Springdales School, Dhaula Kuan

PRACTICE WORKSHEET
Class: XII
Chapter: d and f block elements

1. Define transition elements.

Ans. Transition element is defined as the one which has incompletely filled d orbitals in its ground
state or in any one of its oxidation states.
2. Zinc, cadmium and mercury of group 12 are not regarded as transition metals, Why ?
Ans. Zinc, cadmium and mercury of group 12 have full d10 configuration ( d orbitals are completely
filled ) in their ground state as well as in their common oxidation states and hence, are not
regarded as transition metals
3. Write the general outer electronic configuration of d- block elements. .
Ans. The general outer electronic configuration of d- block elements is (n-1)d1–10 ns1–2
4. Write the general electronic configuration of f- block elements.
Ans. The general electronic configuration of f- block elements (Lanthanoids) is
[Xe] 4f1 – 14 5d 0- 1 6s2
5. Name a member of the lanthanoid series which is well known to exhibit +4 oxidation state.
Ans. Cerium
6. Account for high melting point and boiling points of transition metals.
Ans. The melting and boiling points of transition metals are high because of the involvement of
greater number of electrons from (n-1)d orbitals in addition to the ns electrons in the inter atomic
metallic bonding.
7. What is the trend in melting points of transition metals in a series?
Ans. The melting points of the transition metals in a series rise to a maximum at the middle of the
series (i.e. Cr or Mo or W - element with d 5 configuration ) and fall regularly as the atomic number
increases.
8. Why do transition metals have higher enthalpies of atomization?
Ans. Involvement of a large number of unpaired electrons of d orbitals favour stronger inter atomic
interactions resulting in stronger bonds between the atoms of a metal and higher enthalpies of
atomization.
9. Name one 3d series elements, that do not show variable oxidation states.
Ans. Sc (+3)
10. Transition metals exhibit variable oxidation states in its compounds, why?
Ans. Transition metals exhibit variable oxidation states in its compounds due to the availability of
both ns & (n – 1 ) d electrons for bond formation.
11. Write the spin-only formula used to calculate the magnetic moment of metal ions.
Ans. The magnetic moment is determined by using the spin only formula,
where n is the number of unpaired electrons and μ is the magnetic moment in
units of Bohr magneton (BM).
12. What is Actinoid contraction?
Ans. Actinoid contraction refers to the gradual decrease in the ionic radii with increase in atomic
number of actinoids. 5f electrons improperly shield one another. In the actinoid series, the
nuclear charge and number of 5f electrons increases by one unit.
13. Actinoid contraction is more than lanthanoid contraction. Give reason.
Ans. The actinoid contraction is, more than lanthanoid contraction due to poor shielding by 5f
electrons from nuclear charge.
14. Actionoids show larger number of oxidation states than lanthanoids. Why?
 Ans. In actinoids 5f, 6d and 7s levels are of comparable energies ,hence electrons from these
orbitals are available to lose or share.
15. Give one use of Mischmetall .
Ans. Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
16. Why transition metals forms alloys readily?
Ans. Transition metals readily form alloys with other transition metals because of their similar radii.
17. Give one use of transition metal alloy.
Ans. Ferrous alloys containing chromium, vanadium, tungsten, molybdenum and manganese are
used for the production of a variety of steels.
18. What are interstitial compounds? Give example.
Ans. Interstitial compounds are those which are formed when small atoms like H, C or N are
trapped inside the crystal lattices of transition metals.
Example; TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
19. Give any two physical characteristics of interstitial compounds.
Ans.Two physical characteristics of interstitial compounds are:
a. They have high melting points, higher than those of pure metals.
b. They are very hard and they retain metallic conductivity.
20. Calculate the ‘spin only’ magnetic moment of M 2+ (aq) ion (Z = 27).
Ans. M (z= 27 , 3d7 4s2) → M+2 (3d7 4s0) hence it has 3 unpaired electrons n= 3
= √3(3+2) = 3.87 BM
21. The second ionisation enthalpy is high for Cr and Cu , why?
Ans: The second ionisation enthalpy is unusually high values for Cr and Cu because when M + ion
ionize to M+2 ion , the d5 and d10 configurations of the M+ ions (i.e Cr+ or Cu+) are disrupted, with
considerable loss of exchange energy .
22. Explain the oxidising action of acidified potassium dichromate on (iron(II) salts) Fe +2 ions and
write the ionic equations for the reaction.
Ans. Acidified potassium dichromate oxidises iron(II) salts to iron(III).
Cr2O72− + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O
23. The transition metals generally form coloured compounds, why?
Ans. The compounds of transition elements shows colour due to presence of unpaired electron &
ability to undergo d-d transition. When an electron from a lower energy d orbital is excited to a
higher energy d orbital, the energy of excitation corresponds to the frequency of light absorbed.
This frequency generally lies in the visible region.
24. “transition metals form a large number of complex compounds”. Give reason.
Ans. Transition metals form a large number of complex compounds due to:
(i) Small size & high charge density of the ions of transition metals.
(ii) presence of vacant d orbitals of suitable for bond formation.
25. What is the effect of increasing pH on a solution of potassium dichromate?
Ans. On increasing the pH of the solution Potassium dichromate (orange) becomes potassium
chromate (yellow) Cr2O72- + 2OH- → 2CrO42- + H2O
26. What happens when H2S is passed into potassium dichromate in acidic medium? Give the
equation.
Ans. H2S gets oxidized to sulphur
Cr2O7−2 + 3H2S + 8H+ → 2Cr+3 + 7H2O + 3S
27. What is ‘disproportionation’ of an oxidation state ? Give one example of disproportionation
reaction in aqueous solution.
Ans. A particular oxidation state , which is relatively less stable compared to other oxidation states
 , under goes disproportion. Manganese (VI) which is relatively less stable changes over to
manganese (VII) and manganese (IV) in acid solution.
3 MnO4-2 + 4H+→ MnO2 +2MnO4-+ 2 H2O
28. What is lanthanoid contraction? Write any one consequence of lanthanoid contraction.
Ans. Steady decrease in the size of lanthanides with increase in atomic number is known as
lanthanoid contraction. Due to lanthanoid contraction radii of members of 3rd transition series are
very much similar to corresponding members of 2nd series.
29. Write any two consequences of lanthanoid contraction.
Ans. Two consequences of lanthanoid contrations are
(i) The radii of the members of the third transition series to be very similar to those of the
corresponding members of the second series. Ex. The almost identical radii of Zr (160 pm) and Hf
(159 pm) & Nb (146pm) & Ta (146pm)
(ii) Difficulty in separation of lanthanoids due to similarity in chemical properties.
30. The chemistry of actionoids is more complicated than lanthanoids. Why?
Ans. The actinoids are radioactive elements having half lifes varying. Some members can be
prepared only in nanogram quantities. These facts render their study more difficult.
31. What happens when
(a) A lanthonoid reacts with dilute acids ?
(b) A lanthonoid reacts with water?
Ans.(a) When lanthonoid reacts with dilute acids , it liberates hydrogen gas.
(b)When lanthonoid reacts with water , it forms lanthanoid hydroxide and liberate hydrogen gas.
32. What is the gas liberated when
i) crystals of potassium permanganate is heated to 513K ?
ii) acidified potassium permanganate is treated with oxalate ion at 333K?
Ans. i) When crystals of potassium permanganate is heated to 513K Oxygen (O2) gas is liberated .
ii) Acidified potassium permanganate when treated with oxalate ion at 333K liberates Carbon
dioxide (CO2) gas.
33. Show the interconversion of chromate and dichromate
Ans. The chromates and dichromates are interconvertible in aqueous solution depending upon pH
of the solution.
At pH less than 7: Chromate (yellow) on adding acid becomes dichromate (orange)
2CrO42- + 2H+ → Cr2O72- + H2O
At pH more than 7 : Dichromate (orange) on adding base becomes Chromate (yellow)
Cr2O72- + 2OH- → 2CrO42- + H2O
34. How does the neutral or faintly alkalline potassium permanganate solution react with
(a) Iodide (b) thiosulphite? Write the ionic equations for the reactions.
Ans. In neutral or faintly alkaline solutions:
(a) The oxidation of iodide to iodate:
2MnO4− + H2O + I− ——> 2MnO2 + 2OH− + IO3−
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8MnO4– + 3S2O32– + H2O ——> 8MnO2 + 6SO42– + 2OH–
35. Name the metal of the 1st row transition series that
i) has highest value for magnetic moment
ii) has zero spin only magnetic moment in its +2 oxidation state.
iii) exhibit maximum number of oxidation states.
Ans. i) Chromium ii) Zinc iii) Manganese
36. How is potassium dichromate prepared from iron chromite ore?
Ans.Potassium dichromate is manufactured from chromite ore (FeCr 2O4).
(i) Chromite ore is fused (FeCr2O4) with sodium or potassium carbonate in free access of air to
 get sodium chromate .
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
(ii) The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O
Potassium dichromate prepared by treating the solution of sodium dichromate with potassium
chloride.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Orange crystals of potassium dichromate crystallise out.
37. What happens when potassium permanganate is heated to 513 K ?
Ans. Potassium permanganate decomposes at 513K to potassium manganate, manganese dioxide
and oxygen.
38. Give Reasons:
1. Transition metals show variable oxidation states.
Reason: Since there is a very little difference in the energies of (n-1) d and ns orbitals, both
energy levels can be used for bond formation.
2. Zr and Hf exhibit almost similar properties.
Reason: this is due to lanthanoid contraction which arises due to poor shielding effect of 4f
orbitals which are filled before 5d orbitals.
3. Which is a stronger reducing agent Cr2+ or Fe2+ and why ?
Cr+2 is a stronger reducing agent than Fe+2 because after the loss of one electron Cr²+
becomes Cr3+ which has more stable t2g3, (half filled) configuration in medium like water.
4. Transition metals are paramagnetic in nature.
Reason: Paramagnetism arises from the presence of unpaired electrons.
5. Zn ,Cd, and Hg are not regarded as transition elements.
Reason: The electronic configurations of Zn, Cd and Hg are represented by the general
formula (n-1)d10ns2. The orbitals in these elements are completely filled in the ground state as
well as in their common oxidation states.
6. E0 M2+/M value of Copper is positive. (+0.34v).
Reason: The sum of enthalpies of sublimation and high ionisation is not balanced by low
hydration enthalpy i.e. the high energy to transform Cu(s) to Cu 2+(aq) is not balanced by its
hydration enthalpy.
7. The metallic radii of the third series of transition metals are virtually the same as those of
corresponding group members of the second series.
Reason: this is due to lanthanoid contraction which arises due to poor shielding effect of 4f
orbitals which are filled before 5d orbitals.
8. Transition elements have very high melting and boiling points.
Reasons: It is due to the involvement of greater number of electrons from (n-1)d in addition to
the ns electrons in the inter atomic metallic bonding. So strong metallic bonds exist between
the atoms of these elements and so the MP and BP are quite high.
9. Mn (III) undergoes disproportionation reaction easily
Reason: Mn is less stable and changes to Mn+2 which is more stable due to half-filled d-
orbital configuration. That is why, Mn+2 undergoes disproportionation reaction.
10. Cobalt (II) is stable in aqueous solution but in presence of complexing reagents it is easily
oxidised
Reason: Co(II) has electronic configuration 3d7, 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).
11. The transition metal exhibits higher oxidation states in oxides and fluorides.
Reason: Due to small size and high electronegativity of O or F can oxidise a metal to its highest
oxidation state.
12. Of the d4 species Cr2+ is strongly reducing while manganese (III) is strongly oxidising
Reason: Cr2+ is reducing as its configuration changes from d4 to d3, the latter having a half-
filled t2g level. On the other hand, the change from Mn2+ to Mn3+ results in the half-filled (d5)
configuration which has extra stability.
13. The halides of transition elements become more covalent with increasing oxidation state of
metal.
Reason: Fajan’s rule: higher the OS, more is the polarising power and hence more covalent
behaviour
14. Ionisation enthalpy of Ce, Pr and Nd are higher than Th, Pa and U.
Reason: 5f electrons are better shielded as compared to 4f electrons from the nuclear charge
15. Actinoid contraction is greater from element to element than lanthanoid contraction.
Reason: This is because the 5f electrons themselves provide poor shielding from element to
element in the series.
16. The enthalpies of atomisation of transition metals are quite high.
Because of large number of unpaired electrons in their atoms they have stronger inter-atomic
interaction and hence stronger bonding between atoms resulting in higher enthalpies of
atomisation.
17. The transition metals generally form coloured compounds.
Reason: It is because of d-d transitions. Since the energy gap between t2g and eg orbitals is less,
electrons can gain energy from the white light and show d-d transitions and thus show colours
complimentary to the light absorbed.
18. Transition metals act as good catalysts.
Reason: This is due to
i) their ability to adopt multiple oxidation states and ii) ability to form complexes.
19. They form a large number of complexes.
Reason: This is due to:
(i) comparatively smaller sizes of the metal ions iii) their high ionic charges
(ii) availability of d-orbitals for bond formation.
20. Transition metals form interstitial compounds.
21. Copper (I) has d10 configuration while copper (II) has d9 configuration. Still, copper (II) is
more stable in aqueous solution than copper (I).
Reason: due to much more negative hydration enthalpy of Cu2+ as compared to Cu+
22. La(OH)3 is a stronger base than Lu(OH)3.
Ans. Lu+3 is smaller in size than La+3 due to lanthanoid contraction. Due to smaller size of
Lu+3, Lu-O bond is stronger than La-O bond in the respective hydroxides. Due to weaker La-O
bond, La(OH)3, behaves as a strong base.
23. K2[PtCl6] is a well known compound whereas the corresponding nickel compound is not
known.
Reason: since first four ionisation enthalpies of Ni is very high so it cannot form Ni +4
24. First ionisation energies of 5d elements are higher than those of 3d and 4d elements.
 Reason: Because of 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 lonisation
energies of 5d elements are higher than those of 3d and 4d elements.
25. There is in general an increase in density of element from titanium (Z=22) to copper (Z=29).
Reason: Because of decrease in atomic size from titanium to copper.
26. There occurs much more frequent metal-metal bonding in compounds of heavy transition
elements (3d series).
Reason: Because of high enthalpies of atomization of heavy transition elements.
27. The greatest number of oxidation states are exhibited by the members in the middle of a
transition series.
Reason: Because of the involvement of both (n-1)d and ns electrons in bonding.
28. Cu+1 is not stable in aqueous solution, Why?
Reason: In aqueous solution Cu+1 undergoes disproportionation to form a more stable Cu+2
ion. 2Cu+1 (aq) → Cu2+ (aq) + Cu(s)
The higher stability of Cu+2 in aqueous solution may attributed to its greater negative
hydration enthalpy than that of Cu+1 which compensates for the second ionisation enthalpy
of Cu involved in the formation of Cu+2 ions.
39. 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?
Reason: Lanthanoid contraction: Steady decrease in the size of the lanthanoids with increase in the
atomic number across the period. The electrons of 4f orbitals offer imperfect/poor shielding effect
in the same subshell.
Consequences:
i) Due to this 5d series elements have nearly same radii as that of 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 separation of lanthanides.
40. Arrange the following increasing of acidic character: CrO3, CrO, Cr2O3
Ans: CrO <Cr2O3<CrO3
Reason: Higher the oxidation, more will be acidic character.
41. Lanthanoids form primarily +3 ions, while the actinoids usually have higher oxidation states in
their compounds, +4 or even +6 being typical.
Ans. Lanthanoids exhibit oxidation state of +2, +3 and +4. This is because of 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 same.
42. Calculate the 'spin only' magnetic moment of M2+(aq) ion.(Z=27)
Ans. Electronic configuration of the M+2 ion (Z=27) = (Ar) 3d7. It would contain three unpaired
electrons. The 'spin only' magnetic moment is given by the relation:
µ=[n (n+2)]1/2 BM =√3 (3+2) BM = 3.87 BM
43. Complete the following reactions:-
a. Cr2O72-+Fe2+ + H+ -------->
b. Cr2O72-+ I- + H+ -------->
b) MnO4- + 2H2O + 3e- ----------> MnO2 + 4 OH-
c) 2CrO42- + 2H+ --------> Cr2O72- + H2O
d) CrO2Cl2 + NaOH -------> CrO42- + 2Cl- + 2 H2O
e) MnO2 + KOH + O2 --------> K2MnO4 + H2O
f) Mn2+ + S2O82- +H2O ------->
h) KMnO4 + SO2 + H2O --------> Mn+2 + SO42-
44. Write the structures of the following :-
a) Manganate Ion b) Permanganate Ion

c) Chromate Ion d) Dichromate Ion

45. a) What is meant by disproportionation? Give two examples of such a reaction in aqueous
solution.
b) Write the steps involved in the preparation:-
i. KMnO4 from K2MnO4
ii. KMnO4 from MnO2
iii. K2Cr2O7 from Na2CrO4