the ease
with which it undergo oxidation. Among these pairs, Mn2+/Mn has the most negative reduction
potential or most positive oxidation potential. Therefore, it will be most easily oxidised. Thus, the
decreasing order of their ease of oxidation is Mn > Cr > Fe.
(ii) In the complex K4[Mn(CN)6], Mn is in +2 oxidation state. Magnetic moment 2.2 BM indicates that
it has only one unpaired electron and hence forms inner orbital or low spin octahedral complex. In
presence of CN–, a strong ligand the hybridisation involved is d2sp3.
Q. 4. Account for the following:
(i) Eu2+ is a strong reducing agent.
(ii) Orange colour of dichromate ion changes to yellow in alkaline medium.
(iii) EoM2+/M values for transition metals show irregular variation. [CBSE (F) 2017]
2+ 3+
Ans. (i) This is because Eu tends to change to Eu as +3 is the common oxidation state of lanthanoids.
(ii) In alkaline medium, the orange colour of the solution changes to yellow due to conversion of
dichromate (Cr2O72–) ion to chromate (CrO42–) ion.
Cr2 O72– + 2OH – 2CrO 24– + H 2 O
Orange Yellow
(iii) The irregularity is due to the irregular variation of ionisation enthalpies (∆iH + ∆iH2) and also the
sublimation enthalpies which are relatively much less for Mn (240 kJ mol–1) and V (470 kJ mol–1).

Q. 5. Complete the following reactions: [CBSE 2019 (56/4/1)]
(i) MnO 2 + KOH + O 2
+
(ii) I – + MnO 4– + H
+ +
(iii) Cr2 O 72– + Sn 2 + H
Ans. (i) 2MnO 2 + 4KOH + O 2 2K 2 MnO 4 + 2H 2 O
+ +
(ii) 10I – + 2MnO 4– + 16H 2Mn 2 + 8H 2 O + 5I 2
+ 2+ + +
(iii) Cr2 O 2–
7 + 14H + 3Sn 2Cr3 + 3Sn 4 + 7H 2 O
Q. 6. When a brown compound of manganese (A) is treated with HCl it gives a gas (B). The gas taken in
excess, reacts with NH3 to give an explosive compound (C). Identify compounds A and B.
[NCERT Exemplar] [HOTS]
Ans. A = MnO2 [Manganese (IV) oxide]
B = Cl2 (Chlorine)
C = NCl3 (Nitrogen trichloride)
MnO2 4 HCl

MnCl2 Cl2 2 H 2 O
(A) ( B)
NH3 + 3Cl 2 NCl3 + 3HCl

(excess) (C)
Q. 7. A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or a

green solution depending on pH of the solution. What different stages of the reduction do these
represent and how are they carried out? [NCERT Exemplar]
Ans. Oxidising behaviour of KMnO4 depends on pH of the solution.
In acidic medium (pH < 7),
+ +
MnO 4– + 8H + 5e – Mn 2 + 4H 2 O
^Colourless h
In alkaline medium (pH > 7),

MnO 4– + e – MnO 2–
4
^Green h
In neutral medium (pH = 7),
MnO 4– + 2H 2 O + 3e – MnO 2 + 2OH –
^ Brqwn precipitate h
Q. 8. (i) How would you account for the following:

(a) Highest fluoride of Mn is MnF4 whereas the highest oxide is Mn2O7.
(b) Transition metals and their compounds show catalytic properties. [CBSE 2020 (56/5/1)]
(ii) Complete the following equation:
+
3MnO 42– + 4H [CBSE (F) 2015]
Ans. (i) (a) As oxygen stabilises manganese more than fluorine by forming multiple bonds.
(b) The catalytic activity of transition metals and their compounds is attributed to the following
reasons:
OO Due to their tendency to show variable oxidation states transition metals form unstable
intermediate compounds and provide a new path for the reaction with lower activation energy.
OO In some cases, the transition metals provide a suitable large surface area with free valencies
on which reactants are adsorbed.
(ii) 3MnO 24– + 4H + 2MnO 4– + MnO 2 + 4H 2 O

Manganate ion Permanganate ion

Q. 9. Explain the following observations:
(i) The enthalpies of atomisation of transition metals are quite high.
(ii) There is a close similarity in physical and chemical properties of the 4d and 5d series of the
transition elements, much more than expected on the basis of usual family relationship.
(iii) The members in the actinoid series exhibit larger number of oxidation states than the
corresponding members in the lanthanoid series. [NCERT Exemplar]
Ans. (i) This is because transition metals have strong metallic bonds as they have large number of unpaired
electrons.
(ii) This is because 5d and 4d-series elements have virtually the same atomic and ionic radii due to
lanthanoid contraction. Due to equality in size of Zr and Hf, Nb and Ta, Mo and W, etc., the two
elements of each pair have the same properties.
(iii) The members in the actinoid series exhibit larger number of oxidation states than the corresponding
members in the lanthanoid series due to the fact that the 5f, 6d and 7s levels are of comparable
energies.
Q. 10. Account for the following:
(i) Mn2O7 is acidic whereas MnO is basic.
(ii) Though copper has completely filled d-orbital (d 10) yet it is considered as a transition metal.
(iii) Actinoids show wide range of oxidation states. [CBSE (F) 2016]
Ans. (i) Mn has + 7 oxidation state in Mn2O7 and + 2 in MnO. In low 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. On the other hand, in higher oxidation state of the metal, valence electrons are
involved in bonding and are not available. Instead effective nuclear charge is high and hence it can
accept electrons and behave as an acid.
(ii) Copper exhibits +2 oxidation state wherein it will have incompletely filled d-orbitals (3d 9), hence a
transition metal.
(iii) This is due to comparable energies of 5f, 6d and 7s orbitals.
Long Answer Questions [5 marks]

Q. 1. (i) The elements of 3d transition series are given as:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Answer the following:
(a) Which element has the highest m.p. and why?
(b) Which element is a strong oxidising agent in +3 oxidation state and why?
(c) Which element is soft and why?
(ii) Write the equations involved in the preparation of potassium dichromate from sodium chromate
(Na2CrO4). [CBSE (F) 2016]
Ans. (i) (a) Cr, the highest melting point of Cr is attributed to the involvement of greater number of electrons(5)
from 3d in addition to 4s electrons in interatomic metallic bonding.
(b) Mn, because the change from Mn3+ (d 4) to Mn2+ (d 5) results in the half filled configuration which

has extra stability.
(c) Zn, in Zn (3d 10 4s 2) all the electrons present in d-orbitals are paired and hence metallic bonds

present in it are weak. That is why, it is soft.
(ii) Sodium chromate is acidified with sulphuric acid to give a solution from which orange sodium
dichromate, Na2Cr2O7.2H2O can be crystallised.
2Na2CrO4 + 2H+ Na2Cr2O7 + 2Na+ + H2O

Sodium dichromate is more soluble than potassium dichromate. The latter is therefore, prepared by
treating the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl
Q. 2.
(i) Is the variability in oxidation number of transition elements different from that of non-transition
elements? Illustrate with examples.
(ii) Give reasons:
(a) d-block elements exhibit more oxidation states than f-block elements.
(b) Orange solution of potassium dichromate turns yellow on adding sodium hydroxide to it.
(c) Zirconium (Z = 40) and Hafnium (Z = 72) have almost similar atomic radii.
[CBSE Sample Paper 2017]
Ans. (i) In transition elements, the oxidation states differ from each other by unity, e.g., Fe3+ and Fe2+ etc.,
while in non-transition elements (p-block elements), the oxidation states differ by two, e.g., Pb4+ and
Pb2+, etc.
In transition elements the higher oxidation states are more stable for the heavier elements in a group,
e.g., Mo(VI) is more stable than Cr(VI) whereas in non-transition elements (p-block elements), the
lower oxidation states are more stable for heavier elements due to inert pair effect, e.g., Pb(II) is more
stable than Pb(IV).
(ii) (a) d–block elements exhibit more oxidation states because of less energy gap between d and
s subshell whereas f-block elements have large energy gap between f and d subshell.

(b) On adding NaOH, pH of solution increases and the orange colour of the solution changes to
yellow due to conversion of dichromate ion to chromate ion.
Cr2 O72– + 2OH – 2CrO 24– + H 2 O
Dichromate ion Chromate ion
(Orange) (Yellow)
(c) This is due to filling of 4f-orbitals which have poor shielding effect (Lanthanoid contraction).
Q. 3. (i) Describe the preparation of potassium permanganate from pyrolusite ore. Write balanced
chemical equation for one reaction to show the oxidizing nature of potassium permanganate.
(ii) Draw the structures of chromate and dichromate ions. [CBSE Sample Paper 2017]
Ans. (i) Conversion of pyrolusite (MnO2) into potassium manganate (K2MnO4).
2MnO 2 + 4KOH + O 2 2K 2 MnO 4 + 2H 2 O

Electrolytic oxidation:

K 2 MnO 4 2K + + MnO 2–
4
At anode: MnO 24– MnO 4– + e –

At cathode: H+ + e – H, 2H H2
It oxidises oxalate (C2O42–) to carbon dioxide (CO2) in acidic medium.
MnO 4– + 8H + + 5e – Mn 2+ + 4H 2 O] # 2
C 2 O 24– 2CO 2 + 2e –] # 5
2MnO 4– + 5C 2 O 24– + 16H + 2Mn 2+ + 10CO 2 + 8H 2 O
(ii) O O O
Cr Cr Cr
– – –
O O O O O–
O O O
Chromate ion Dichromate ion

Q. 4. (i)Compare non transition and transition elements on the basis of their
(a) Variability of oxidation states
(b) Stability of oxidation states.
(ii) Give chemical reactions for the following observations:
(a) Potassium permanganate is a good oxidising agent in basic medium.
(b) Inter convertibility of chromate ion and dichromate ion in aqueous solution depends upon
pH of the solution.
(c) Potassium permanganate is thermally unstable at 513K. [CBSE Sample Paper 2013]
Ans. (i) (a) Oxidation states of transition elements differ from each other by unity. In non-transition elements
oxidation states normally differ by a unit of two.
(b) In transition elements higher oxidation states are favoured by heavier elements whereas in non-
transition elements lower oxidation state is favoured by heavier elements.
(ii) (a) MnO 4– + 2H 2 O + 3e – MnO 2 + 4OH –] # 2
I – + 6OH – IO3– + 3H 2 O + 6e –
2MnO 4– + I – + H 2 O IO3– + 2MnO 2 + 2OH –
Acid (pH less than 7
(b) 2CrO 24– + 2H +
Cr2 O72– + H 2 O
Alkali (pH more than 7)
513 K

(c) 2KMnO 4 K 2 MnO 4 + MnO 2 + O 2
Q. 5.
(i) In the titration of FeSO4 with KMnO4 in the acidic medium, why is dil. H2SO4 used instead of
dil. HCl?
(ii) Give reasons:
(a) Among transition metals, the highest oxidation state is exhibited in oxoanions of a metal.
(b) Ce4+ is used as an oxidising agent in volumetric analysis. [CBSE 2019(56/2/3)]
2+ 2+
(c) Zn salts are white while Cu salts are blue.
OR
Why is Cu2+ ion coloured while Zn2+ ion is colourless in aqueous solution?[CBSE 2020 (56/3/1)]
Ans.
(i) Dil. H2SO4 is an oxidising agent and oxidises FeSO4 to Fe2(SO4)3. Dil. HCl is a reducing agent and
liberates chlorine on reacting with KMnO4 solution.
Hence, the part of the oxygen produced from KMnO4 is used up by HCl.
(ii) (a) In these oxoanions the oxygen atoms are directly bonded to the transition metal.
Since oxygen is highly electronegative, the oxoanions bring out the highest oxidation state of the
metal.
(b) Ce4+ has the tendency to attain +3 oxidation state which is more stable and so it is used as an
oxidising agent in volumetric analysis.
(c) Zn2+ ion has all its orbitals completely filled whereas in Cu2+ ion there is one half-filled 3d-orbital.
Therefore, due to d-d transition Cu2+ has a tendency to form coloured salts whereas Zn2+ has no
such tendency.
Q. 6. A violet compound of manganese (A) decomposes on heating to liberate oxygen and compounds (B)
and (C) of manganese are formed. Compound (C) reacts with KOH in the presence of potassium
nitrate to give compound (B). On heating compound (C) with conc. H2SO4 and NaCl, chlorine gas is
liberated and a compound (D) of manganese along with other products is formed. Identify compounds
A to D and also explain the reactions involved. [NCERT Exemplar] [HOTS]
Ans. A = KMnO4 (Potassium permanganate), B = K2MnO4 (Potassium manganate),
C = MnO2 (Manganese (IV) oxide), D = MnCl2 (Manganese (II) chloride)
D
2KMnO 4 K 2 MnO 4 + MnO 2 + O 2
( A) (B) (C)

MnO2 2KOH KNO3
K 2 MnO 4 H 2 O KNO2
(C) ( B)
MnO 2 + 4NaCl + 4H 2 SO 4 MnCl 2 + 4NaHSO 4 + 2H 2 O + Cl 2

( D)
Q. 7. When an oxide of manganese (A) is fused with KOH in the presence of an oxidising agent and
dissolved in water, it gives a dark solution of compound (B). Compound (B) disproportionates in
neutral or acidic solution to give purple compound (C). An alkaline solution of compound (C) oxidises
potassium iodide solution to a compound (D) and compound (A) is also formed. Identify compounds
A to D and also explain the reactions involved. [NCERT Exemplar] [HOTS]
Ans. A = MnO2 (Manganese (IV) oxide), B = K2MnO4 (Potassium manganate),

C = KMnO4 (Potassium permanganate), D = KIO3 (Potassium iodate)
2MnO 2 + 4KOH + O 2 2K 2 MnO 4 + 2H 2 O
( A) (B)
3K 2 MnO 4 4 H
2KMnO 4 MnO2 2 H 2 O 4K
(C)
2MnO 4– + H 2 O + KI 2MnO 2 + 2OH – + KIO3

( A) ( D)
Q. 8. (i)
Write balanced equations to represent what happens when
(a) Cu2+ is treated with KI.
(b) Acidified potassium dichromate solution is reacted with iron (II) solution. (ionic equation)
(ii)
(a) The figure given illustrates the first ionization enthalpies of first, second and third series of
transition elements. Answer the question that follows:
Which series amongst the first, second and third series of transition elements have the
highest first ionization enthalpy and why?
(b) Separation of lanthanoid elements is difficult. Explain. [CBSE 2020 (56/5/1)]
2+ 2+ 2+
(c) Sm , Eu and Yb ions in solutions are good reducing agents but an aqueous solution of
Ce4+ is a good oxidising agent. Why? [CBSE Sample Paper 2015]
900 Ir
Au
Os
Pt 3rd series
800 Pd
W Re
Hf Ta Fe
Co
I.E 1 (kJ mol –1)
Cu 1st series
Mn Ni
Ru
700 Mo Rh
Zr Ag 2nd series
Nb Tc
Ti
V Cr
TRANSITION ELEMENTS
Ans. (i) (a) 2Cu 2+ + 4I – Cu 2 I 2 + I 2

(b) Cr2 O72– + 14H + + 6e –
2Cr3+ + 7H 2 O
Fe 2+ Fe3+ + e –] # 6
Cr2 O72– + 6Fe 2+ + 14H + 2Cr3+ + 6Fe3+ + 7H 2 O
(ii) (a) Third series has the highest first ionization energy due to poorest shielding effect of the fully filled
4f subshell.

(b) Due to lanthanoid contraction, some pair of elements have almost similar size and as a result, such
pairs have very similar properties which makes their separation difficult.
(c) Sm2+, Eu2+ and Yb2+ ions are good reducing agents as they tend to acquire common oxidation
state of + 3 shown by lanthanoids by the loss of one electron while Ce4+ gains one electron to
attain + 3. Hence, Ce4+ is an oxidising agent.
Q. 9. (i) Account for the following:
(a) Transition metals form large number of complex compounds. [CBSE 2019 (56/2/1)]
(b) The lowest oxide of transition metal is basic whereas the highest oxide is amphoteric or acidic.
(c) Eo value for the Mn3+/Mn2+ couple is highly positive (+ 1.57 V) as compare to Cr3+/Cr2+.
(ii) Write one similarity and one difference between the chemistry of lanthanoid and actinoid
elements. [CBSE Delhi 2017]
Ans. (i) (a) The tendency to form complex compounds is due to:
—Small size and high charge on metal ion.
—The availability of d orbitals for accommodating electrons donated by the ligand.
(b) In low 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. On the other hand,
in higher oxidation state of the metal, valence electrons are involved in bonding and are not
available. Instead effective nuclear charge is high and hence it can accept electrons and behave as
an acid.
(c) Much large third ionisation energy of Mn (where the required change is stable half filled d 5 to d 4)
is mainly responsible for this.
(ii) Similarities
— Both show mainly an oxidation state of +3.
— Actinoids show actinoid contraction like lanthanoid contraction is shown by lanthanoids.
— Both are electropositive and very reactive. (Any one)
Differences
— Except promethium (Pm) lanthanoids are non-radioactive whereas actinoids are radioactive.
— Lanthanoids do not form oxocation whereas actinoids form oxocation.
— Lanthanoids have less tendency towards complex formation whereas actinoids have greater
tendency towards complex formation. (Any one)
Q. 10. Assign reasons for the following:
(i) The enthalpies of atomisation of transition elements are high.
(ii) The transition metals and many of their compounds act as good catalysts.
(iii) From element to element, the actinoid contraction is greater than the lanthanoid contraction.
(iv) The E0 value for the Mn3+/Mn2+ couple is much more positive than that of Cr3+/Cr2+.
(v) Scandium (Z = 21) does not exhibit variable oxidation states and yet it is regarded as a transition
element. [CBSE 2019 (56/2/3)]
Ans. (i) This is because transition metals have strong metallic bonds as they have a large number of unpaired
electrons.
(ii) The catalytic activity of transition metals is attributed to the following reasons:
(a) Because of their variable oxidation states, transition metals form unstable intermediate compounds
and provide a new path with lower activation energy for the reaction.
(b) In some cases, the transition metal provides a 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-electrons in the lanthanoids.
(iv) This is due to much larger third ionisation energy of Mn as Mn2+ is very stable on account of stable
d 5 configuration.
(v) This is because scandium has partially filled d-orbitals in the ground state (3d 1 4s 2).

Self-Assessment Test
Time allowed: 1 hour Max. marks: 30
Choose and write the correct answer for each of the following. (3 × 1 = 3)
1. Why is HCl not used to make the medium acidic in oxidation reactions of KMnO4 in
acidic medium?
(a) Both HCl and KMnO4 act as oxidising agents.
(b) KMnO4 oxidises HCl into Cl2 which is also an oxidising agent.
(c) KMnO4 is a weaker oxidising agent than HCl.
(d) KMnO4 acts as a reducing agent in the presence of HCl.
2. Which element among the lanthanides has the smallest atomic radius?
(a) Cerium (b) Lutetium
(c) Europium (d) Gadolinium
3. In acidic medium, one mole of MnO4 ion accepts how many moles of electrons in a redox
–
process?
(a) 1 (b) 2
(c) 5 (d) 6
In the following questions, two statements are given—one labeled Assertion (A) and the other labeled
Reason (R). Select the correct answer to these questions from the codes (a), (b), (c) and (d) as given below:
(a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct explanation of
the Assertion (A).
(b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation
of the Assertion (A).
(c) Assertion (A) is correct, but Reason (R) is incorrect statement.
(d) Assertion (A) is incorrect, but Reason (R) is correct statement. (3 × 1 = 3)
4. Assertion Separation of Zr and Hf is difficult.

(A) :
Reason Because Zr and Hf lie in the same group of the periodic table.
(R) :
5. Assertion Actinoids form relatively less stable complexes as compared to lanthanoids.
(A) :
Reason Actinoids can utilise their 5f orbitals along with 6d orbitals in bonding but
(R) :
lanthanoids do not use their 4f orbital for bonding.
6. Assertion (A) : Cu cannot liberate hydrogen from acids.
Reason (R) : Because it has positive electrode potential.
Answer the following questions:
7. Why lanthanoids are called as f-block elements? (1)
8. Name a member of the lanthanoid series which is known to exhibit +4 oxidation state. (1)
9. Account for the following:.
(i) Cobalt (III) is stable in aqueous solution but in the presence of complexing reagents, it is
easily oxidised.
(ii) The d 1 configuration is very unstable in ions. (2)
10. Complete the following equations:
(i) MnO4 4H 3e
(ii) Cr2O72 2OH
(2)

11. (i) Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic number
is 25.
(ii) While filling up of electrons in the atomic orbitals, the 4s orbital is filled before the
3d orbital but reverse happens during the ionisation of the atom. Explain why.
[NCERT Exemplar] (2)
12. Explain the following observations:
(i) Colour of KMnO4 disappears when oxalic acid is added to its solution in acidic medium.
(ii) A green solution of potassium manganate turns purple when CO2 gas is passed through
the solution. (2)
13. Assign suitable reasons for the following:
(i) The Mn2+ compounds are more stable than Fe2+ towards oxidation to their +3 state.
(ii) Sc3+ is colourless in aqueous solution whereas Ti3+ is coloured.
(iii) The highest oxidation state is exhibited in oxo-anions of a metal. [CBSE (F) 2014] (3)
14. When pyrolusite ore MnO2 is fused with KOH in presence of air, a green coloured compound
(A) is obtained which undergoes disproportionation reaction in acidic medium to give a purple
coloured compound (B).
(i) Write the formulae of the compounds (A) and (B).
(ii) What happens when compound (B) is heated? [CBSE (South) 2016] (3)
15. (i) With reference to structural variability and chemical reactivity, write the differences
between lanthanoids and actinoids.
(ii) Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
(iii) Out of Mn3+ and Cr3+, which is more paramagnetic and why?
(Atomic nos.: Mn = 25, Cr = 24) (3)
16. On the basis of lanthanoid contraction, explain the following:
(i) Nature of bonding in La2O3 and Lu2O3.
(ii) Trends in the stability of oxo salts of lanthanoids from La to Lu.
(iii) Stability of the complexes of lanthanoids.
(iv) Radii of 4d and 5d block elements.
(v) Trends in acidic character of lanthanoid oxides. (5)
Answers
1. (b) 2. (b) 3. (c) 4. (b) 5. (d) 6. (a)
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Chapter–8

The d- and f- Block Elements 303

304 Xam idea Chemistry–XII

The d- and f- Block Elements 305

(ii) It oxidises stannous to stannic.

(iii) It oxidises sulphur dioxide to sulphuric acid.

(iv) It oxidises hydrogen sulphide to sulphur.

(v) It oxidises iodides to iodine.

Cr2 O72– + 2OH – 2CrO 24– + H 2 O

Potassium dichromate is used as primary standard in volumetric analysis.

306 Xam idea Chemistry–XII

(ii) Ferrous to ferric

(iii) Oxalate to carbon dioxide

(iv) Hydrogen sulphide to sulphur

The d- and f- Block Elements 307

(vi) Nitrite to nitrate

2. In neutral or faintly alkaline solutions potassium permanganate oxidises:

Inner Transition Elements (f-Block Elements)

308 Xam idea Chemistry–XII

The d- and f- Block Elements 309

NCERT Intext Questions

has more stable t 32g (half-filled) configuration in a medium like water.

310 Xam idea Chemistry–XII

NCERT Textbook Exercises

The d- and f- Block Elements 311

312 Xam idea Chemistry–XII

The d- and f- Block Elements 313

314 Xam idea Chemistry–XII

The d- and f- Block Elements 315

316 Xam idea Chemistry–XII

The d- and f- Block Elements 317

For n = 1, µ = 1 (1  2)  3  1.73; For n = 2, µ = 2(2 + 2)  8  2.83

318 Xam idea Chemistry–XII

The d- and f- Block Elements 319

320 Xam idea Chemistry–XII

The d- and f- Block Elements 321

322 Xam idea Chemistry–XII

Short Answer Questions–I [2 marks]

The d- and f- Block Elements 323

8MnO4– + 3S2O32– + H2O 8MnO2 + 6SO42– + 2OH–

(ii) Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O

324 Xam idea Chemistry–XII

Short Answer Questions–II [3 marks]

From the given data of Eo values, answer the following questions:

The d- and f- Block Elements 325

326 Xam idea Chemistry–XII

MnO2  4 HCl 

NH3 + 3Cl 2 NCl3 + 3HCl

Q. 7. A solution of KMnO4 on reduction yields either a colourless solution or a brown precipitate or a

In alkaline medium (pH > 7),

Q. 8. (i) How would you account for the following:

on which reactants are adsorbed.

(ii) 3MnO 24– + 4H + 2MnO 4– + MnO 2 + 4H 2 O

The d- and f- Block Elements 327

Long Answer Questions [5 marks]

328 Xam idea Chemistry–XII

2MnO 2 + 4KOH + O 2 2K 2 MnO 4 + 2H 2 O

At anode: MnO 24– MnO 4– + e –

The d- and f- Block Elements 329

330 Xam idea Chemistry–XII

For n = 1, µ = 1 (1 2) 3 1.73; For n = 2, µ = 2(2 + 2) 8 2.83

MnO2 4 HCl