D & F BLOCK ELEMENTS…..

IMPORTANT QUESTIONS WITH ANSWERS

Q 1 :The transition metals are well-known for the formation of interstitital compounds. Explain.

Sol. This is because they have voids in which small atoms C and H can fit forming interstitial compounds.

Q2 :Which element in the first series of transition elements does not exhibit variable oxidation states
and why ?

Sol. Scandium does not exhibit variable valency. It shows +3 oxidation state only. This is because after
losing 3 electrons, it attains stable noble gas structure.

Q 3 :Write chemical equations for the reactions involved in the manufacture of potassium
permanganate from pyrolusite ore.

Sol. Relevant equations for the manufacture of KMnO4 from pyrolusite ore are :

(i) 2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O

(ii) MnO42– MnO4 - + e-

Q 4: The outer electronic configurations of two transition metals are (i) 3d54s2 and 3d64s2, respectively
Based on this information predict the relative stability of +2 and +3 oxidations states of these metals.
Which one of the two exhibits larger number of oxidations states?

Sol. Metal with configuration 3d54s2 will show +2 oxidation state more readily than +3 because of
greater stability of half filled d-orbitals. Metal with configuration 3d6 4s2 will be more stable in +3
oxidation state than +2 due to stable electronic configuration having half filled d-orbitals. Metals with
3d54s2 will exhibit largers number of oxidation states : +2, +3, +4, +5, +6, +7.

Q 5 :Explain why the first ionisation energies of the elements of the first transition series do not vary
much with increasing atomic number.

Sol. Ionisation enthalpy normally increases with increase in atomic number along a given transition
series. However, we find that there is not much variation in ionisation energy (enthalpy) in the first
transition series. This can be explained by saying that the removal of an electron alters the relative
energies of 4s and 3d orbitals. Thus, there is reorganisation energy accompanying ionisation. This results
into release of exchange energy which increases as the number of electrons increase in the d-orbitals
and also from the transference of electrons into d-orbitals.

Q 6 :Of the ions Co2+, Sc3+ and Cr3+, which one will give coloured aqueous solutions and how will each
of them respond to a magnetic field and why ? [Atomic numbers of Co = 27, Sc = 21, Cr = 24]

Sol. Co2+ and Cr3+ are coloured and attracted in magnetic field whereas Sc3+ is colourless and repelled
by magnetic field. It is because Co2+ (3d7) and Cr3+ (3d3) have unpaired electrons and can undergo d-d
transitions by absorbing light from visible region. Sc3+ does not have unpaired electron and cannot
undergo d-d transitions.

Q.7Explain why the largest number of oxidation states are exhibited by manganese in the first series of
transition elements.
Sol : Mn (25) : 4s2 3d5 have five unpaired electrons in d-orbitals and two electrons in s-orbital which can
take part in bond formation. Therefore, it shows maximum number of oxidation states.

Q.8 : Describe the steps involved in the preparation of either potassium dichromate from sodium
chromate or potassium permanganate from manganese dioxide.

Sol : 2Na2CrO4 + H2SO4 Na2SO4 + Na2Cr2O7 + H2O

Na2Cr2O7 + 2KCl K2Cr2O7 + 2NaCl or

MnO2 + 2KOH + ½ O2 K2MnO4 + H2O

MnO42– MnO4– + e–

Q.9 Mention the direct consequence of the following factors on the chemical behaviour of the transition
elements

(i) They have incompletely filled d-orbitals in the ground state or in one of the oxidised states of their
atoms.

(ii) They contribute more valence electrons per atom in the formation of metallic bonds.

Sol : (i) (a) They can from complex compounds.(b) They show variable oxidation states.(c) They are used
as catalyst.

(ii) (a) They are hard. (b) They have high melting and boiling points.

(c) They have high enthalpy of atomisation (d) They are malleable and ductile.

Q.10 Among ionic species Sc3+, Ce4+, and Eu2+, which one is a good oxidising agent ? Give a suitable
reason for your answer. [Atomic numbers of Sc = 21, Ce = 58, Eu = 63]

Sol : Ce4+ is a good oxidising agent because after gaining electron, it acquires more stable configuration
in lower oxidation state, i.e., in +3 oxidation state.

Q.11 (a) Describe the general trends in the following properties of the first series of the transition
elements :

(i) Stability of +2 oxidation state (ii) Formation of oxometal ions.

(b) Assign reason for each of the following :

(i) Transition elements exhibit variable oxidation states

(ii) Transition metal ions are usually coloured.

Sol : (a) (i) Most of transition metals show +2 oxidation state. Mn2+ is more stable due to half filled d-
orbitals.

(ii) They form oxometal ions because they show variable oxidation states and form stable oxo anions like

MnO4–, CrO42– and Cr2O72–.

(ii) Transition metals ions have unpaired electrons. They can undergo d-d transition by absorbing light
from visible region and radiating complementary colour.

Q.12 It is difficult to separate lanthanoid elements in pure state. Explain

Sol : 1 It is because lanthanoids have similar ionic size and similar properties that their separation
becomes difficult

Q.13 The outer electronic configuration of atoms of two members of lanthanoid series are given below :

(i) 4f15d16s2 (ii) 4f75d06s2

Find their atomic numbers. What oxidation states will possibly be exhibited by these elements ?

Sol : Elements with electronic configurations (i) and (ii) are Cerium (Ce) and Euporium (Eu) respectively.
Their atomic numbers are Ce = 58 and Eu = 63. Ce shows + 4 oxidation state. Eu shows +2 oxidation
state.

Q14 ; Why do actionids, in general, exhibit a greater range of oxidation states than the lanthanoids ?

Sol. The energies of 5f, 6d and 7s are comparable. So all of these electrons take part in bond formation.
Therefore, actinoids, in general, exhibit a greater range of oxidation states.

Q 15 :What is meant by ‘lanthanoid contraction’ ? State one use each of lanthanoid metals and their
oxides.

Sol. The decrease in atomic and ionic size with increase in atomic number in lanthanoids is called
lanthanoid contraction.

Uses : Lanthanoids are used for production of alloy steels for plates and pipes. Mixed oxides of
lanthanoid metals are used as catalyst in petroleum cracking.

Q16 : How do you account for the following :

(i) All scandium salts are white ? (ii) The first ionisation enegies of the 5d transition elements are higher
than those of the 3d and 4d transition elements in respective groups ?

Sol. (i) In scandium salts, scandium has +3 oxidation state. Sc3+ does not have unpaired electrons and
has empty d-orbitals. Therefore, there is no d-d transitions, hence its salts are white.

(ii) Due to poor shielding effect of 5d and 4f-electrons, effective nuclear charge increases, hence
ionization energy of 5d transition elements is more than that of 3d and 4f transition elements in
respective groups.

Q 17 :Explain the following observations :

(a) The elements of the d-series exhibit a larger number of oxidation states than the elements of f-
series.

(b) The Cu+ salts are colourless while Cu2+ salts are coloured. [Atomic number of Cu = 29]
Sol. (a) In d-series, there are large number of unpaired electrons which take part in bond formation due
to less effective nuclear charge, therefore number of oxidation states are more. In f-block, there is more
effective nuclear charge due to poor shielding effect of f-orbitals. Therefore, less number of electrons
take part in bond formation.

(b) Cu+ does not have unpaired electron, therefore the electrons cannot undergo d-d transitions. That is
why Cu+ salts are colourless. Cu2+ salts are coloured due to presence of one unpaired electron, it can
undergo d-d- transition by absorbing light from visible region and radiating blue colour.

Q 18: With the help of ionic equations describe what happens when

(i) pH of a solution of dichromate ions is raised.

(ii) Potassium manganate is electrochemically oxidised.

Sol. (i) The reactions are described with the help of the following ionic equations

Cr2 O7 2- + 2OH- 2Cr O4 - + H2O

When pH is increased, i.e., solution is more basic, orange coloured dichromate ion changes to yellow

coloured chromate ion.

(ii) MnO4 2- MnO4 - + e-

When potassium manganate is electrochemically oxidised, i.e., it undergoes, electrolytic oxidation, it

Q19 : The transition elements form interstitial compounds. Explain

Sol. The transition metals have voids in their crystal lattice into which small atoms like H, C can fit
resulting in formation of interstitial compounds.

Q20 : Identify the first row transition metal ions which have outer electronic configurations of 3d4 and
3d6 and describe their oxidation states.

Sol. First row transition metal ions which have configurations 3d4 and 3d6 are Cr2+ and Fe2+
respectively. Cr shows oxidation states of +3 and +6. Iron shows +2 and +3 oxidation states.

Q21 :How would you account for the following ?

(i) Sc, the first member of first transition series does not exhibit variable oxidation state

(ii) K2PtCl6 is well-known compound whereas corresponding compound of nickel is not known.

(iii) Only transition metals form complex compounds with ligands such as CO.

Sol. (i) It loses all the three electrons (3d14s2) to show +3 oxidation state and has stable inert gas
configuration.

(ii) K2PtCl6 is known because energy required to remove four electrons in Pt is less as compared to that
in Ni, therefore, corresponding compound of Ni is not known.
(iii) Transition metals are smaller in size and have vacant d-orbitals of suitable energy which can accept
lone pair of electrons from CO to form coordinate bond.

Q22 : Complete the following equations: (i) Cr2O72– + 2OH– (ii) MnO4– + 4H+ + 3e– (b) Account
for the following :

(i) Zn is not considered as a transition element.

(ii) Transition metals form a larger number of complexes.

(iii)The E° value for the Mn3+/ Mn2+ couple is much more positive than that for Cr3+/Cr2+ couple.

Sol. (a) (i) Cr2O72– + 2OH– 2CrO4–2 + H2O (ii) MnO4– + 4H+ + 3e– MnO2 + 2H2O

(b) (i) In Zn inner 3d-subshell is full filled.

(ii) Conditions required to form complex are : (I) Metal ion must have high charge density. (II) Metal ion

must have vacant orbitals. Transition elements follow these requirements. Hence, they form complexes.

(iii)For Mn '+2' oxidation state is more stable than '+3' oxidation state while for Cr '+3' oxidation state is

more stable '+2' oxidation state.

*************************************************************************************
****