The d- and f-Block elements

Give Reasons:
1. Zn, Cd and Hg of group 12 are not regarded as transition elements.

A. These metals have completely filled d orbital(d10) in ground state as

well as in their common oxidation states.

2. Electronic cofig of Cr(Z=24) is [Ar] 3d54s1 instead of 3d44s2.Likewise

Cu(Z=29) is [Ar] 3d104s1 instead of [Ar]3d94s2.

A.because half and completely filled sets of orbitals are relatively more
stable and this is possible because the energy gap between 3d and 4s
sets of orbitals is small.

3. Cu has completely filled 3d orbital. Why it is a transition element?

A. In +2 state it has incompletely filled 3d orbital.(3d9)

4. Silver has outer configuration 4d105s1 in its ground state,it is still a

transition metal.

A.Silver(Z=47) exhibits +2 state wherein it will have incompletely filled

4d orbitals hence a transition metal. Ag =[Kr] 4d10 5s1 Ag2+= [Kr[ 4d9

5. Transition metals have high melting and boiling points.

A.Due to involvement of both ns and (n-1)d electrons in bonding

resulting in strong interatomic metallic bonds.
6. In any row of d block elements the Melting of metals rise to
maximum at d5 (except for Mn and Tc) and then fall regularly.

A. because from d6 config onwards due to pairing of electrons in d

orbitals number of unpaired electrons are less. i.e, interatomic
bonds get weaker. However Mn and Tc show anomalous behavior.

7. In many of the properties of the d block elements the maximum

occur at about the middle of each series.

A. This indicates that one unpaired electron per d orbital is particularly

a favourable configuration for strong interatomic interaction.

8. Transition metals are hard, have high densities and high enthalpies
of atomization.(transition metal has high enthalpy of atomization)

i)because of large no of unpaired e.

ii)strong interatomic metallic bonds

iii)strong interatomic interaction

9. Metals of 2nd and 3rd transition series(4d and 5d series) have greater
enthalpies of atomization than the corresponding elements of 1st
series(3d series).

A.Due to much more frequent metal-metal bonding in the heavier

transition metals.

10. Successive ionization enthalpies for block elements do not

increase as steeply as in the main group elements with
increasing atomic number.

A.Loss of variable number of electrons from (n-1)d orbitals is not

energetically favourable.
11. In the series Sc(Z=21) to Zn(Z=30), the enthalpy of atomization of
zinc is the lowest .

A. In the case of Zn, no electrons of 3d orbitals are involved in the

formation of metallic bonds. Zn has completely filled d orbital, has no
unpaired electrons. while in all other metals the electrons of 3d orbitals
are involved in the formation of metallic bonds.

12.d-block elements are also called transition metals.

A. It is because of their position between the s-Block and the p-

Block elements.

13. Atomic and Ionic radii (ions of same charge) in a given series of
d block progressively decrease with increase in atomic number.

A. This is because the new electron enters a d orbital each time the
nuclear charge increases by unity. The poor shielding effect of d
electrons, hence the net electrostatic attraction between the nucleus
and outermost electron increases and radii decreases.

14. There is an increase in radii from 3d to 4d series but the radii of 5d

series are nearly the same as as those of corresponding members of 4
d series.

A. The 5d series of elements have fully filled 4f orbitals(i.e they

follow lanthanoids). Due to very weak shielding of 4f electrons
there is a regular decrease in atomic radii. This effect is called
Lanthanoid Contraction which compensates for the expected
increase in atomic size with increasing atomic number down the
group.
15. The 2nd and 3rd transition series e.g;Zr(Zirconium) and Hf(Hafnium)
or Nb(Niobium) and Ta(Tantalum) have similar physical and chemical
properties much more than that expected from usual family
relationship.(Zr and Hf have similar properties.)

A. This is due to similarity in their radii(Due to lanthanoid

contraction)because of poor shielding effect of 4f electrons.

16. From Ti(Z=22) to Cu(Z=29) there is a significant increase in density.

A. The decrease in metallic radius coupled with increase in atomic mass

results in an increase in density of these elements.

17. Ionisation enthalpy increase along each series.

A. Due to Increase in nuclear charge which accompanies the filling of

inner d electron, coupled by weak shielding effect of the d electrons.

18. The trend in Ionisation enthalphy of 3d metals is irregular.

A. Removal of one electron alters the relative energies of 4s and 3d
orbitals. So the unipositive ions have dn configuration with no 4s
electrons. There is reorganization energy accompanying ionization and
exchange energy increases as number of d electrons increases. Value of
Cr is low because of no change in d config but value of Zn is higher
because of ionization from 4s orbital.

19. Cr and Cu have unusally high 2nd ionization enthalpy value and Zn
correspondingly low.

A. 24Cr 1s22s22p63s23p63d54s1

29Cu 1s22s22p63s23p63d104s1

30Zn 1s22s22p63s23p63d104s2

In Cr and Cu the stable half filled and fully filled d5 and d10
configurations of the ions are disrupted while Zn2+ allows the
production of stable d10 state.

20. Mn2+ compounds are more stable than Fe2+ towards oxidation to
their +3 state.

25Mn = [Ar] 3d54s2

Mn2+ = [Ar]3d5(a stable half - filled 3d5config) Therefore Mn2+

resists oxidation to Mn3+

26Fe =[Ar] 3d64s2

Fe2+ =[Ar] 3d6

Fe3+ =[Ar] 3d5(stable half-filled 3d5 config)

Fe3+ has stable half -filled configuration, Fe2+ tends to easily get
oxidized to more stable +3 state.
21.The +2 state becomes more and more stable in the first half of the
3d series with increasing atomic number.

A. Except scandium (which shows +3) , all other first row transition
elements show +2.This is due to loss of two 4s electrons. In the first
half, as we move from Ti2+ to Mn 2+, the electronic configuration
changes from 3d2 to 3d5 i.e more and more d orbitals are half filled
imparting greater stability to +2.Fe2+ to Zn2+ the electronic configuration
changes from 3d6 to 3d10 i.e the electrons is 3d orbitals pair up and
number of half- filled orbital decreases. Hence stability Of +2 state
decreases.

22. Transition metals show variable oxidation state.

A. Due to the participation of the ns as well as (n-1) d electrons

in bonding.
 Zinc has lowest enthalpy of atomization in 3d series.

23. The elements which give the greatest number of oxidation state
occur in or near the middle of the series (e.g Mn or Cr) Mn=+2 to
+7, Cr= + 2 to +6

A. Due to the availability of greater number of unpaired d electrons for

bonding.

24. How does transition element differ from non-transition elements?

A.The variation in oxidation state for transition elements is by

unity, While for non -transition elements(p blocks) it is by 2.
Mn =+2 +3 +4 +5 +6 +7 P= +3 +5

25. The variation in oxidation state for transition elements is by

unity, While for non -transition elements (p blocks) it is by 2.

A.In transition elements variability in O.S arises due to incompletely

filled or partially filled d orbitals while in non - transition elements it is
due to inert pair effect and excitation of electrons.

e.g O.S of V= +2, +3, +4, +5

Mn= +2 to +7 ; Cr= +2 to +6

while for Pb= +2, +4

S= +2, +4, +6

P= +3, +5

26. Cr2+ is reducing and Mn3+ is oxidizing when both have d4 config.
A.Cr2+ is reducing(i.e acts as reducing agent) as its config changes from d4
to more stable d3 . Cr2+ get oxidized to Cr3+ d3is more stable because it
has a stable half - filled t2g level. whereas Mn3+ is oxidizing(i.e acts as an
oxidizing agent)because it gets reduced to Mn2+ to acquire stable half
filled 3d5 configuration.
25Mn = [Ar] 3d54s2
+3
25Mn = [Ar] 3d4
Mn2+ = [Ar]3d5

Cr = [Ar] 3d54s1

Cr+2 = [Ar] 3d4

Cr+3 = [Ar] 3d3

Note
Mn has stable electronic configuration (3d5 half filled, 4s2fully filled)

27. In aqueous medium Cr2+ is better reducing agent than Fe2+.

A.In case of Cr2+ d4d3 ( Cr3+)

for Fe2+ d6d5 (Fe3+)

Water acts as ligands and in the presence of ligands the 3d orbitals form
2 sets t2g and eg. In Cr3+ there is half filled config in t2g level. Therefore
Cr3+ is a stronger reducing agent.
28. The highest oxidation state of a metal in exhibited state in its oxide
or fluoride.

A. because of small size and high electronegativity of oxygen and

fluorine they can oxidize the metal to its highest oxidation state.

29. In the 3d series Mn exhibits largest number of oxidation states.

A. Mn(Z=25) because it has the maximum number of unpaired

electrons. Mn=[Ar] 3d54s2

30. Co(II) is stabe in aqueous solution but in the presence of

complexing reagents it is readily oxidized to (III) state.

A. Due to crystal field splitting energy which more than compensates

the 3rd ionization enthalpy.

31. The d1 configuration is very unstable for ions.

A. The ions with d1 configuration have tendency to lose the only

electron present in d subshell to acquires the nearest noble gas
configuration (d0). The hydration or lattice energy more than
compensates the ionization enthalpy involved in removing electron
from d1.
32. In the 3d series Cu exhibits +1 state most

frequently. (which element of 3d series exhibit +1 state

most frequently)

33. A. because Cu+ has stable 3d10 config.

34. Cu+ ion is not stable in aqueous solution.

A. 2Cu+(aq)Cu2+(aq) + Cu(s)

Cu+ undergoes disproportionation.The E0 value for this reaction is

favourable.Cu2+ has also higher hydration energy that Cu+ which
compensates the 2nd I.E of Cu

35. The highest oxidation state is exhibited in oxoanions of a metal.

A. Small size and high electronegativity of oxygen oxidize metal to

highest O.S oxygen can also form multiple bonds with metal.

36. The lowest oxide of transition metal is basic, the highest amphoteric
or acidic.

A.In lower oxidation state of metal the oxides are ionic and ionic oxides
are basic.While in higher oxidation state they are covalent and
covalent oxides are either amphoteric or acidic.

37. The E0(M2+/M) values for first row series are irregular.

A.E0 values depend on I.E1 + I.E2 as well as hydration and sublimation

energies which show irregular variation.

38. The E0(Cu2+/Cu) value for copper is positive (0.34V) while for all
other metals of 3d series it is negative.

A.Due to its high sublimation energy and low hydration energy ; The
energy required to change CuCu2+ is not balanced.

39. E0(M3+/M2+)values of Sc and Fe are low but that of Zn and Mn are

high.
A. Low values indicate +3 state is more stable than

+2. Sc3+ state -stable because it has a noble gas config

of Ar. Fe3+ is more stable due to half -filled 3d5 config.

Zn2+ is more stable-3d10

config (completely filled 3d

orbital)

In Mn2+ - stable(half filled

3d5 config)

[E0 indicates reduction potential, high E0 indicates high tendency to

get reduced ie. from M3+ to M2+]

40. Increasing oxidizing power is 5+VO2 < +6Cr2O72- < +7MnO4-

A. This is due to increasing stability of the lower species to which they

are reduced ie Mn2+,Cr3+ and V2+.

41. E0 value for Mn3+/Mn2+ couple much more positive than that for
Cr3+/Cr2+ or Fe3+/Fe2+.

A. Mn2+ more stable than Mn3+.Mn2+ has half -filled 3d5 config. Mn3+
easily reduced to Mn2+ while Cr3+ and Fe3+ are more stable so they are
less readily reduced.

42. Transition metals and many of their compounds show paramagnetic

behaviour.

A.Due to the presence of one more unpaired electrons in the orbitals.

(use spin only formula to calculate magnetic moment

where n= no.of.unpaired electrons. unit of
μ=BM(Bohr Magneton) higher the n value, greater the degree of
paramagnetism, greater is the magnetic moment)
Sc3+,Cu+,Zn2+ are diamagnetic due to the absence of unpaired e’s.

43. The transition metals generally from coloured compunds or

coloured ions.

A.In compounds or complexes the d orbitals of the transition metal split

into 2 sets of orbitals of slightly different energies - eg and t2g .In
transition elements with partly filled d orbitals ( presence of unpaired
electrons) electrons can move from one set of d orbitals to another.
This is called d-d transition.The energy required for this is available in
the visible region.The colour observed is complementary to the colour
of light absorbed.Ions with empty d orbitals(d0 config) or fully filled d
orbitals(d10 config) will be colourless.

e.g Sc3+,Zn2+,Cu+- colourless ( no unpaired electrons, d-d transition does

not take place)
 Cr3+,Mn2+,Ni2+- coloured(presence of unpaired electrons,

d-d transition takes place)

42.Transition metals form a large number of complex

compounds.

A.Due to small size of metal ions, their high ionic charges and
availability of empty d orbitals for bond formation.

43. Transition metals and their many compounds act as good catalyst.

A.This is due to their ability to adopt multiple oxidation state and to

form complexes. They provide a suitable surface for adsorption of
reactant molecules. They can form unstable intermediate complexes
with the reactants and provide a new path for the reaction with lower
activation energy.

44. Transition metals form interstitial compounds easily.

A. because small atoms like H, C, N, B etc. are trapped in the interstitial

sites in the crystal lattice of these metals.

45. Transition metals form alloys easily.

A. Alloys are homogeneous solid solution. Alloys are formed by atom

whose radii are with 15% of each other. Due to similar radii, they
form alloys easily.

46. K2Cr2O7 is preferred over Na2Cr2O7 as oxidizing agent in volumetric

analysis.

A. Na2Cr2O7 is hygroscopic ie. It absorbs moisture from air, so it cannot

be used as a primary standard in volumetric analysis.
47. Orange colour of K2Cr2O7 turns yellow on adding alkali(NaOH).

48. A.Due to the formation of yellow chromate ions CrO42-

Cr2O72- + 2OH-  2CrO42- + H2O

orange yellow

49. In permanganate and dichromate ions MnO4- and Cr2O 72- all the
bonds between the metal and oxygen are covalent.

A. Because Mn and Cr are in +7 and +6 state respectively. In higher

oxidation states bonds are covalent.

50. HCI is not used to acidify KMnO4 or K2Cr2O7 during volumetric

analysis.

A. KMnO4 and K2Cr2O7 are strong oxidizing agents and they oxidise HCl to
Cl2.This will affect volumetric estimation. Therefore, H2SO4 is preferred.

51. Though common Oxidation state of lanthanoids is +3, Ce and Tb

exhibits +4 state also and Eu and Yb exhibit +2 state as well.

A. Ce in +4 has stable noble gas configuration of Xe. Tb4+ has stable half
filled 4f7 config. Eu2+ and Yb2+ have stable 4f7 and 4f14 config
respectively.
52. Eu2+ and Yb2+ are reducing agents while Ce4+ and Tb4+ are oxidants.

A. Eu2+ and Yb2+ are oxidized to +3 state, to acquire the most common
oxidation state +3 of lanthanoids while Ce4+ and Tb4+ are reduced to
the +3 state.

53. Most of the lanthanoids and actinoids are paramagnetic and

coloured.

A.Due to the presence of unpaired electrons in 4f and 5f orbitals of

these metals.

54. The basic strength of hydroxides of lanthaniods M(OH)3 decreases

from LaLu.

A.Due to lanthanoid contraction there is a steady decrease in size of

M3+ ions from La to Lu. Therefore M-OH bond strength increases and
basic strength decreases.

55. Actinoid contraction is greater from element to element than

lanthanoid contraction.

A.Due to weaker shielding effect of 5f electrons from element to

element in the series.

56. Separation of lanthanoid elements from one another is difficult .

A. Due to similar radii,their chemical properties are similar. This makes

their separation difficult in pure state.

57. The chemistry of actinoids is more complex than lanthanoids.

A. Due to the ability of actinoids to exist in more no.of oxidation

states than lanthanoids. Lanthanoids-, +2+3,+4 Actinoids-
+3,+4,+5,+6,+7

57.There is greater range in O.S in actinoids than lanthanoids.

A.because 5f, 6d and 7s levels are of comparable energies.

58.Ionisation enthalpy of actinoids less than of corresponding

lanthanoids.

A.Penetration of 5f electrons are less than 4f electrons so 5f electrons

are better shielded from the nucleus than 4f electrons. so it is easier
to remove outer electrons in actinoids than from lanthanoid.

59.MnO is basic while Mn2O7 is acidic.

A. In MnO, Mn is in +2 oxidation state, while in Mn2O7, Mn is in +7

oxidation state. In lower oxidation state bond formed is ionic, so the
oxides are basic. While in higher oxidation state bond formed is
covalent.

60.The highest Mn fluoride is MnF4, highest oxide is Mn2O7.

A. This is due to ability of oxygen to form multiple bond with Mn.

61.Ni(II) compounds are more stable than Pt(II) compounds.

A. Smaller the ionization enthalpy of the metal, most stable is its

compound. Sum of the first two ionization enthalpy of nickel is less
then platinum.

62. K2PtCl6 is a well-known compound of Pt, corresponding nickel

compound is not known.

A. Pt is in +4 oxidation state. Sum of the first four ionization enthalpy

of platinum is less than nickel.

63.What is the general electronic configuration of lanthanoids.

A, = [Xe ]4f 1-14 5d0-1 6s2