CHEMISTRY MATTERS

DR. SAHAS AGGARWAL

THE d & f -BLOCK

ELEMENTS

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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.1 What is a transition element? Give the classification of d-block elements.

Ans. The elements which have partially filled d-subshells and show the properties like colour, magnetism,
variable oxidation states and catalytic nature are called transition elements. Their general electronic
configuration is (n-1)d1-10 ns0-2.
Q.2 Copper in the ground state or as cuprous ion cannot be considered as transition element but cupric
ion is considered. Explain why?
Ans. Cu(29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (completely filled d-subshell)
Cu+ (cuprous ion) = 1s2 2s2 2p6 3s2 3p6 3d10
Cu+2 (cupric ion) = 1s2 2s2 2p6 3s2 3p6 3d9
Cu in the ground state or as cuprous ion is not considered as a transition element (but it is d-block
element) because it does not have partially filled d-subshell. So, it does not exhibit the characteristic
properties of transition elements. However, Cupric ion has incomplete d-subshell and hence it is a
transition ion.
Similarly, Zn, Cd, Hg have d10 configuration. They show properties different from rest of the
members of transition series elements. So, they are not called transition elements but are placed along
with them for the sake of continuity.
Q.3 Give the classification of d-block elements.
Ans. The transition series of elements have been classified into four series:
(i) First transition series from Sc21 to Zn30.
(ii) Second transition series from Y39 to Cd48.
(iii) Third transition series from La57 to Hg80.
(iv) Fourth transition series from Ac89 followed by elements with atomic number 104 onwards.
Q.4 Fe is a transition element while Na is not. Why?
Ans. This is explained on the basis of electronic configuration.
Na11 = 1s2 2s2 2p6 3s1 ; Fe26 = 1s2 2s2 2p6 3s2 3p6 3d6 4s2. Since, iron has a partially filled d-
subshell so it shows the properties of transition elements while sodium does not.
Q.5 Why a transition element called a transition element?
Ans. The transition elements are called transition elements because they represent a change in behavior
from the electropositive elements on their left to the electronegative elements to their right of the
periodic table.
Q.6 Give the main difference between transition elements and representative elements.
Ans. The transition elements differ from normal or representative elements in the manner that whereas in
normal elements, the last electron enters the valence s or p-subshell, in transition elements, the last
electron enters the d-subshell of penultimate shell as well as the outermost shell and in the inner
transition elements, the last electron enters the f-subshell of the ante-penultimate shell i.e. in normal
elements, the subshells of outermost shell may be partially filled. In transition elements, there may be
two partially filled subshells, one of outermost and the other of penultimate shell. In f-block elements,
there may be three partially filled subshells present in three different shells.
Q.7 Explain the physico-chemical properties of transition elements in detail.
Ans. (a) Atomic radii: As we move from left to right in a transition series, the atomic radius firstly
decreases, then becomes constant and after that it increases. E.g. in first transition series, the atomic
radii are given as under:
Element: Sc21 Ti22 V23 Cr24 Mn25 Fe26 Co27 Ni28 Cu29 Zn30
Atomic size (pm): 144 132 122 117 117 117 116 115 117 125
This variation is explained on the basis that the atomic size of the transition elements depends upon
the nuclear charge and screening effect. As we move from left to right in a transition series, the
atomic number increases. So, the number of electrons as well as protons i.e. nuclear charge also
increases. The force of attraction between the nucleus and the electrons should increase and the size
should decrease. However, in transition elements the incoming electron enters (n-1)d subshell. As we
move from left to right in the series, with the increase in number of electrons in (n-1)d subshell, the
screening effect due to intervening electrons increases and force of attraction between the nucleus
and outermost electron should decrease and size should increase. In the start of the transition series,
the screening effect is not significant and the nuclear charge is predominant. So, the size decreases
sharply. In the middle of the series, the increase in nuclear charge is balanced by the increase in
screening effect, so, the size almost remains constant. In the end of the series, the screening effect
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overpowers the effect of increased nuclear charge and size increases.

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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

(b) Coloured ions: Most of the transition elements and their ions are coloured in nature. This is
explained on the basis that these elements have partially filled d-subshells. When white light falls on
transition elements, the electrons get excited within the same subshell by absorbing a certain definite
amount of radiation from white light. The residual radiation is no longer white. It is deficient in the
colour corresponding to the one which is absorbed i.e. the colour which we observe for a transition
atom or ion is complementary to the one which is absorbed. Since, different transition elements have
different electronic configuration, so, they are of different colours.
NOTE: s and p-block elements are colourless because in these cases, the excitation of electrons take
place from a lower level to a higher level and the residual radiation does not lie in the visible region.
(c) Density: From left to right, the density increases. This is explained on the basis that on moving
from left to right, the atomic radius decreases due to increased nuclear charge. The atomic volume
thus decreases but the atomic mass increases, so, density increases.
(d) Magnetic properties: Most of the transition metal atoms and their ions are magnetic in nature i.e.
they are attracted by the external magnetic field. The origin of magnetism in transition metal atoms is
explained on the basis that an electron in an atom has two types of motions i.e. orbital motion as well
as spin contribution. The orbital motion of an electron is quenched by the electrostatic field of
neighbouring atom and only spin contribution persists. An electron being a charged particle while
spinning generates magnetism. As the number of unpaired electrons increases, the magnetism
generated by the atoms increases. The magnetic moment in case of transition metal atoms and ions is
given by the formula μspin = √n(n+2) B.M. where n = number of unpaired electrons. 1 B.M.(Bohr
magneton) = eh/4πmc. As the number of unpaired electrons increases, the paramagnetic character
increases. Since, the number of unpaired electrons are maximum in the middle of the series and after
that it decreases i.e. in the first transition series Mn2+ (3d5) has maximum paramagnetic character.
(e) Metallic nature: Most of the transition metals are hard metals. They have higher melting and
boiling points. This is explained on the basis that these elements form metallic bonds due to the
presence of ns electrons and at the same time, the d-orbitals of one atom overlap with the d-orbitals
of the other atom to form d-d overlap. Due to this covalent bonding (d-d overlap) and strong metallic
bonds, the hardness and melting and boiling points of transition elements are more than alkali
metals. As we move from left to right in a transition series, the hardness, the melting and boiling
points increase upto the middle and then they decrease. This is explained on the basis that upto the
middle of the series, due to the presence of more unpaired electrons, the d-d overlap is more and
after the middle, the pairing of electrons starts and number of unpaired electrons decreases and
strength of metallic bond also decreases.
(f) Catalytic properties: A number of transition metals are very good catalysts. Some of the catalysts of
transition metals are given as under:
(i) Vanadium is used as a catalyst as V2O5 in the contact process.
(ii) Co is used as a catalyst in Fischer-Trope’s process for the preparation of artificial petrol.
(iii) Finely divided Ni is used as a catalyst in the hydrogenation of oils.
(iv) Pt is used as a catalyst in Contact process for the preparation of H 2SO4 and in Ostwald’s process
for HNO3.
Q.8 Cu(I) is colourless while Cu(II) is bluish green in colour. Explain.
Ans. This is explained as under:
Cu(29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (completely filled d-subshell)
Cu(I) (cuprous ion) = 1s2 2s2 2p6 3s2 3p6 3d10 (no unpaired electron)
Cu(II) (cupric ion) = 1s2 2s2 2p6 3s2 3p6 3d9 (one unpaired electron)
Since, Cu(II) has a partially filled d-subshell, when white light falls on Cu(II), the excitation of
electrons can take place within the same subshell. As a result, it is coloured in nature. However, in
Cu(I), since, the configuration is fully-filled, the excitation of electrons is not possible with white
light and it is colourless.
Q.9 [Ti(H2O)6]3+ is purple in colour. Explain.
Ans. In [Ti(H2O)6]3+, the d-orbitals split up into two levels i.e. lower energy level called t2g level and
higher energy level called eg level within which excitation of electrons can take place by white light.
The residual radiation is violet in colour due to which this complex is violet in colour.
Octahedral splitting in [Ti(H2O)6]3+:
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.10 Cu(I) is diamagnetic whereas Cu(II) is paramagnetic. Explain.

Ans. This is explained as under:
Cu(I) = [Ar] 3d10; number of unpaired electrons = 0; Therefore, μ = √0(0+2) = 0
Cu(II) = [Ar] 3d9; number of unpaired electrons = 1; Therefore, μ = √1(1+2) = √3 = 1.732 B.M.
Since, there is no unpaired electron in Cu(I), so, it is diamagnetic while Cu(II), having one unpaired
electron, is paramagnetic.
Q.11 Out of Fe3+ and Fe2+, which has more magnetic moment?
Ans. Fe3+ is more magnetic than Fe2+. This is explained as under:
Fe2+ = 1s2 2s2 2p6 3s2 3p6 3d6 4s0 ; so, n = 4
Fe3+ = 1s2 2s2 2p6 3s2 3p6 3d5 4s0 ; so, n = 5
More the number of unpaired electrons, more is the magnetic moment. Fe3+ has more number of
unpaired electrons than Fe2+ , so, Fe3+ is more magnetic than Fe2+.
Q.12 Transition elements form a number of interstitial compounds. Explain.
Ans. Most of the transition elements on treatment with non-metals like hydrogen, boron, carbon, nitrogen,
form non-stoichiometric compounds called interstitial compounds. These are hard and rigid. In these
compounds, the non-metals occupy interstitial sites of metal lattice. E.g. steel and cast iron are
interstitial compounds. In interstitial compounds, the malleability and ductility is less but tensile
strength is more. They show conductivity like that of pure metal.
They are mainly formed due to variable valency of transition metals and also due to defects in crystal
lattices. E.g. TiH1.7, VH0.56 etc.
Q.13 Transition metals form a number of alloys. Explain.
Ans. Transition metals have comparable sizes due to which the atoms of one metal can occupy the
positions in the crystal lattice of the other. They are generally harder, have higher melting points and
are more resistant to corrosion than individual metals. They are formed by mixing of metals in the
molten state. The metals like Cr, V, Mo, Mn, W are used to form alloy steels and stainless steels.
Q.14 Why do transition elements exhibit tendency to form complexes? Explain giving examples.
Ans. Transition elements form a number of coordinate or complex compounds by accepting electrons
from ligands. The more complex forming tendency of transition metal atoms is due to
(i) Their smaller size
(ii) More effective nuclear charge
(iii) A number of vacant d-orbitals due to which they have variable oxidation states.
The examples of complexes are [Ag(NH3)2]Cl, [Cu(NH3)4]SO4, K4[Fe(CN)6] etc.
Q.15 Mn lies in the middle of the series even then it has low melting and boiling point. Explain.
Ans. The low melting and boiling point of Mn is explained on the basis that it has stable half-filled d5
electronic configuration. So d-d overlap is less in case of Mn.
Q.16 Ni+2 is more stable than Pt+2 while Pt+4 is more stable than Ni+4. Explain.
OR
K2PtCl6 is known but K2NiCl6 is not. Explain.
Ans.
Element I.E1 + I.E2 (kj/mol) I.E3 + I.E4 (Kj/mol) Total I.E (I.E1+I.E2+I.E3+I.E4) (Kj/mol)
Ni 2.49 x 103 8.80 x 103 11.29 x 103
Pt 2.66 x 10 3 6.70 x 10 3 9.36 x 103
The sum of first two ionization energies of Ni is less than that of Pt. So, Ni+2 is more stable than Pt+2.
However, the sum of first four ionization energies of Pt is less than that of Ni. So, Pt +4 is more stable
than Ni+4.
Q.17 Transition metal compounds generally act as catalysts. Give reasons.
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Ans. Reasons are:

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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

(i) The catalytic activity of transition elements is due to variable oxidation states and tendency to
form complexes. Thus, they possess the ability to absorb and re-emit wide range of energies which
makes the required activation energy available.
(ii) They provide a suitable large surface area with free valencies on which the reactants are
adsorbed. Hence, the reaction rate increases.
(iii) In some cases, they form intermediate compounds due to variable oxidation states and provide a
new reaction path with lower activation energy.
X + Catalyst X.Catalyst (complex) + Y(another reactant) XY + Catalyst
(reactant)(transition metal)(intermediate unstable compound) (product)(regenerated)
Q.18 Cu+2 is more stable than Cu+ in aqueous solution. Explain.
Ans. Cu+ (cuprous ion) = 1s2 2s2 2p6 3s2 3p6 3d10; Cu+2 (cupric ion) = 1s2 2s2 2p6 3s2 3p6 3d9
Cu+2(aq) + 2 e– → Cu(s); E0reduction = + 0.34 V; Cu+(aq) + 1 e– → Cu(s); E0reduction = + 0.52 V
Although, Cu+ has fully-filled, more stable symmetrical electronic configuration, even then Cu +2 is
more stable than Cu+ in aqueous solution. This is explained on the basis that Cu +2 ions undergo
hydration to a larger extent due to higher charge and smaller size. As a result, its reduction electrode
potential is less in comparison to that of Cu+. So, Cu+2 is more stable than Cu+ in aqueous solution.
However, in solid or gaseous states, Cu+ is more stable than Cu+2.
Q.19 Why do transition elements exhibit variable oxidation states?
Ans. The most important property of transition elements is their tendency to show variable oxidation
states. This is explained on the basis that they have their valence electrons in two different sets of
orbitals i.e. (n-1)d and ns. Since, there is very little difference in energies of these orbitals, both
energy levels can be used for bond formation. That is why, they exhibit variable oxidation states.
Highest oxidation state shown by an element is +8.
Q.20 How is iron extracted from its ore?
Ans.

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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Varieties of iron: The three commercial varieties of iron differ in their carbon contents. These are;
(1) Cast iron or Pig-iron : It is most impure form of iron and contains highest proportion of carbon
(2.5–4%).
(2) Wrought iron or Malleable iron : It is the purest form of iron and contains minimum amount of
carbon (0.12–0.25%).
Q.21 Explain the flow sheet for the extraction of copper.
Ans. Copper pyrites (CuFeS2)
↓
Crushed and sieved
↓
Concentration by froth floatation
Powdered ore + water + pine oil + air → sulphide ore in the froth
↓
Roasting in reverberatory furnace in presence of air
S + O2 → SO2; 2 As + 3 O2 → 2 As2O3; 2 CuFeS2 + O2 → Cu2S + 2 FeS + SO2
↓
Silica + coke → roasted ore
↓
Smelting in blast furnace in presence of air
2 FeS + 3 O2 → 2 FeO + 2 SO2; FeO + SiO2 → FeSiO3 (slag)
↓
Silica is added → matte (Cu2S, FeS)
↓
Bessemerisation in Bessemer convertor in presence of air
2 FeS + 3 O2 → 2 FeO + 2 SO2; FeO + SiO2 → FeSiO3 (slag)
2 Cu2S + 3 O2 → 2 Cu2O + 2 SO2; 2 Cu2O + Cu2S → 6 Cu + SO2 (auto-reduction)
↓
Blister copper (98% Cu + 2% impurities)
↓
Electrolytic refining
Anode = impure Cu plates, Cathode = pure Cu plates, electrolyte = CuSO 4 solution + H2SO4
Pure Cu deposited at cathode
↓
Pure copper (99.6% to 99.9%)
Q.22 Explain the flow sheet for the extraction of silver.
Ans. Silver ore (argentite, Ag2S)
↓
Concentration by froth floatation process
Powdered ore + H2O + pine oil + air → froth carrying sulphide particles
↓
Cyanidation (Mac Arthur Forest cyanide process)
Concentrated ore + NaCN solution (0.4 – 0.6%) + air
Ag2S + 4 NaCN ↔ 2 NaAg(CN)2 + Na2S; 4 Na2S + 5 O2 + 2 H2O → 2 Na2SO4 + 4 NaOH + 2 S
↓ filterate
Precipitation of silver with zinc
2 NaAg(CN)2 + Zn → 2 Ag + Na2Zn(CN)4; black ppt. of Ag + KNO3 → compact mass silver metal
(Black ppt.) fuse
↓
Electrolytic refining
Anode = impure Ag, Cathode = pure silver plate, electrolyte = AgNO3 solution + HNO3
Pure silver deposited at cathode
Silver dissolves in excess of mercury to form an amalgam. It is washed and then distilled when Ag is left
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behind in retort.
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Q.23 Name the heaviest and lightest elements in terms of density among the transition elements.
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Ans. Lightest element = Scandium; Heaviest element = Iridium (density=22.61 g/cc) and Osmium
(density=22.59 g/cc).
Q.24 Zn2+ salts are white while Cu2+ salts are blue. Why?
Ans. This is explained as under:
Zn2+ = 1s2 2s2 2p6 3s2 3p6 3d10 4s0; Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9 4s0
Since, Cu2+ has one unpaired electron while Zn2+ has no unpaired electron, so, Cu2+ is coloured i.e.
blue while Zn2+ is white.
Q.25 Calculate the equivalent mass of KMnO4 in acidic, neutral and basic medium.
Ans. In acidic medium:
2 KMnO4 + 3 H2SO4 → K2SO4 + 2 MnSO4 + 3 H2O + 5 [O]
2x158=316g 5x16=80g
80 parts of oxygen are evolved from KMnO4 = 316 g
1 part of oxygen are evolved from KMnO4 = 316/80
8 parts of oxygen are evolved from KMnO4 = (316 x 8)/80 = 31.6 g
i.e. equivalent mass = molecular mass/5
In neutral medium:
2 KMnO4 + H2O → 2 KOH + 2 MnO2 + 3 [O]
2x158=316g 3x16=48g
48 parts of oxygen are evolved from KMnO4 = 316 g
1 part of oxygen are evolved from KMnO4 = 316/48
8 parts of oxygen are evolved from KMnO4 = (316 x 8)/48 = 52.67 g
i.e. equivalent mass = molecular mass/3
In alkaline medium:
(i) In strongly alkaline medium:
2 KMnO4 + 2 KOH → 2 K2MnO4 + H2O + [O]
2x158=316g 16 g
16 parts of oxygen are evolved from KMnO4 = 316 g
1 part of oxygen are evolved from KMnO4 = 316/16
8 parts of oxygen are evolved from KMnO4 = (316 x 8)/16 = 158 g
i.e. equivalent mass = molecular mass/1
(ii) In weakly alkaline medium: K2MnO4 is further reduced to MnO2.
K2MnO4 + H2O → MnO2 + 2 KOH + [O]
So the complete reaction is: 2 KMnO4 + H2O → 2 MnO2 + 2 KOH + 3 [O]
2x158=316g 3x16=48g
48 parts of oxygen are evolved from KMnO4 = 316 g
1 part of oxygen are evolved from KMnO4 = 316/48
8 parts of oxygen are evolved from KMnO4 = (316 x 8)/48 = 52.67 g
i.e. equivalent mass = molecular mass/3; which is the same as that in neutral medium.
Q.26 Give the method of preparation of potassium permanganate (KMnO4).
Ans. It is prepared from pyrolusite (MnO2). The ore is finely powdered and is fused with a base and an
oxidizer when green coloured K2MnO4 is obtained.
2 MnO2 + 4 KOH + O2 → 2 K2MnO4 + 2 H2O
(potassium manganate; green mass)
Or 2 MnO2 + 2 K2CO3 + O2 → 2 K2MnO4 + 2 CO2;
Or MnO2 + 2 KOH + KNO3 → K2MnO4 + KNO2 + H2O
Or 3 MnO2 + 6 KOH + KClO3 → 3 K2MnO4 + KCl + 2 H2O
The green coloured mass is extracted with water and the filterate is treated with an oxidizing agent
when K2MnO4 gets oxidized to purple coloured KMnO4, which on concentrating forms crystals of
KMnO4.
3 K2MnO4 + 2 CO2 → 2 KMnO4 + MnO2 + K2CO3;
Or 2 K2MnO4 + Cl2 → 2 KMnO4 + 2 KCl
Or 2 K2MnO4 + H2O + O3 → 2 KMnO4 + 2 KOH + O2
Potassium manganate is also oxidized electrochemically to permanganate. The electrode reactions
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taking place are:

At anode: 2K 2 MnO4  H2O  O   2KMnO4  2KOH
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

or MnO24 
 MnO4  e
Green Purple
 
At cathode: 2H  2e   H2 
Q.27 Explain the properties of KMnO4.
Ans. Potassium permanganate, also called as Condy's crystals or hypermangan, is a very useful inorganic
chemical with disinfectant properties.
Physical properties: KMnO4 is found as a bright purple colored crystalline solid. It is odorless and has
a density of 2.70 g/mL, and a melting point of 240 °C. It is available commercially as powder,
crystals or tablets.
Chemical Properties: Potassium permanganate is a purple crystalline solid melting at 523 K. It is
slightly soluble in cold water. The solubility increases in hot water.
(i) Action of heat: Potassium permanganate decomposes to oxygen, potassium manganate and
manganese dioxide when heated to 746 K.

2KMnO4   K 2 MnO 4  MnO 2  O 2
(ii) Action of concentrated sulphuric acid: When treated with cold concentrated sulphuric acid
potassium permanganate is converted to Mn2O7 (green oil) which decomposes on warming to MnO 2
(The reaction is highly explosive).
2KMnO4  2H 2SO4 
 Mn 2O7  2KHSO4  H 2O

2Mn 2O7   4MnO2  3O2
(iii) Oxidizing properties: Potassium permanganate is a strong oxidizing agent and the reaction is pH
dependent.
In alkaline solution: In strongly alkaline solution, MnO24 ion is produced as shown in the reaction.
2KMnO4  2KOH 
 2K 2 MnO4  H2O  [O] or MnO4  e 
 MnO42
The MnO24 ion gets further reduced to MnO2 ,
K2 MnO4  H2O 
 MnO2  2KOH  [O] or MnO24  2H2O  2e 
 MnO2  4OH
Thus, the complete reaction is
2KMnO4  H2O   2MnO2  KOH  3O or MnO4  2H2O  3e  MnO2  4OH
A few examples of oxidation by KMnO4 in alkaline medium are:-
(a) Potassium iodide is oxidized to potassium iodate
2KMnO4  H2O  KI   2MnO2  2KOH  KIO3 or I  6OH 
 IO3  3H2O  6e
(b) Potassium permanganate is used in oxidation of olefinic compounds to glycols. It is known by the
name of Baeyer’s reagent in these reactions.
CH2 CH2OH
+ H2O + [O]
CH2 CH2OH
In acidic medium: In the presence of dilute sulphuric acid, the following reaction takes place,
2KMnO4  3H2SO4   K 2SO4  2MnSO4  3H2O  5[O] Or MnO4  8H  5e   Mn 2  4H2O
Potassium permanganate acts as a very strong oxidizing agent in acidic medium. Few examples of
oxidation by acidic potassium permanganate solution are:
(a) Oxidation of H2S to S
2KMnO4  3H 2SO4   K 2SO4  2MnSO 4  3H 2O  5[O]
2{H S  O 
 H O  S} 5
2
____________________________________________________
2KMnO4  3H 2SO4  5H 2S  K 2SO4  2MnSO4  8H 2O  5S
or 2MnO4  16H  5S2   2Mn 2  8H2O  5S
(b) Oxidation of ferrous sulphate to ferric sulphate
2KMnO 4  3H 2SO 4   K 2SO 4  2MnSO 4  3H 2O  5[O]
{2FeSO 4  H 2SO 4  [O] 
 Fe 2 (SO 4 )3  H 2O} 5
_____________________________________________________________
2KMnO4  8H 2SO4  10FeSO4   K 2SO 4  2MnSO 4  5Fe 2 (SO 4 )3  8 H 2O
2MnO4  16H  10Fe2 
 2Mn 2  18H2O  10Fe3
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or
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(c) Oxidation of potassium iodide to iodine:

 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

2KMnO4  3H2SO4 
 K 2SO4  2MnSO4  3H2O  5[O]
{2KI  H2SO4  [O] 
 K 2SO4  I2  H2O} 5
_____________________________________________________
2KMnO4  8H 2SO4  10KI   6K 2SO4  2MnSO4  8H 2O  5I 2
or 2MnO4  16H  10I   2Mn 2  8H2O  5I2
In neutral medium: In neutral medium, potassium permanganate is weakly oxidizing and the
reaction involved is
2KMnO4  H2O   2KOH  2MnO2  3[O] Or MnO4  2H2O  3e   MnO2  4OH
The alkali (KOH) produced renders the solution basic as the reaction proceeds and the reaction given
above is then essentially same as that for alkaline medium.
Examples of oxidation by potassium permanganate in neutral solution:
(i) It oxidizes hot manganese sulphate to manganese dioxide
2KMnO4  H 2O   2KOH  2MnO2  3[O]
3MnSO4  3H 2O  3[O]   3MnO2  3H 2SO4
2KOH  H 2SO4   K 2SO4  2H 2O
__________________________________________________
3MnSO4  2KMnO4  2H 2O   5MnO2  K 2SO4  2H 2SO4
(ii) It oxidizes sodium thiosulphate to sodium sulphate
3Na 2S2O3  8KMnO4  H2O   3Na 2SO4  8MnO2  3K 2SO4  2KOH
(iii) It oxidizes hydrogen sulphide to sulphur
2KMnO4  4H2S   2MnS  S  K 2SO4  4H2O
Q.28 A student accidentally added concentrated H2SO4 to solid KMnO4. An explosion occurred in the
laboratory. Write what happened chemically.
Ans. 2 KMnO4 + H2SO4 → Mn2O7 + 2 KHSO4 + H2O
(conc.) (manganese heptaoxide, explosive)
2 Mn2O7 → 4 MnO2 + O2
The cause of explosion was that explosive Mn2O7 was formed in the reaction mixture.
Q.29 Explain the structure of permanganate ion.
Ans. In KMnO4, the anion is MnO4– in which hybridization state of central atom is sp3 and it has
tetrahedral structure as shown.

Q.30 How is potassium dichromate (K2Cr2O7) prepared?

Ans. It is prepared from chrome iron or ferrochrome or chromite (FeO.Cr 2O3). Chrome iron is heated
with Na2CO3 and O2 in a reverberatory furnace when it is converted into sodium chromate. Quick
lime keeps the mass porous and facilitates oxidation.
4 FeO.Cr2O3 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
(sodium chromate, yellow)
The roasted mass is extracted with water. The solution contains Na2CrO4. The solution is acidified
with H2SO4 when it is oxidized to sodium dichromate.
2 Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
(sodium dichromate)
The solution obtained above is cooled when Na2SO4.10H2O gets crystallised and Na2Cr2O7 remains in
the solution. To the solution, KCl solution is added when sodium dichromate changes to potassium
dichromate.
9

Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl

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(potassium dichromate, orange)

The solution on cooling crystallises K2Cr2O7.
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.31 Explain how the colour of K2Cr2O7 solution depends upon pH of solution.
Ans. K2Cr2O7, which is orange in colour, on treatment with an alkali forms yellow coloured K 2CrO4.
pH>7(↑e in pH)
K2Cr2O7 + 2 KOH 2 K2CrO4 + H2O
(orange) pH<7(↓e in pH) (yellow)
The potassium chromate formed above on treatment with H2SO4 again changes into orange coloured
K2Cr2O7.
2 K2CrO4 + H2SO4 → K2Cr2O7 + K2SO4 + H2O
(yellow) (orange)
This interconversion is explained on the basis that in dichromate solution, the Cr2O72– ions are in
equilibrium with CrO42– ions at pH = 4, i.e.
pH = 4
Cr2O72– + H2O 2 CrO42– + 2 H+
(orange red, dichromate) (yellow, chromate)
On adding alkali (i.e. increasing the pH of the solution), the H + ions are used up and according to Le
Chatelier principle, the reaction shifts in the forward direction producing yellow chromate solution.
On the other hand, when an acid is added (i.e. pH of the solution is decreased), the concentrations of
H+ ions is increased and the reaction shifts in the backward direction producing orange red
dichromate solution.
Q.32 Explain the properties of K2Cr2O7.
Ans. Properties of potassium dichromate:
Potassium dichromate is an orange-red crystalline solid which melts at 669 K. It is moderately
soluble in cold water but freely soluble in hot water. Some important properties are as follows:
(i) Action of heat: When heated potassium dichromate decomposes with evolution of oxygen

4K 2Cr2 O7   4K 2CrO 4  2Cr2O3  3O 2
(ii) Action of concentrated sulphuric acid: Red crystals of chromic anhydride (chromium trioxide) are
formed when potassium dichromate is treated with cold concentrated sulphuric acid
K 2Cr2O7  2H 2SO4 
 2CrO3  2KHSO4  H 2O
(Re d)
On the other hand, heating of potassium dichromate with concentrated sulphuric acid results in
evolution of oxygen
2K2Cr2O7  8H2SO4   2K 2SO4  2Cr2 (SO4 )3  8H2O  3O2
(iii) Oxidizing properties: Potassium dichromate is a powerful oxidizing agent. In the presence of dilute
sulphuric acid, one mole of potassium dichromate produces three moles of oxygen atoms as indicated
by the equation.
K 2Cr2O7  4H 2SO4 
 K 2SO4  Cr2 (SO4 )3  4H 2O  3[O]
Cr2O72  14H   6e 
 2Cr 3  7H 2O
Where chromium in +6 oxidation state in Cr2O72 ion is being reduced to Cr3 (+3 oxidation state)
Let us examine the action of acidified potassium dichromate solution as an oxidizing agent by taking
few examples:
(a) It liberates I2 from KI
K 2Cr2O7  4H 2SO4   K 2SO4  Cr2 (SO 4 )3  4H 2O  3[O]
6KI  3H 2SO4  3[O]  3K 2SO4  3I 2  3H 2O
_______________________________________________________
K 2Cr2O7  7H 2SO4  6KI 
 4K 2SO 4  Cr2 (SO 4 )3  3I 2  7H 2O
or Cr2O72  14H   6I  
 2Cr 3  3I2  7H 2O
(b) It oxidizes ferrous salts to ferric salts.
K 2 Cr2 O7  4H 2SO 4   K 2SO 4  Cr2 (SO 4 )3  4H 2O  3[O]
{2FeSO 4  H 2SO 4  [O]   Fe 2 (SO 4 ) 2  H 2O} 3
K 2 Cr2 O7  7H 2SO 4  6FeSO 4  K 2SO 4  Cr2 (SO 4 )3  3Fe 2 (SO 4 ) 3  7H 2O
10

________________________________________________________________
or Cr2O72  14H  6Fe2   2Cr 3  6Fe3  7H2O
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The above two reactions are used in the volumetric estimation of iodine and iron (II).
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

(c) In oxidizes H2S to sulphur.

K 2Cr2O7  4H 2SO 4  K 2SO 4  Cr2 (SO 4 )3  4H 2O  3[O]
{H 2S  [O] 
 H 2O  S} 3
_____________________________________________________________________
K 2Cr2O7  4H 2SO 4  3H 2S 
 K 2SO 4  Cr2 (SO 4 )3  3S  7H 2O
or Cr2O72  8H   3H 2S 
 2Cr 3  3S  7H 2O
(d) It oxidizes ethyl alcohol to acetaldehyde and acetic acid
K 2Cr2O7  4H 2SO4   K 2SO4  Cr2 (SO4 )3  4H 2O  3[O]
CH 2CH 2OH  [O] 
 CH3CHO  H 2O
Etheyl alcohol Acetaldehyde
CH3CHO  [O]   CH3COOH
Acetaldehyde Acetic acid
(e) It oxidizes sulphides to sulphates
K 2Cr2O7  4H 2SO4   K 2SO4  Cr2 (SO4 )3  4H 2O  3[O]
{Na 2SO3  [O]   Na 2SO4 }  3
_________________________________________________
K 2Cr2O7  4H 2SO4  3Na 2SO3 
 K 2SO  Cr2 (SO 4 )3  4H 2O  3Na 2SO 4
or Cr2O72  8H   2SO32  2Cr 3  3SO 24  7H 2O
(f) It oxidizes SO2 to sulphuric acid
K 2Cr2O7  4H 2SO4   K 2SO4  Cr2 (SO4 )3  4H 2O  3[O]
{SO2  [O]  H 2O   H 2SO4 } 3
_______________________________________________
K 2Cr2O7  H 2SO4  3SO2 
 K 2SO4  Cr2 (SO4 )3  H 2O
or Cr2O72  2H   3SO2   Cr2 (SO 4 )3  H 2O
(g) It oxidizes halogen acids to halogen.
K2Cr2O7  14HCl   2KCl  2CrCl3  7H2O  3Cl2
Q.33 Explain the chemistry of chromyl chloride test.
Ans. (Reaction with a Cl– and concentrated H2SO4).
When heated with concentrated HCl or with a chloride and strong H 2SO4, reddish brown vapours of
chromyl chloride are obtained. This is chromyl chloride test and is used for the detection of chloride
ions.
K2Cr2O7 + 4 KCl + 6 H2SO4 → 2 CrO2Cl2 + 6 KHSO4 + 3 H2O
(chromyl chloride, reddish brown)
Chlorides of Ag, Hg, Pb and Sn do not give this test.
Q.34 Explain the structures of chromate and dichromate ion.
Ans. Structure of chromate ion, CrO42–: It has a tetrahedral structure as shown. All bonds are equal due to
resonance.
Structure of dichromate ion, Cr2O72–: In Cr2O72– ion, the two Cr – O bonds which share an oxygen
atom at the common vertex of two tetrahedral units are longer than the other six equivalent Cr – O
bonds. So, all the Cr – O bonds are not equivalent.
11
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.35 Explain the cause of colour of chromate and dichromate ions.

Ans. Both in CrO42– and Cr2O72–, Cr(VI) has d0 configuration. Hence, yellow colour of chromate and
orange colour of dichromate are not due to d-d transition but due to charge transfer (charge transfer
spectra), i.e. momentary transfer of charge from O-atom to metal atom thereby changing O2– to O–
ion and reducing the oxidation state of Cr from +6 to +5.
Q.36 What happens when TiCl4 is hydrolysed?
Ans. TiCl4 on hydrolysis with water forms TiO2. TiCl4 + 2 H2O → TiO2 + HCl
Q.37 Write the structure of CuCl2 and CuBr2.
Ans. Both CuCl2 and CuBr2 have infinite chain structure forming covalent bonds. Their structure is
identical. The structure of CuCl2 is given as under:

Cl Cl
Cu Cu Cu
Cl Cl

Cl Cl Cl
Cu Cu Cu Cu
Cl Cl Cl

Q.38 Explain the following terms: (i) Quenching (ii) Tempering (iii) Annealing.
Ans. (i) Quenching or hardening: If the steel is heated to red heat (1123K) and then suddenly cooled by
plunging it into cold water or oil, the process is called quenching. It makes the steel brittle. It has very
low elasticity.
(ii) Tempering: If the quenched steel is reheated to a temperature between 503 K and 573 K and then
allowed to cool slowly, the process is called tempering. Such steel is neither too hard nor too brittle.
In the process of tempering, a thin film of the oxide is formed on the steel surface. The colour of the
oxide film depends on the temperature at which the quenched steel is heated.
Temperature range Colour of the oxide film
200 – 2300C yellow
225 – 2700C brown
3000C blue
(iii) Annealing: If the steel is heated to a temperature well above red heat and then is cooled slowly,
the process is called annealing. It makes the steel soft and ductile. This type of steel is used in
fabrication process.
Q.39 What happens when chromyl chloride vapours are passed through NaOH solution?
Ans. When chromyl chloride vapours are passed through NaOH solution, yellow coloured solution is
obtained.
4 NaOH + CrO2Cl2 → Na2CrO4 + 2 NaCl + 2 H2O
(yellow solution)
Q.40 Anhydrous CuSO4 is colourless while hydrated CuSO4 is bluish green. Explain.
Ans. Anhydrous CuSO4 → no splitting of field (as not a coordinate compound)
Hydrated CuSO4 → CuSO4.5H2O or [Cu(H2O)4]SO4.H2O shows crystal field splitting so coloured due
to d-d transition. From the white light falling on it, red wavelength is absorbed for excitation of
electron from lower to higher energy level (d-d transition). The complementary colour i.e. blue is
12

reflected. Thus, CuSO4.5H2O is blue.

Q.41 Why does a transition series contain 10 elements?
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Ans. There are five d-orbitals in an energy level and each orbital contains two electrons. As we move from
an element to the next, an electron is added and for completing five d-orbitals, ten electrons are
added.
Q.42 Name three elements of transition series which have abnormal electronic configuration.
Ans. Niobium, Molybdenum and Palladium.
Q.43 Why do transition elements show similarities along horizontal period?
Ans. This is because the electronic configuration remains same in the outermost shell of transition
elements.
Q.44 Why does Mn(II) ion show maximum paramagnetism among bivalent ions of first transition series?
Ans. This is explained on the basis of electronic configuration of Mn(II) ion, which is,
Mn2+ = 1s2 2s2 2p6 3s2 3p6 3d5 4s0. Since, it has maximum number of unpaired electrons in 3d-
orbitals i.e. (n-1)d orbitals, so, Mn(II) shows maximum paramagnetism
Q.45 The magnetic moment of transition metal is found to be 3.87 B.M. Calculate the number of unpaired
electrons in it.
Ans. μspin = √n(n+2) B.M
3.87 = √n(n+2)
Squaring and solving, we get, n = 3 i.e. number of unpaired electrons = 3.
Q.46 Why is Cr used for electroplating?
Ans. Because it prevents corrosion by forming an protective oxide layer.
Q.47 How is pure iron prepared chemically?
Ans. It is prepared by thermal decomposition of pentacarbonyliron. Fe(CO) 5 298 K Fe + 5 CO
Q.48 Explain the following:
Ans. (i) Jeweller’s rough: Ferric oxide is used as a red pigment and as a metal polish and is called
Jeweller’s rough.
(ii) Tincture ferriperchloride: Alcoholic solution of ferric chloride is used as medicine under the
name tincture ferriperchloride.
(iii) Matte: Mixture of molten sulphide of copper(I) and iron(II).
(iv) Bordeaux mixture: Solution of CuSO4.5H2O and slaked lime i.e. Ca(OH)2 and is used as a
fungicide.
(v) Tough pitch copper: 99.5 % pure copper is called tough pitch copper.
(vi) Pharaoh’s serpents: Pellets made from the dry powder of mercuric thiocyanate when ignited,
form long snake like tubes of ash called pharaoh’s serpents.
(vii) Spelter: Impure Zn is called spelter. It is 97 – 98% pure Zn.
Q.49 In the transition series, starting from Lanthanum (57), the next element Hafnium (72) has an atomic
number 72. Why do we observe this jump in atomic number?
Ans. This is explained on the basis of the fact that Cerium (Ce58) onwards, the 4f-subshell tends to become
more stable than the 5d-subshell. Consequently, the next 14 elements (atomic number 58 to 71),
(Ce58 → Lu71) after lanthanum, the differentiating electron enters 4f-orbitals. The 4f-subshell gets
completely filled at Lu71 and in case of hafnium (Hf72), the last electron enters in 5d-subshell.
Q.50 Explain why transition elements are metals.
Ans. Due to their relatively low I.E and small kernel size, strong metallic bonding is present in transition
elements. Thus, transition elements show all the properties of metals such as hardness, high density,
good conductors of heat and electricity etc. Hence, these elements behave as typical metals.
Q.51 Why is the ionisation energy of 5d elements greater than 3d elements?
Ans. In the 5d series, after lanthanum (57), there is lanthanide contraction. In each group, the size of 5d
element is smaller while nuclear charge is greater than 3d element. Hence I.E of 5d elements is
greater than 3d elements.
Q.52 Give plausible reason for the fact that transition metals have high enthalpy of atomization.
Ans. The interatomic forces between transition metal atoms are very strong because of their small size and
presence of additional covalent bonding due to d-d overlapping. This results in high heat of
atomization in transition metals.
Q.53 Zn, Cd and Hg are volatile metals. Explain.
Ans. In case of Zn, Cd and Hg, the electronic configuration is fairly stable because all the penultimate d-
13

orbitals are fully-filled [(n-1)d10 ns2] and therefore, d-d overlap does not occur. Thus, these metals do
not have multiple bonding. The weak interatomic forces in them are due to metallic bonds. Thus, they
Page

have comparatively low melting and boiling points. Hence, these metals are volatile. In fact, Hg is
liquid at room temperature.
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.54 E0 for Cu is + 0.34 V and that of Zn is – 0.76 V. Explain.

Ans. This is due to completely filled 3d and 4s orbitals, Zn forms weak metallic bonds and hence its
∆Hsublimation is quite low (131 Kj/mol) while Cu has high ∆H sublimation (340 Kj/mol). As a result, E0 for
Zn has a negative value.
Q.55 Why are transition metals weaker reducing agents than s-block elements?
Ans. Transition elements are weaker reducing agents than s-block elements due to high values of
reduction potentials. The high value of reduction potential of these metals are due to their
(i) high I.E (ii) low ∆Hsolvation (iii) high ∆Hsublimation
Q.56 Solution of KMnO4 is slowly decomposed by exposure to light. Why?
Ans. There is small concentration of H+ ions due to the self-ionization of water which decomposes the
KMnO4 solution. The reaction is catalysed by light.
4 MnO4– + 4 H+(from water) → 4 MnO2 + 3 O2 + 2 H2O
Q.57 Why do transition elements show similarities along a horizontal row (period) and down a vertical
column (group)?
Ans. The properties of atoms depend upon the number of valence electrons. As we move along a period,
the electrons are added in (n-1) d subshell, so, the valence electrons remain unaffected i.e. ns2. That
is why they show similarities in properties along a period. As we move down a group, (n-1) d and ns
electrons are same in number. Therefore, they show similarities along a group also.
Q.58 Atomic radii decrease along a period, but atomic radii of Ni, Cu, Zn follow the order Ni < Cu < Zn.
Explain.
Ans. This is because when additional electrons are added in 3d-subshell abruptly and the extent of their
inter-electronic repulsions overpowers the magnitude of attractive forces due to increased nuclear
charge.
Q.59 Why Mohr’s salt solution is preferred to ferrous sulphate for standardization of KMnO 4?
Ans. Mohr’s salt is not readily oxidized by atmospheric oxygen or air while ferrous sulphate is easily
oxidized by air. For this reason, Mohr’s salt solution is preferred.
Q.60 Why is HCl not used to acidify a permanganate solution in volumetric estimation of Fe 2+ and C2O42–?
Ans. This is because a part of oxygen produced from KMnO 4 + HCl is used up in oxidizing HCl to Cl2.
4 HCl + 2 [O] → 2 H2O + Cl2
Q.61 Why does AgNO3 produce a black stain on the skin?
Ans. As AgNO3 comes in contact with organic matter (skin), it gets reduced to very fine particles of Ag
which produce a black stain. 2 AgNO3 → 2 Ag + 2 NO2 + O2
Q.62 What is mercury tree?
Ans. When a little of Hg is poured into a AgNO 3 solution, a tree like growth of silver amalgam is
produced. This is called mercury tree.
Q.63 A photograph when placed in a solution of gold chloride acquires a golden tinge but nothing
happens to it when it is placed in a CuSO4 solution. Explain.
Ans. Because Ag is more reactive than Au, so, it displaces Au but being less reactive than Cu, it cannot
displace Cu from the aqueous solution of its salt.
Q.64 What are typical and non-typical transition elements?
Ans. Elements of group 3 namely Sc, Y, La and Ac, also differ from transition elements in the facts that
they do not show variable oxidation state i.e. they show oxidation state of +3 only, their compounds
are diamagnetic and colourless while those of other transition elements are paramagnetic and
coloured. That is why elements of group 3 and group 12 are called non-typical transition elements
while rest are called typical transition elements.
Q.65 In a given transition series, the difference in the I.E between any two successive d-block elements is
very much less than the difference in case of successive s or p-block elements. Explain.
Ans. This is explained on the basis that the addition of d-electrons in penultimate (n-1) d subshell with
increase in atomic number provides a screening effect and thus shields the outer s-electrons from
inward nuclear pull. Thus the effects of increased nuclear charge and addition of d-electrons tend to
oppose each other. This is due to their counter effects that the I.E shows a little variation on moving
along a period of d-block elements.
Q.66 Why Zn2+ salts are white and Ni2+ salts are blue?
14

Ans. This is explained as under:

Zn2+ = 1s2 2s2 2p6 3s2 3p6 3d10 4s0; Ni2+ = 1s2 2s2 2p6 3s2 3p6 3d8 4s0
Page

Since, Ni2+ has two unpaired electrons while Zn2+ has no unpaired electron, so, Ni2+ salts are
coloured i.e. blue while Zn2+ salts are white.
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.67 Transition elements have high enthalpy of hydration. Why?

Ans. This is due to their small size and large nuclear charge. This is so because when we move along any
transition series, the nuclear charge increases and size decreases.
Q.68 Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their +3 state?
Ans. Mn2+ = 1s2 2s2 2p6 3s2 3p6 3d5 4s0; Fe2+ = 1s2 2s2 2p6 3s2 3p6 3d6 4s0
2+
Since, Mn has exactly half-filled electronic configuration so due to more symmetry and exchange
energy, it is more stable and does not lose any electron further. But in case of Fe 2+, electronic
configuration is 3d6. So, it can lose one electron very easily to attain more stable exactly half-filled
configuration and hence, can form Fe3+.
Q.69 Of the d4 species, Cr(II) is strongly reducing while Mn(III) is strongly oxidizing. Explain.
Ans. This is explained on the basis of their standard reduction electrode potential values, which are as
follows:
E0Cr3+/Cr2+ = - 0.41 V and E0Mn3+/Mn2+ = +1.57 V. Since the reduction electrode potential value
for Cr3+/Cr2+ is negative, so, Cr3+ has very little tendency to be reduced and hence act as oxidizing
agent. Hence, it has more tendency to be oxidized and act as reducing agent. On the other hand
Mn3+/Mn2+ has standard reduction electrode potential value as positive, so, Mn3+ has more tendency
to get reduced and act as oxidizing agent.
Q.70 Co(II) is stable in aqueous solution but in presence of complexing agents, it is easily oxidized.
Explain.
Ans. This is explained on the basis that in presence of a complexing agent, oxidation state of Co changes
from +2 to +3.
Q.71 Why is d1 configuration very unstable in ions?
Ans. This is because after the loss of ns electrons, d1 is easily lost to attain stable electronic configuration
i.e. they are reducing or they undergo disproportionation.
Q.72 Why a green layer appears on the surface of Cu vessel after some time?
Ans. In presence of atmospheric oxygen, CO2 and water vapours, green coloured basic copper carbonate
is formed on the surface of Cu vessel.
2 Cu + O2 + CO2 + H2O → Cu(OH)2.CuCO3
(basic copper carbonate, green)
Q.73 Why does Zn become dull in moist air?
Ans. This is because in presence of moist air, Zn forms a thin layer of bluish grey basic zinc carbonate
which dulls its luster.
4 Zn + 2 O2 + CO2 + 3 H2O → ZnCO3.3Zn(OH)2
(basic zinc carbonate)
Q.74 The species [CuCl4]2– exists but [CuI4]2– does not exist. Explain.
Ans. This is explained on the basis that I– being a stronger reducing agent than Cl– ion, reduces Cu2+ to
Cu+, which is more stable than Cu2+. As a result, CuI2 is converted into CuI and hence [CuI4]2– does
not exist.
Cu+ = 1s2 2s2 2p6 3s2 3p6 3d10 (fully filled so more stable); Cu+2 = 1s2 2s2 2p6 3s2 3p6 3d9.
Q.75 Explain the nature of bonding in blue vitriol.
Ans. Blue vitriol is CuSO4.5H2O (copper sulphate pentahydrate). In this, four molecules of water are
linked by coordinate bonds to the central Cu2+ ion while the fifth is attached to sulphate ion by
hydrogen bonding (most tightly held).
15

It has four types of bonds i.e. ionic, covalent, co-ordinate and hydrogen bonds.
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Q.76 What happens when AgNO3 solution is added to sodium thiosulphate solution?
Ans. A white precipitate of Ag2S2O3 is obtained which turns yellow, brown and finally black on keeping.
2 AgNO3 + Na2S2O3 → Ag2S2O3 + 3 NaNO3; Ag2S2O3 + H2O → Ag2S + H2SO4
(black ppt.)
Q.77 What happens when?
(i) Mercuric chloride is treated with excess of KI solution
(ii) Ammonia is passed through Nessler’s reagent.
Ans. (i) First, scarlet precipitate of HgI2 is formed which dissolves in excess of KI to form the complex
K2HgI4 called Nessler’s reagent.
HgCl2 + 2 KI → HgI2 + 2 KCl; HgI2 + 2 KI → K2[HgI4] (Nessler’s reagent)
(ii) A brown precipitate of ‘iodide of Millon’s base’ is obtained.
HgI2 + 2 NH3 → I–Hg–NH2 + NH4I
NH2–Hg–I + H – O – H + NH2–Hg–I → NH2–Hg–O–Hg–I + NH4I
(iodide of Millon’s base)
Q.78 Name the oxometal anions of the first series of the transition metals in which metal exhibits the
oxidation state equal to its group number.
Ans. Cr2O72– (group number of Cr = oxidation state of Cr = 6); MnO4– (group number of Mn= oxidation
state of Mn = 7).
Q.79 Why is AgBr used in photography?
Ans. This is explained on the basis that out of all silver halides, AgBr is most sensitive to light and
undergoes photo-reduction to metallic silver instantaneously on exposure to light.
2 AgBr light, hv 2 Ag + Br2
Q.80 In what way do the d-block elements differ from alkali and alkaline earth metals?
Ans.
d-block elements Alkali and alkaline earth metals
1. They are less metallic 1. They are more metallic
2. The last electron enters d-orbital 2. The last electron enters s-orbital
3. Most of them form complexes 3. Very few of them form complexes
4. Their salts are mostly coloured 4. Their salts are white
5. They are usually used as catalysts 5. Very few of them are used as catalysts
Q.81 Nitrogen is obtained in the reaction of aqueous NH3 with KMnO4. Explain. (IIT)
Ans. 2 KMnO4 + H2O → 2 KOH + 2 MnO2 + 3 [O]
2 NH3 + 3 [O] → N2 + 3 H2O
2 KMnO4 + 2 NH3 → 2 MnO2 + 2 KOH + 2 H2O + N2
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Nitrogen gas is evolved.

Q.82 CrO3 is an acid anhydride. Explain.
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Ans. CrO3 + H2O → H2CrO4

 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Since, on adding water, it forms chromic acid so it has been formed by the loss of a water molecule
from chromic acid.
Q.83 Explain why mercury (I) ion exists as Hg22+ ion while copper (I) ion exists as Cu+ ion.
Ans. This is explained as under:
The electronic configuration of Hg (I) i.e. Hg+ is [Xe] 4f14 5d0 6s1 and thus has one electron in its
valence 6s orbital. If this had been there then all Hg (I) compounds must have been paramagnetic
but actually they are diamagnetic. This is explained on the basis that singly filled 6s orbitals of two
Hg+ ions overlap to form Hg – Hg covalent bond. Thus, Hg+ ion exists as dimeric species i.e. Hg22+.
On the other hand, electronic configuration of Cu (I) i.e. Cu + is [Ar] 3d10. Therefore, it has no
unpaired electron and cannot form dimeric species Cu22+. So, it always exists as Cu+ ion.
Q.84 HgCl2 and SnCl2 cannot exist together in an aqueous solution. Why?
Ans. This is explained on the basis that SnCl2 is a strong reducing agent and hence reduces HgCl2 first to
Hg2Cl2 (white) and then to Hg (black).
SnCl2 + 2 HgCl2 → SnCl4 + Hg2Cl2; SnCl2 + Hg2Cl2 → SnCl4 + 2 Hg
(white) (black)
Q.85 Out of Na+ and Ag+, which is a stronger Lewis acid and why?
Ans. Ag+ is a stronger Lewis acid than Na+. This is explained on the basis of Fajan’s rules. Since, Ag + has
pseudo noble gas configuration so it has more polarizing power. So, it can attract electrons easily.
Q.86 During qualitative analysis of a mixture containing Cu2+ and Zn2+ ions, H2S gas is passed through an
acidified solution containing these ions in order to test Cu 2+ ions. Explain.
Ans. This is explained on the basis that Ksp of Cu2+ ions is lower than that of Zn2+ ions. So, Cu2+ ions get
precipitated as CuS when H2S is passed through an acidified solution while Zn 2+ ions remain in the
solution.
Cu2+ + H2S → CuS↓ + 2 H+
(black ppt.)
The black precipitate of CuS is dissolved in dilute HNO3 and tested for Cu2+ ions.
Q.87 Why is it that anhydrous Cu (II) chloride is covalent while anhydrous Cu (II) fluoride is ionic in
nature?
Ans. This is explained on the basis of Fajan’s rules. Since, Cl – is larger in size than F–, so, its polarisability is
more and hence Cu (II) chloride has more covalent character and Cu (II) fluoride has more ionic
character. This can also be explained on the basis of electronegativity difference.
Q.88 For some of the first row transition elements, the E0 values are
Element V Cr Mn Fe Co Ni Cu
0 2+
E M /M (in volts) - 1.18 - 0.91 -1.18 - 0.44 - 0.28 - 0.25 + 0.34
Give suitable explanation for the irregular trend in these values.
Ans. There is no regular trend in the values of reduction potentials as the I.E values (I.E1 and I.E2) and
sublimation energies of these metals do not show any regular trend.
Q.89 KMnO4 is a stronger oxidizing agent in an acidic medium than in an alkaline medium. Explain.
Ans. This is explained as under:
In acidic medium:
2 KMnO4 + 3 H2SO4 → K2SO4 + 2 MnSO4 + 3 H2O + 5 [O]
In alkaline medium:
2 KMnO4 + 2 KOH → 2 K2MnO4 + H2O + [O]
In acidic medium, more nascent oxygen is released, so, KMnO 4 is stronger oxidizing agent in acidic
medium than in alkaline medium.
Q.90 What may be the stable oxidation state of transition elements with 3d 5 and 3d8 electronic
configurations?
Ans. The two important species with this configuration 3d5 (or d5) are Mn2+ and Fe3+. Fe3+ may however,
be reduced to Fe2+. For 3d8 (or d8) configuration, Ni2+ is the most important species.
Q.91 For coinage metals, the chemical activity decreases from Cu to Au. Why?
Ans. This is because of progressive increase in reduction potentials from Cu → Ag → Au.
Q.92 How is paramagnetic character expressed?
Ans. It is expressed in terms of magnetic moment having units of Bohr Magneton. The Bohr magneton is
17

defined in SI units by
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 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

and in Gaussian CGS units by Where e is the elementary charge, ħ is

the reduced Planck constant (=h/2π), me is the electron rest mass and c is the speed of light.
Q.93 How is cathodic protection of iron different from its galvanisation?
Ans. In cathodic protection, the iron article is protected by connecting it to more electropositive metal like
Mg, Al etc. On the other hand, galvanisation is a process of protecting the iron article by coating it
with Zn.
Q.94 The entropy of copper sulphate solution increases when a chelating agent is added to it. Explain.
Ans. This is explained on the basis that copper sulphate solution consists of central cupric ion (Cu 2+),
associated with surrounded water molecules, [Cu(H2O)n]2+. When a chelating agent is added, more
than one surrounding water molecules are displaced by each added chelating group. As a result, the
total number of species in the solution increases. Hence, the entropy of solution increases.
Q.95 AgF is fairly soluble in water while other silver halides are insoluble. Give reason.
Ans. This is explained on the basis of two reasons:
(i) Hydration energy of AgF is quite higher than its lattice energy because of smaller size of F – ion and
thus AgF is soluble in water. In other halides, lattice energy is higher than hydration energy, so, they
are insoluble.
(ii) Due to smaller size of F–, AgF is most ionic in nature, hence, soluble in water. Other halides are
predominantly covalent in nature, so, insoluble in water. (Fajan’s rules)
Q.96 What is silvering of mirror? How can it be done?
Ans. The process of depositing a thin and uniform layer of silver on a clear glass surface is known as
silvering of mirrors. It is based on reduction of ammonical silver nitrate solution by some reducing
agent like formaldehyde, glucose etc. The silver film deposited on the glass surface is first coated with
a varnish and finally painted with red lead to prevent its loss due to scrap.
Q.97 Volumetric titrations involving KMnO4 are carried out only in presence of dilute H2SO4 but not in
presence of HCl or HNO3. Explain.
Ans. This is because oxygen produced from KMnO4 + dilute H2SO4 is used only for oxidizing the reducing
agent. Moreover, H2SO4 does not give any oxygen of its own to oxidize the reducing agent. In case
HCl is used, the oxygen produced from KMnO4 + HCl is partly used up to oxidize HCl and in case of
HNO3, it itself acts as an oxidizing agent and partly oxidizes the reducing agent.
Q.98 A green compound, A, on fusion with alkali gave a yellow compound, B, which on acidification gives
orange compound, C. C on reaction with NH4Cl gives orange compound, D, which on heating gives
back A. Identify A, B, C, D and write the structure of C.
Ans. Cr2O3 (A) fusion with alkali, NaOH Na2CrO4 (B) (yellow)
∆↑ ↓ H2SO4 (acidifying)
(NH4)2Cr2O7 (D) NH4Cl Na2Cr2O7 (C) (orange)
(orange)
Cr2O3 (A) + 4 NaOH+ 3/2 O2 → 2 Na2CrO4 (B) + 2 H2O
2 Na2CrO4 (B) + H2SO4 → Na2Cr2O7 (C) + Na2SO4 + H2O
Na2Cr2O7 (C) + 2 NH4Cl → (NH4)2Cr2O7 (D) + 2 NaCl
(NH4)2Cr2O7 (D) → Cr2O3 + N2 + 4 H2O
Structure of C i.e. Na2Cr2O7 is given on page 6 above.
Q.99 How can a drunken driver be tested?
Ans. The person is asked to breathe into the acidified K2Cr2O7 solution taken in a test tube. If the orange
colour of the solution changes to green colour (due to the formation of Cr 2(SO4)3), the driver is
drunk, otherwise not.
K2Cr2O7 + 4 H2SO4 → K2SO4 + Cr2(SO4)3 + 4 H2O + 3[O]
CH3CH2OH + [O] → CH3CHO + H2O, CH3CHO + [O] → CH3COOH
Q.100 Why is Na2Cr2O7 not used in volumetric analysis?
Ans. Because it is deliquescent.
Q.101 Explain the colour of KMnO4.
18

Ans. In MnO4–, Mn is in +7 oxidation state with d0 configuration. Thus d-d transition is not possible. The
deep purple colour of KMnO4 is due to charge transfer from oxygen to Mn, reducing the oxidation
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state of Mn from +7 to +6 momentarily.

Q.102 Why in permanganate ion, there is covalency between Mn and oxygen?
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

Ans. In permanganate ion, Mn is in highest oxidation state i.e. +7. In high oxidation state, transition
metals form covalent bonds.
Q.103 How is the variability of oxidation states of the transition elements different from that of non-
transition elements? Illustrate with examples.
Ans. The variability of oxidation states of transition metals is due to the incomplete filling of d-orbitals in
such a way that their oxidation states differ from each other by unity e.g. Fe 2+ and Fe3+, Cu+ and Cu2+
etc. In case of non-transition elements, the oxidation states differ by units of two, e.g. Pb 2+ and Pb4+,
Sn2+ and Sn4+ etc. Moreover, in transition elements, the higher oxidation states are more stable for
heavier elements in a group. E.g. in group 6, Mo (VI) and W (VI) are more stable than Cr (VI). In p-
block elements, the lower oxidation states are more stable for heavier members due to inert pair
effect. E.g. in group 14, Pb (II) is more stable than Pb (IV).
Q.104 Name a transition element which does not exhibit variable oxidation state.
Ans. Scandium (Z=21) has the electronic configuration 3d1 4s2 and shows an oxidation state of +3 only.
It does not show variable oxidation states.
Q.105 How would you account for the irregular variation of ionization enthalpies (first and second) in first
series of the transition elements?
Ans. Irregular variation in first I.E.:As we move from left to right along the first transition series, as
effective nuclear charge increases, it is expected in general that the first I.E should show an
increasing trend. However, the trend is irregular because removal of an electron alters the relative
energies of 4s and 3d orbitals. Thus, there is a reorganization energy accompanying ionization. This
results into the release of exchange energy which increases as the number of electrons increases in
the dn configuration and also from the transference of s-electrons into d-orbitals. Cr has low first I.E
because loss of one electron gives stable configuration (3d 5). Zn has very high I.E because electron
has to be removed from 4s orbital of the stable configuration (3d 10 4s2).
Irregular variation in second I.E.: After the loss of one electron, the removal of second electron
becomes difficult. Hence, second I.Es are much higher and in general increase from left to right.
However, Cr and Cu show much higher values because the second electron has to be removed from
the stable configurations of Cr+ (3d5) and Cu+ (3d10).
Q.106 The 4d and 5d series of transition metals have more frequent metal-metal bonding in their
compounds than do the 3d metals. Explain.
Ans. In the same group of d-block elements, the 4d and 5d transition element has larger size than that of
3d element. Thus, the valence electrons are less tightly held and hence can form metal-metal bond
more frequently. (That is why melting points of 4d and 5d series as well as enthalpies of atomization
are higher than those of 3d series).
Q.107 Explain the various processes and reactions involved in photography. (IIT 2000)
Ans. Photography: It is a process of getting an exact impression of an object on an art paper with the help
of light. It is based on the principle that the silver halide, AgBr, decomposes in presence of light. The
entire operation is completed in the following steps:
(1) Preparation of photographic plate: Photographic plate consists of a glass plate or a thin strip of
celluloid, which is coated with the thin layer of emulsion of AgBr dispersed in gelatin. In order to
prepare the emulsion, a solution of AgNO3 is mixed with the solution of NH4Br containing gelatin.
NH4Br + AgNO3 gelatin AgBr + NH4NO3
The mixture is kept warmed at a temperature of 450C for some time. AgBr particles grow bigger in
size and also become more sensitive to light. This process is called ripening of the emulsion. After
sufficient interval of time, the emulsion is cooled in ice so that it solidifies. It is then washed with
water to remove NH4NO3. The solid jelly is melted and is spread over a glass plate or a celluloid film.
All these operations are carried in dark room, which is free from dust particles.
(2) Exposure: The sensitive plate or film is loaded in a camera and the image of the object to be
photographed is focused on it. Now the shutter of the camera lens is opened for a short time so that
the film is exposed to light reflecting from the object. Depending upon the colour shade and the
intensity of light reflected from the different parts of the object, the proportionate decomposition of
silver halides set in. 2 AgBr → 2 Ag + Br2
Inverted image of the object which is formed on the plate is not visible and so, this is called latent
19

image.
(3) Developing: The latent image formed during the exposure of the sensitive plate is made more
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prominent by immersing the exposed plate into the solution of developer. A developer is a weak
reducing agent such as potassium ferrous oxalate or organic reducing agents like quinol, amidol or
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

metol. The main function of developer is to complete the reaction started by the light during
exposure and to liberate proportionate amount of Ag.
AgBr + developer → Ag + oxidized developer; e.g. C6H4(OH)2 + 2 AgBr → 2 Ag + C6H4O2 + 2 HBr
(light affected) (black) (quinol)
The developer does not affect those parts of film which are not affected by light. After the developing
process, the bright spots of the object which reflect more light become darker in plate due to more
deposition of Ag and vice-versa. The image now becomes visible and now has a negative relationship
with the object i.e. has exactly opposite shades as compared to those of the object. The plate is,
therefore, called a negative plate.
(4) Fixing of the image: After the developing, the sensitive emulsion of silver halide is still present on
the plate in the parts unaffected by light. It is necessary to remove it in order to get the permanent
image. The process is called fixing of the image. The negative plate after washing is dipped in a
strong solution of sodium thiosulphate (hypo solution) which is also called fixer. The fixer dissolves
unaffected AgBr forming soluble complex sodium argento thiosulphate. Thus, it saves the plate from
turning all black when brought into light.
2 Na2S2O3 + AgBr → Na3[Ag(S2O3)2] + NaBr
Sodium dithiosulphatoargentate(I)
The plate is thoroughly washed after the treatment with the hypo solution and is subsequently dried.
The developing and fixing operations are carried out in the dark room or the presence of blood red
colour or dark green colour. The negative plate after developing and fixing can be taken into light.
(5) Printing: The process of precipitation of negative is repeated in printing process. Printing out
paper (POP) or bromide paper is generally used for printing process. The printing paper is placed
below the negative and then exposed to light for a fraction of second. The developing paper is then
subjected developing and fixing as usual whereby shades of negative are reversed on a printing
paper. Thus, a print can be considered to be a negative of the negative plate and has shades exactly
similar to those of the object.
(f – BLOCK ELEMENTS)
Q.108 What are f-block elements? Give their classification.
Ans. The elements in which the last electron enters (n-2) f-subshell of the ante-penultimate shell are
called f-block elements or inner transition elements. They are called inner transition elements
because they exist in between transition elements. The f-block elements are made up of two series:
(i) Lanthanides: The elements in which the last electron enters one of the 4f-orbitals are called
lanthanides. Elements from Ce58 to Lu71 are lanthanides. Their general electronic configuration is 4f1-
14 5d0-1 6s1-2.

(ii) Actinides: The elements in which the last electron enters one of the 5f-orbitals are called
actinides. Elements from Th90 to Lr103 are actinides. Their general electronic configuration is 5f1-14
6d0-1 7s1-2.
Q.109 What is lanthanide contraction? What is its cause and consequencies?
Ans. Lanthanide contraction: The slow or gradual decrease in the size of lanthanide atoms and ions as we
move from left to right in a lanthanide series is called lanthanide contraction i.e. in a lanthanide
series, on moving from left to right, the size decreases slowly. This is in contrast to s and p-block
elements where it decreases sharply with increase in atomic number and also to d-block elements
where it firstly decreases then remains constant and then increases. The ionic size of tripositive
lanthanides is given as under:
La3+ Ce3+ Pr3+ Nd3+ Pm3+ Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+ Yb3+ Lu3+
106 103 99 98 96 95 94 92 91 89 88 87 86 85 84
Cause of lanthanide contraction:
(i) On moving from left to right in a lanthanide series, atomic number increases. The number of
protons as well as number of electrons also increases. Thus, the effective nuclear charge also
increases. The force of attraction between the nucleus and the outermost electron should increase
and size should decrease.
(ii) In lanthanides, the electrons are added to (n-2) f-subshell. Since f-electrons are 14 in number,
the screening effect due to f-electrons should increase and force of attraction between the outermost
20

electron and the nucleus should decrease and size should increase. In case of lanthanides, the
screening effect due to f-electrons is not proper. This is due to structure of f-orbitals. Thus, force of
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attraction between the outermost electron and the nucleus is not properly shielded by the intervening
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

electrons. As a result, there is a slow or gradual decrease in size of lanthanides which is called
lanthanide contraction.
Consequencies of lanthanide contraction:
(i) Difficulties in the separation of lanthanides: lanthanides have almost comparable sizes. Their
nuclear charges are also comparable. So, their properties are identical and they occur along with one
another in the earth’s crust and their separation is difficult.
(ii) Basicity of oxides and hydroxides: La2O3 is more basic than Lu2O3 and La(OH)3 is more basic than
Lu(OH)3. This is explained on the basis that with the decrease in size from La to Lu, electropositive
character decreases and so basicity also decreases.
(iii) Similarity in the size of elements belonging to same group of second and third transition series:
Due to lanthanide contraction, the sizes of the elements of second and third transition series become
comparable and their properties resemble. E.g. Zr-40 and Hf-72 have similar properties due to
lanthanide contraction. Similarly, Nb-41 and Ta-73 also have similar properties.
(iv) Complex forming tendency: lanthanides have larger sizes in comparison to d-block elements and
as a result, they how little complex forming tendency.
Q.110 Write a note on oxidation state of lanthanides.
Ans. The most stable oxidation state of lanthanides is +3. But however, some lanthanides show oxidation
state of +2 or +4. This is probably due to more stable electronic configurations in these cases.
(i) Eu and Yb show an oxidation state of +2. This is because they have exactly half and fully-filled
electronic configurations. i.e. Eu2+ = [Xe] 4f7 (exactly half-filled); Yb2+ = [Xe] 4f14 (exactly fully-
filled).
(ii) Ce and Tb show an oxidation state of +4. This is because they have exactly half and fully-filled
electronic configurations. i.e. Ce4+ = [Xe] 4f0 (fully-filled); Tb4+ = [Xe] 4f7 (exactly half-filled).
(iii) La, Gd and Lu show +3 oxidation states because of empty, half-filled and fully-filled f-subshells.
(iv) Lanthanides show limited number of oxidation states because the energy gap between 4f and 5d
subshells is large.
(v) Transition elements can show many different oxidation states because in transition elements, the
d-electrons are present in (n-1) d-subshell which can easily participate in bond formation but in case
of lanthanides, the f-electrons are present in deeper (n-2) f-subshell which cannot participate in
bond formation.
Q.111 Write a note on colour of f-block elements.
Ans. f-block elements are themselves silvery white but their ions are coloured in nature. The colour in
case of f-block element is explained on the basis of f-f transition. An interesting feature of colour of f-
block elements is that f-block metal ion having n unpaired electrons has the same colour as the one
having (14-n) f-electrons i.e. there is a perfect periodicity in the colour of f-block metal ions. E.g.
La3+ and Lu3+ are colourless, Sm3+ and Dy3+ are yellow and Eu3+ and Tb3+ are pink.
Q.112 Write a note on magnetic properties of f-block elements.
Ans. f-block elements are magnetic in nature. The magnetic nature of f-block elements is due to both
orbital motion as well as spin contribution. The magnetic moment of f-block elements is given by the
relation μ = √4s(s+1) + l(l+1) where s = spin quantum number and l = secondary quantum
number. The variation of magnetic moment for lanthanides is given as under:

Dy Ho
Tb Em
Magnetic moment ↑ Pr Nd Gd Tm

Ce Pm Eu Yb
Sm
La Lu
Atomic number →
The variation of paramagnetism of f-block elements is quite complex. There are two maxima in this
curve and unlike d-block elements it cannot be explained easily.
NOTE: f-block elements are more magnetic than d-block elements.
21

Q.113 Differentiate between lanthanides and actinides.

Ans.
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Lanthanides Actinides
1. Most probable oxidation state is +3. Also show +2 1. Along with +3, they show +4, +5, +6, +7
 CHEMISTRY MATTERS
DR. SAHAS AGGARWAL

& +4 states.
2. Lesser tendency for complex formation 2. They have more complex forming tendency
3. They are less basic 3. They are more basic
4. They do not form oxocations 4. They form oxocations like UO22+ and
PuO22+
5. Except Promethium, they are non-radioactive 5. They are radioactive
6. Magnetic properties are explained comparatively 6. Magnetic properties cannot be easily
easily explained
7. Most of their ions are colourless 7. Most of their ions are coloured
Q.114 What is actinide contraction?
Ans. Actinide contraction is the steady decrease in the size of the atoms and ions along the actinide series.
This is due to poor screening of nuclear charge by f-electrons. (Causes same as lanthanide
contraction)
Q.115 Lanthanides do not have much tendency to form complexes. Explain.
Ans. This is because of low charge density in lanthanides due to their large sizes. The tendency to form
complexes and their stability increases with increase in their atomic number.
Q.116 Why is it not appropriate to call lanthanides as rare earth elements?
Ans. Earlier lanthanides were called as rare earth elements because for many years the compounds of
these elements were difficult to obtain. Now the term rare earth is not appropriate because many of
these elements are very abundant.
Q.117 Why Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents but an aqueous solution of Ce4+
is a good oxidizing agent?
Ans. This is explained on the basis that the most stable oxidation state of lanthanides is +3. Hence ions in
+2 oxidation state tend to change to +3 oxidation state by losing electrons and those in +4 state tend
to change to +3 by gaining electrons.
Q.118 Use Hund’s rule to derive the electronic configuration of Ce3+ ion and also calculate its magnetic
moment on the basis of spin only formula.
Ans. Ce58 = [Xe] 4f1 5d1 6s2; Ce3+ = [Xe]54 4f1 i.e. it has only one unpaired electron. Hence, n=1.
μspin = √n(n+2) B.M = √1(1+2) = √3 = 1.73 B.M.
Q.119 How would you account for the fact that actinides exhibit a larger number of oxidation states than
the corresponding lanthanides?
Ans. Actinides show a larger number of oxidation states because the energy gap between 5f, 6d and 7s
subshells is very small and hence all the electrons present in these subshells can participate in
bonding whereas lanthanides show a limited number of oxidation states because the energy gap
between 4f and 5d subshells is large and all the electrons in these subshells cannot participate in
bonding.
Q.120 Briefly explain why electronic configurations of lanthanides are not known with certainty.
Ans. In the lanthanides, 4f and 5d subshells are very close in energy. The outermost 6s orbital remains
filled with 2 electrons (6s2). The electron can easily jump from 4f to 5d or vice-versa. Hence, their
electronic configurations are not known with certainty.
Q.121 Of the lanthanides, cerium forms a tetrapositive ion in aqueous solution. Why?
Ans. Ce (III) having the configuration 4f1 5d0 6s0 can easily lose an electron to acquire the configuration
4f0 and form Ce (IV). In fact, this is the only (+IV) lanthanide which exists in solution.
22
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