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d & f -block elements

Worksheets

1. Why do transition elements show variable oxidation states?

The variability of the oxidation state of transition elements is due to incompletely filled d-
orbitals and the presence of unpaired electrons, i.e. (ns) and (n -1) d electrons have approximate
equal energies.
2. Generally, there is an increase in density of elements from titanium (Z = 22) to copper (Z
= 29) in the first series of transition elements.
From titanium to copper the atomic size of elements decreases and mass increases as a result
of which density increases.
3. Transition elements and their compounds are generally found to be good catalysts in
chemical reactions.
The catalytic properties of the transition elements are due to the presence of unpaired electrons
in their incomplete d- d-orbitals and variable oxidation states.
4. Transition elements generally form coloured compounds.
Because of the presences of unpaired d electrons, which undergoes d-d transition by absorption
of energy from visible region and then the emitted light shows complementary colours. This is
how transition elements form coloured compounds.
5. Zinc is not regarded as a transition element.
Zinc in its common oxidation state of +2 has completely filled d-orbitals. Hence considered a
non-transition element.
6. Copper (I) ion is not known in aqueous solution.
Cu2+(aq) is much more stable than Cu+(aq). This is because although the second ionization
enthalpy of copper is large Δhyd (hydration enthalpy) for Cu2+(aq) is much more negative than
that for Cu+(aq) and hence it more than compensates for the second ionization enthalpy of copper.
Therefore, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation as follows:
2Cu+ → Cu2+ + Cu
7. Actinoids exhibit a greater range of oxidation states than lanthanoids.
Because of very small energy gap between 5f, 6d and 7s sub-shells all their electrons can take
part in bonding and shows variable oxidation states.
8. Manganese exhibits the highest oxidation state of +7 among the 3d series of transition
elements.
Manganese exhibits highest oxidation of +7 among 3d series of transition elements because all
the oxidation states are exhibited from +2 to +7 by Mn and no other element of this series shows
this highest state of oxidation.
9. Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an
oxidising agent.
Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half-filled t2g orbitals.
Therefore, Cr2+ is a reducing agent. While Mn2+ has a stable half-filled d5 configuration. Hence
Mn3+ easily changes to Mn2+ and acts as an oxidising agent.
10. In a transition series of metals, the metal which exhibits the greatest number of oxidation
states occurs in the middle of the series.
Due to the presences of more unpaired electrons and the use of all 4s and 3d electrons in the
middle of the series.
11. Unlike Cr3+, Mn2+, Fe3+ and the subsequent other M2+ ions of the 3d series of elements, the
4d and the 5d series metals generally do not form stable cationic species.

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Because high enthalpies of atomisation of 4d and 5d series and high ionization enthalpies, the
M.P. and B.P. of heavier transition elements are greater than those of first transition series
which is due to stronger intermetallic bonding. Hence 4d and 5d series metals generally do not
form stable cationic species.
12. Transition metals and their compounds are generally found to be good catalysts.
The catalytic properties of the transition elements are due to the presence of unpaired electrons
in their incomplete d- orbitals and variable oxidation states.
13. Metal-metal bonding is more frequent for the 4d and the 5d series of transition metals
than that for the 3d series.
Metal-metal bonding is more frequent for the 4d and the 5d series of transition metals than that
for the 3d series as these have their electrons of outer most shell at greater distance from the
nucleus, as compared to atoms of 3d transition metals.
14. Transition metals and their compounds generally exhibit a paramagnetic behaviour.
Because of presence of unpaired electrons in their d-subshell in atomic and ionic state.
15. The chemistry of actinoids is not so smooth as that of lanthanoids.
Lanthanoids show limited number of oxidation state, viz. +2, +3 and +4 (out of which +3 is
most common) because of large energy gap between 4f and 5d subshells. Actinoids also show
stable +3 oxidation state but show a number of oxidation states i.e. +4, +5 and + 6, +7 due to
small energy difference between 5f, 6d and 7s subshells.
16. The enthalpies of atomization of transition metals are quite high.
In transition elements, there are large number of unpaired electrons in their atoms, thus they
have a stronger inter atomic interaction and thereby stronger bonding between the atoms. Due
to this they have high enthalpies of atomization.
17. The transition metals (with the exception of Zn, Cd and Hg) are hard and have high
melting and boiling points.
Because of stronger metallic bonding and high enthalpies of atomization.
18. The ionization enthalpies (first and second) in the first series of the transition elements
are found to vary irregularly.
Due to irregulaties in the electronic configuration there is irregularities in the enthalpies of
atomisation. Hence there is irregular variation in I.E.
19. The highest oxidation state of a transition metal is usually exhibited in its oxide.
The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high
electronegativity, low ionisation energy and small size.
20. Transition elements exhibit paramagnetic behaviour.
Because of presence of unpaired electrons in their d-subshell in atomic and ionic state.
21. Co2+. is easily oxidised in the presence of a strong ligand.
Co2+ ion is easily oxidised to Co3+ ion in presence of a strong ligand because of its higher crystal
field energy which causes pairing of electrons to give inner orbital complexes (d2sp3).
22. Both O2 and F2 stabilize high oxidation states of transition metals but the ability of oxygen
to do so exceeds that of fluorine.
The ability of O2 to stabilize higher oxidation states exceeds that of fluorine because oxygen
can form multiple bonds with metals.
23. Transition metals generally form coloured compounds.
Because of presence of unpaired electrons in d-orbital, which undergoes d-d transition by
absorption of energy from visible region and then the emitted light shows complementary
colours.
24. The transition metals and their compounds are usually paramagnetic.
The transition metals and their compounds are usually paramagnetic because of the presence of
unpaired electrons in their d-orbitals.
25. The transition metals exhibit variable oxidation states.

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The transition metals exhibit variable oxidation states because of very close energies of
incompletely filled (n – l)d orbitals and ns orbitals due to which both can participate in bonding.
26. Actinoids show a wide range of oxidation states.
Due to comparable energies of 5f, 6d and 7s orbitals.
27. Zn is not regarded as a transition element.
Zinc Atomic no. 30 has E.C 3d10, 4s2. It has completely filled ‘d’ orbitals.
28. Cr2+ is a strong reducing agent.
Cr+2 (3d4) after losing one electron forms Cr+3 (d3). It has t32g e0g configuration. Hence more
stable. Hence Cr+2 acts as a reducing agent.
29. The copper atom has completely filled d orbitals (3d10) in its ground state, yet it is
regarded as a transition element.
The copper atom has completely filled d orbitals (3d10) in its ground state, yet it is regarded as
a transition element due to incompletely filled d-orbital in its ionic states i.e. Cu2+ (3d9).
30. Cr2+ is a stronger reducing agent than Fe2+ in aqueous solutions.
The highest oxidation state for Cr is +6, therefore it can lose 3 more electrons, whereas Fe needs
to lose only 1 electron to achieve its highest oxidation state of +3. Thus, Cr3+ is more reducing
than Fe2+.
31. Silver atom has completely filled d-orbitals (4d10) in its ground state, yet it is regarded as
a transition element.
Because silver has incomplete d-orbital (4d9) in its +2 oxidation state, hence it is a transition
element.
32. The E0 value for Mn3+ /Mn2+ couple is much more positive than Cr3+/Cr2+.
The large positive E° value for Mn3+/Mn2+ shows that Mn2+ is much more stable than Mn+3 due
to a stable half-filled configuration (3d5). Therefore the 3rd ionisation energy of Mn will be
very high and Mn3+ is unstable and can be easily reduced to Mn2+. E° value for Cr3+/Cr2+ is
positive but small i.e. Cr3+ can also be reduced to Cr2+ but less easily. Thus Cr3+ is more stable
than Mn3+
33. Zn2+ salts are colourless.
Zn2+ salts are colourless due to the absence of unpaired electrons in their ground state and ionic
state i.e. Zn2+ = [Ar] 3d104s04p0
34. Copper has an exceptionally positive E0M2+/M value.
The E0 M2+/M for any metal is related to the sum of the enthalpy changes taking place in the
following steps:
M(g) + ΔaH → M(g) (ΔaH = enthalpy of atomization)
M(g) + ΔiH → M2+(g) (ΔiH = ionization of atomization)
M2+(g) + Δaq → M2+(g) + ΔhydH (Δhyd H= hydration atomization)
Copper has high enthalpy of atomization (i.e. energy absorbed and low enthalpy of hydration
(i.e. energy released). Hence E0M2+/M for copper is positive. The high energy required to
transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.
35. The metallic radii of the third (5d) series of transition elements are virtually the same as
those of the corresponding members of the second series.
Due to lanthanoid contraction in the second series after lanthanum, the atomic radii of elements
of the second and third series become almost the same and hence show similarities in properties.
36. There is a greater range of oxidation states among the actinoids than among the
lanthanoids.
Because of very small energy gap between 5f, 6d and 7s subshells, all their electrons can take
part in bonding and shows variable oxidation states.
37. The atomic radii of the metals of the third (5d) series of transition elements are virtually
the same as those of the corresponding members of the second (4d) series.
Due to lanthanoid contraction in the second series after lanthanum, the atomic radii of elements
of the second and third series become almost the same and hence show similarities in properties.

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38. The E° value for the Mn3+/Mn2+ couple is much more positive than that for Cr3+/Cr2+
couple or Fe3+/Fe2+ couple.
The electronic configuration of the Mn2+ ion is more symmetrical as compared to that of the
Cr2+ ion. So 3rd ionisation potential of Mn2+ is much higher. As a result, E° value of the Mn3+/
Mn2+ couple is much more positive than for the Cr3+/Cr2+ and Fe3+/Fe2+ couple.
39. The highest oxidation state of a metal is exhibited in its oxide or fluoride.
The highest oxidation state of a metal is exhibited in its oxide or fluoride due to its high
electronegativity.
40. Many of the transition elements are known to form interstitial compounds.
The transition metals form a large number of interstitial compounds in which small atoms such
as hydrogen, carbon, boron and nitrogen occupy the empty spaces in the crystal lattices of
transition metals.
41. The metallic radii of the third (5d) series of transition metals are virtually the same as
those of the corresponding group members of the second (4d) series.
Because of lanthanoid contraction.
42. Lanthanoids form primarily +3 ions, while actinoids usually have higher oxidation states
in their compounds, +4 or even +6 being typical.
This is due to comparable energies of 5f, 6d, and 7s orbitals in actinoids.
43. The actinoids exhibit a larger number of oxidation states than the corresponding
members in the lanthanoid series.
Due to comparable energies of 5f 6d and 7s orbitals of actinoids, these show a larger number
of oxidation states than corresponding members of lanthanoids.
44. Most of the transition metal ions exhibit characteristic in colours in aqueous solutions.
Due to the presence of unpaired electrons in the d-orbital, transition metal exhibits colours in
aqueous solution or due to d-d transition.
45. The enthalpies of atomization of transition elements are quite high.
In transition elements, there are a large number of unpaired electrons in their atoms, thus they
have a stronger inter-atomic interaction and thereby stronger bonding between the atoms. Due
to this, they have high enthalpies of atomization.
46. There occurs much more frequent metal-metal bonding in compounds of heavy transition
metals (i.e. 3rd series).
Because of high enthalpy of atomisation of 3rd series, there occurs much more frequent metal-
metal bonding in compounds of heavy transition metals.
47. Mn2+ is much more resistant than Fe2+ towards oxidation.
The 3d orbital in Mn2+ is half-filled and is more stable compared to Fe2+ has 6 electrons in the
3d orbital. Mn2+ prefers to lose an electron or get oxidised whereas Fe2+ will readily lose one
electron or get oxidised. Therefore, Mn2+ is much more resistant than Fe2+ towards oxidation.
48. Among lanthanoids, Ln (III) compounds are predominant. However, occasionally in
solutions or in solid compounds, + 2 and + 4 ions are also obtained.
Among lanthanoids, Ln (III) compounds are predominant. However, +2 and +4 ions in solution
or in solid compounds are also obtained. This is because they have empty, half-filled and
completely filled 4/sub-shells respectively which show extra stability.
49. The metallic radii of the third (5d) series of transition metals are nearly the same as those
of the corresponding members of the second series.
Because of lanthanoid contraction the metallic radii of the third (5d) series of transition metals
are nearly the same as those of the corresponding members of the second series.
50. Many of the transition elements are known to form interstitial compounds.
The transition metals form a large number of interstitial compounds in which small atoms such
as hydrogen, carbon, boron and nitrogen occupy the empty spaces in the crystal lattices of
transition metals.
51. There is a general increase in density from titanium (Z = 22) to copper (Z = 29).

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From titanium to copper the atomic size of elements decreases and mass increases as a result
of which density increases.
52. The members of the actinoid series exhibit a larger number of oxidation states than the
corresponding members of the lanthanoid series.
This is due to comparable energies of 5f 6d and 7s orbitals in actinoids.
53. Actinoids exhibit a much larger number of oxidation states than the lanthanoids.
Due to comparable energies of 5f, 6d and 7s orbitals actinoids exhibit a much larger number of
oxidation states than the lanthanoids.
54. There is hardly any increase in atomic size with increasing atomic numbers in a series of
transition metals.
Along a transition series, the nuclear charge increases which tends to decrease the size but the
addition of electrons in the penultimate d-subshell increases the screening effect which
counterbalances the effect of increased nuclear charge. Thus, the atomic radius does not change
much.
55. Sc (21) is a transition element but Ca (20) is not.
Sc (21) is regarded as a transition element due to the presence of an incomplete d- d-subshell
(3d14s2) but Ca (20) does not have any d-subshell.
56. Zr (Z = 40) and Hf (Z = 72) have almost identical radii.
Zr and Hf have almost identical radii due to lanthanoid contraction which is due to weak
shielding of d-electrons.
57. Transition metals are much harder than the alkali metals.
In transitional elements, in addition to metallic bonding, there is extra covalent bonding due to
presence of unpaired electrons in their ‘d’ orbitals, hence they are much harder.
58. From element to element actinoid contraction is greater than the lanthanoid contraction.
The actinoid contraction is greater than lanthanoid contraction due to poorer shielding of 5f
electrons as they are extended in space beyond 6s and 6p orbitals whereas 4f orbitals are buried
deep inside the atom.
59. Actinoid contraction is greater than lanthanoid contraction.
Actinoid contraction is greater than lanthanoids because 5f electrons (in actinoids) have a
poorer shielding effect than 4f electrons (in lanthanoids).
60. Actinoids show irregularities in their electronic configurations.
This happens because the energy difference between 5f, 6d and 7s subshells of the actinoids is
very small and hence electrons can be accommodated in any of them.
61. Mn shows the highest oxidation state of +7 with oxygen but with fluorine, it shows the
highest oxidation state of +4.
Because oxygen stabilizes the highest oxidation state (+7 of Mn) even more than fluorine i.e.,
+4 since oxygen has the ability to form multiple bonds with metal atoms.
62. Compounds of transition elements are generally coloured.
The catalytic properties of the transition elements are due to the presence of unpaired electrons
in their incomplete d- d-orbitals and variable oxidation states. The colour of transition metal
ions is due to d-d transition. When electrons jump from one orbital to another in their partially
filled d-orbitals, another light is emitted due to which the compounds of transition elements
seem to be coloured.
63. MnO is basic while Mn2O7 is acidic.
MnO is basic while Mn2O7 is acidic because the basic nature decreases as the oxidation state or
number of oxygen atoms increases i.e. MnO (+4) and Mn2O7 (+7)
64. The greatest number of oxidation states are exhibited by the members in the middle of a
transition series.
Due to presence of more unpaired electrons and the use of all 4s and 3d electrons in the middle
of the series.
65. The enthalpies of atomization of the transition elements are quite high.

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Enthalpy of atomization is the amount of heat required to break the metal lattice to get free
atoms. As transition metals contain a large number of unpaired electrons, they have strong
interatomic attractions (metallic bonds). Hence they have high enthalpies of atomization.
66. The third ionization enthalpy of manganese (Z = 25) is exceptionally high.
Because the third electron has to be removed from stable half-filled 3d-orbitals (Z = 25 has 3d5
4s2).
67. La3+ (Z = 57) and Lu3+ (Z = 71) do not show any colour in solutions.
La3+ ion has the configuration of xenon which is highly stable, Lu3+ also has a stable electronic
configuration i.e. these completely filled valence orbital occur so they do not form any colour
ion or compounds.
68. Among the divalent cations in the first series of transition elements, manganese exhibits
the maximum paramagnetism.
The Mn(II) ion has 5 unpaired electrons in the 3d subshell which is the maximum value for a
transition metal ion and the paramagnetic property is directly related to unpaired electrons
hence Mn(II) shows a maximum paramagnetic property.
69. Mn3+ is a good oxidising agent.
Mn3+ has electronic configuration 3d44s0. On reduction, it gains one electron to become 3d54s0
which is half half-filled stable configuration. Hence it is a good oxidising agent.
70. E°M2+/M values are not regular for first-row transition metals (3d series).
E°M2+/M values are not regular for first-row transition metals due to abnormalities and
irregularities in their ionization enthalpies (IE1 + IE1) and sublimation enthalpies.
71. Zirconium (Z = 40) and Hafnium (Z = 72) have almost similar atomic radii.
Zirconium and Hafnium have almost similar atomic radii due to the effect of lanthanoid
contraction.
72. d-block elements exhibit more oxidation states than f-block elements.
d-block elements exhibit more oxidation states due to small energy gap between ns and (n– 1)d
subshell while f – block elements show less oxidation state due to large energy gap between ns
and (n -2)f subshell.
73. The variation in oxidation states of transition metals is of different type from that of the
non-transition metals.
In transition elements, the successive oxidation state differs by unity, e.g, Mn shows all the
oxidation states from +2 to +7. On the other hand non-transition metals exhibit variable
oxidation states which differ by two units, e.g. Pb(II), Pb(IV), Sn(II), Sn(IV) etc.
74. The orange solution of potassium dichromate turns yellow on adding sodium hydroxide
to it.
The orange-coloured potassium dichromate solution when treated with basic NaOH solution,
is converted to chromate which gets a faint colour like yellow.
The reaction is given as: K2Cr2O7 + 2NaOH → K2CrO4 + Na2CrO4 + H2O.
This formation of chromate (CrO4–) ion converts the colour of solution to yellow.
75. Transition metals form a large number of complexes.
Because of the smaller size of their ions, high ionic charge and availability of vacant d-orbitals,
transition metals from a large number of complexes.
76. Cu2+ salts are coloured while Zn2+ salts are white.
Cu2+ has the configuration 3d9 with one unpaired electron which gets excited in the visible
region to impart its colour while Zn2+ has a 3d10 configuration without any unpaired electron so
no d – d transition is possible and hence colourless.
77. The lowest oxide of transition metal is basic whereas the highest oxide is amphoteric or
acidic.
The lowest oxide of transition metal is basic because of the low oxidation state some of the
valence electrons are not involved in bonding and act as bases by donating electrons. However

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in higher oxides due to a high oxidation state, it cannot donate electrons but can accept electrons
due to high effective nuclear charge. Hence, they are acidic in nature.
78. HCl is not used to acidify KMnO4 solution.
HCl is not used to acidify KMnO4 solution because KMnO4 is a very strong oxidizing agent
and it can oxidize HCl to liberate chlorine gas.
79.

Raguram K. MSc., M.Phil., B.L.I.S., (PhD) Chemistry