Que 1. Cu+ is not stable in an aqueous solution. Why?

Ans 1. In an aqueous solution, Cu+ undergoes disproportionation to form a more

stable Cu2+ ion. 2Cu+ (aq) → Cu2+ (aq) + Cu(s)
The higher stability of Cu2+ in an aqueous solution may be attributed to its greater
negative ∆hydH
than that of Cu+. It compensates for the second ionization enthalpy of Cu involved
in the formation of Cu2+ ions.
Que 2. Which is a stronger reducing agent Cr2+ or Fe2+ and
why?
Ans 2. Cr2+ is a stronger reducing agent than Fe2+ because after the loss of one
electron Cr2+ becomes Cr3+ which has a more stable t2g3 (half-filled) configuration
in a medium like water.
Que 3. Arrange the following increasing order of acidic
character: CrO3, CrO, Cr2O3
Ans 3. CrO <Cr2O3<CrO3. The higher the oxidation state the more will be the
acidic character.
Que 4. Calculate the ‘spin only’ magnetic moment of M2+
(aq) ion. (Z=27)
Ans 4. The electronic configuration of the M2+ ion (Z=27) would be M2+(aq):
(Ar) 3d7 It would contain three unpaired electrons. The ‘spin only’ magnetic
moment is given by the relation:
µ = n (n + 2) BM = 3 (3 + 2) BM = 3.87 BM
Que 5. Why do Zr and Hf exhibit almost similar properties?
Ans 5. Zr and Hf have similar ionic sizes due to their lanthanoid contraction. So,
they exhibit similar properties.
Que 6. Why are Zn, Cd, and Hg not regarded as transition
elements?
Ans 6. Zn, Cd, Hg neither in their ground state nor in the oxidized state have
partially filled d‐orbital. Thus, they are not regarded as transition elements.
Que 7. What are alloys? Name one important alloy which
contains some of the lanthanoid metals. Mention its use.
Ans 7. Alloys are homogeneous mixtures of metals with metals or non‐metals.
Misch metal (pyrophoric alloy) consists of lanthanoid metal Ce = 40.5%,
neodymium 44%, iron 4‐5%, and traces of S, C, Ca, and Al. Misch metal is used to
make bullets, shells, and light flints.
Que 8. La(OH)3 is a stronger base than Lu(OH)3. Why?
Ans 8. Lu3+ is smaller in size than La3+ due to lanthanoid contraction. Due to the
smaller size of Lu3+, the Lu‐O bond is stronger than the La‐O bond in the
respective hydroxides. Due to the weaker La‐O bond, La(OH)3 behaves as a
stronger base.
Que 9. Lanthanoids form primarily +3 ions, while the
actinoids usually have higher oxidation states in their
compounds, +4 or even +6 being typical.
Ans 9. Lanthanoids exhibit oxidation states of +2, +3, and +4. This is because
of the large energy gap between 4f, 5d, and 6s subshells. Actinoids show +3, +4,
+5, +6, and +7 oxidation states because 5f, 6d, and 7s energy levels are nearly the
same.
Que 10. What is meant by the term lanthanoid
contraction? What is it due to and what consequences
does it have on the chemistry of elements following
lanthanoids in the periodic table?
Ans 10. Lanthanoid contraction: Steady decrease in the size of the lanthanoids
with an increase in the atomic number across the period. The electrons of 4f
orbitals offer imperfect/poor shielding effect in the same subshell.
Consequence:
i) Due to this 5d series elements have nearly the same radii as that of the 4d series.
ii) Decrease in the basic strength from La(OH)3 to Lu(OH)3.
iii) Due to similar atomic size there is difficulty in the separation of lanthanides.
Que 11. Compare lanthanoids and actinoids with reference
to their:
a. Electronic configuration of atoms.
b. Atomic and ionic sizes.
c. Oxidation states of elements.
d. The general chemical reactivity of elements.
Ans 11. (a) Electronic configuration: lanthanoids have general
electronic configuration [Xe]4f1−145d0−16s2. Actinoids have general electronic
configuration [Rn]5f1−146d0−17s2.
In lanthanoids, 4f orbital is filled and in actinoids, 5f orbital is filled.
(b) Atomic and ionic sizes: The atomic and ionic sizes of lanthanoids
and actinoids decrease with an increase in the atomic number due to lanthanoid and
actinoid contraction.
(c) Oxidation state: Apart from the +3 oxidation state, lanthanoids show
+2 and +4 oxidation states due to a large energy gap between 4f and 5d subshells.
Whereas actinoids show a large number of oxidation states due to a small energy
gap between 5f and 6d subshells.
(d) Chemical reactivity: Highly electropositive lanthanoids have almost
similar chemical reactivity. Actinoids (electropositive and highly reactive) are
more reactive (especially in the finely divided state) than lanthanoids.
Que 12. How would you account for the following?
a). Mn(III) undergoes disproportionation reaction easily.
b). Co(II) is easily oxidized in the presence of strong
ligands.
Ans 12. a). Mn3+ is less stable and changes to Mn2+ which is more stable due to
the half‐filled d‐ orbital configuration. That is why Mn3+ undergoes
disproportionation reaction.
b). Co(II) has electronic configuration 3d74s0, 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 oxidized to Co(III).
Que. 13 Give reasons for the following:
i) First ionization energies of 5d elements are higher than
those of 3d and 4d elements.
ii) Actinoid contraction is greater from element to element
than lanthanoid contraction.
Ans 13. i) Because of the weak shielding (or screening) effect of 4f electrons,
the effective nuclear charge acting on the valence electrons in 5d elements is quite
high. Hence, the first ionization energies of 5d elements are higher than those of 3d
and 4d elements.
ii) This is because the 5f electrons themselves provide poor shielding from element
to element in the series.
Que 14. Explain the following observations about the
transition/inner transition elements:
i) There is, in general, an increase in the density of
elements from titanium (Z=22) to copper (Z=29).
ii) There occurs much more frequent metal‐metal bonding
in compounds of heavy transition elements (3rd series).
iii) The greatest number of oxidation states are exhibited
by the members in the middle of a transition series.
Ans 14. i) Because of the decrease in atomic size from titanium to copper.
ii) Because of high enthalpies of atomization of heavy transition elements.
iii) Because of the involvement of both (n‐1)d and ns electrons in bonding.
Q 15: Assign reasons for the following:
a) The enthalpies of atomization of transition elements
are high.
b) The transition metals and many of their compounds act
as good catalysts.
c) There is a gradual decrease in the atomic sizes of
transition elements in a series with increasing atomic
numbers.
d) The transition elements have a great tendency for
complex formation.
e) Transition metals generally form coloured compounds.
Ans 15: a) This is because transition elements have strong metallic bonds as
they have a large number of unpaired electrons, therefore they have greater
interatomic overlap.
b) The catalytic activity of transition metals is attributed to the following reasons‐
i) Because of their variable oxidation state, transition metals form unstable
intermediate compounds and provide a new path with the lower activation energy
for the reaction.
ii) In some cases, the transition metal provides a suitable large surface area with
free valencies on which reactants are adsorbed.
c) There is a gradual decrease in the atomic sizes of transition elements in a series
with increasing atomic numbers due to poor shielding effects of the d‐electrons, the
net electrostatic attraction between the nucleus and the outermost electrons
increases
d) orbitals of suitable energy, the small size of cations, and higher nuclear charge.
e) Due to the presence of unpaired electrons in d‐orbitals which undergoes a d‐d
transition.
Que 16. Explain briefly how the +2 state becomes more
and more stable in the first half of the first-row transition
elements with increasing atomic number?
Ans 16. In transition elements, there are greater horizontal similarities in the
properties in contrast to the main group elements because of similar ns 2 common
configuration of the outermost shell. An examination of common oxidation states
reveals that excepts scandium, the most common oxidation state of first-row
transition elements is +2 which arises from the loss of two 4s electrons. This means
that after scandium, d-orbitals become more stable than the s-orbital. Further, the
+2 state becomes more and more stable in the first half of first-row transition
elements with increasing atomic number because 3d orbitals acquire only one
electron in each of five 3d orbitals (i.e. remains half-filled) and electronic repulsion
is the least, and nuclear charge increases. In 2nd half of first-row transition
elements, electrons start pairing up in 3d orbitals. (Ti2+ to Mn2+ electronic
configuration changes from 3d2 to 3d5 but in 2nd half i.e. Fe2+ to Zn2+ it changes
from d6 to d10).
Que 17. 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 17. Among the actinoids, there is a greater range of oxidation states as
compared to lanthanoids. This is in part due to the fact that 5f, 6d, and 7s levels are
of very much comparable energies and the frequent electronic transition among
these three levels is possible. This 6d-5f transition and a larger number of
oxidation states among actinoids make their Chemistry more complicated
particularly among the 3rd to 7th elements. following examples of oxidation states
of actinoids. Justify the complex nature of their Chemistry.
(i) Uranium exhibits oxidation states of +3, +4, +5, +6 in its compounds. However,
the dominant oxidation state in actinoids is +3.
(ii) Nobelium, No is stable in +2 state because of completely filled f 14 orbitals in
this state.
(iii) Berkelium, Bk in +4 oxidation state is more stable due to f 7 (exactly half-
filled) configuration.
Que 18. Write complete chemical equations for:
(i) Oxidation of Fe2+ by Cr2O72– in acid medium.
(ii) Oxidation of S2O32– by MnO4– in neutral aqueous solution.
Ans 18. (i) 6Fe2+ + Cr2O72– + 14 H+ →6Fe3+ + 2Cr3+ + 7H2O
(ii) 2MnO4– + 3S2O32– + H2O → 2MnO2 + 3SO42– + 3S + 2OH–.
Que 19. (i) A black mineral (A) on treatment with dilute
sodium cyanide solution in presence of air gives a clear
solution of (B) and (C).
(ii) The solution (B) on reaction with zinc gives a
precipitate of a metal (D).
(iii) (D) is dissolved in dilute HNO3 and the resulting
solution gives a white precipitate (E) with dilute HCl.
(iv) (E) on fusion with sodium carbonate gives (D).
(v) (E) dissolves in ammonia solution giving a colourless
solution of
(F). Identify (A) to (F) and give chemical equations for
reactions at steps (i) to (v).
Ans 19. On the basis of the given data, the black mineral (A) is a silver glance,
Ag2S. It is confirmed by the following:
(i) It dissolves in sodium cyanide solution in presence of air.
Que 20. Explain which one of the following is a good
oxidizing agent: Sc3+, Ce4+or Eu2+ (atomic of Sc=21, Ce=58,
Eu=63)
Ans 20. The electronic configuration of Sc, Ce and Eu are
21Sc= [Ar] 3d 4s
1 2

58Ce= [Xe] 4f 5d 6s
2 1 1

60Eu= [Xe] 4f 5d 6s
7 0 2

Due to the stable configuration of Sc3+and Eu2+they will not gain electron whereas
Ce4+can take one electron and become stable thus Ce4+is good oxidizing agent.