d and f block elements

1. Though copper, silver and gold have completely filled sets of d-orbitals yet they are
considered as transition metals. Why?
Answer: These metals in their common oxidation states have incompletely filled d-
orbitals.eg Cu+ has 3d9 configuration.
2. Zinc,cadmium and mercury are generally not considered as transition metals. Give
reason.
Answer: These elements have completely filled d-orbitals in their ground state and
also in their most common oxidation state i.e +2 oxidation state.
3. Why does Mn(II) show maximum paramagnetic character amongst the bivalent ions
of the first transition series?
Answer: Mn+2 has maximum number of unpaired electrons.
4. Why Zn+2 salts are white while Ni+2 salts are bluish green?
Answer: Zn+2 has completely filled d-orbitals while Ni+2 has incompletely filled d-
orbitals (3d8).
5. Giving reason indicate which one of the following would be coloured?
Cu+, VO+2, Sc+3 and Ni+2
Ans: Ni2+ due to incompletely filled d-orbitals. (3d8).
6. K2PtCl5 is a well known compound whereas corresponding Ni compound is not
known. State reason for it.
Answer: This is because Pt4+ is more stable than Ni4+ as the sum of four ionization
enthalpies of Pt is less than that of Ni.
7. Why do the transition elements have high enthalpy of hydration?
Answer: This is so because when we move along any transition series, the nuclear
charge increases and size decreases.
8. Why do transition elements show variable oxidation state?
Answer: In the transition elements, the energies of (n-1)d-orbital and ns orbital are
very close. Hence, electrons from both can participate in bonding.
9. The melting and boiling point of Zn, Cd and Hg are low. Why?/ Why Zn, Cd and Hg
are soft and have low melting point?
Answer: In Zn, Cd and Hg all the electrons in d-orbitals are paired. Hence, the
metallic bond present in them is weak. That is why they have low melting and
boiling point.
10. Transition metals exhibit higher enthalpies of atomization. Explain why.
Answer: As transition metals have large number of unpaired electrons, they have
strong interatomic attractions and hence high enthalpies of atomization.
11. E⁰ for Mn3+/Mn2+ couple is much more positive than for the Fe3+/Fe2+. Why?
 Answer: Large positive values of E⁰ for Mn3+/Mn2+ couple is due to the large third
ionization enthalpy of Mn when it becomes Mn3+( due to the 3d5 configuration of
Mn2+).
The large positive value E⁰ for Mn3+/Mn2+ means that Mn3+ can be easily reduced to
Mn2+ as it goes to stable d5.
12. Which of the two V(IV) and V(V) is paramagnetic? Give reasons.
23V =[Ar] 3d 4S , V(IV) =[Ar]3d , V(V)=3d
5 2 1 0

Thus V(IV) has one unpaired electron hence it is paramagnetic in nature.

13. The paramagnetic character of 3d transition series elements increases upto Mn and
the decreases.
Answer: As we move from Sc to Mn , the number of unpaired electrons increases
and hence paramagnetic character increases. After Mn, pairing of electrons in the d-
subshell starts and hence the paramagnetic character decreases.
14. Scandium forms no coloured ions, yet it is regarded as a transition element. Explain
why?
Answer: Scandium in the ground state has one electron in the 3d-subshell. Hence, it
is regarded as a transition element. However, in its common oxidation state +3, it
has no electron in 3d sub shell. Hence, it does not form coloured ions.
15. i) Of the ions Ag+, Co2+ and Ti4+, which one will be coloured in aqueous solution?
ii) If each one of the above ionic species is in turn placed in a magnetic field, how
will it respond and why?
Answer: i) Co2+ will be coloured because it has unpaired electrons.
ii) Co2+ will be attracted by magnetic field due to the presence of unpaired electrons,
whereas Ag+ and Ti4+ will not be attracted by magnetic field because Ag+ has
completely filled d-orbitals and Ti4+ has empty d-orbitals.
16. Why is hydrochloric acid is not used to acidify KMnO4 in the volumetric estimation
of Fe2+ and C2O42-?
Answer: This is because a part of oxygen produced from KMnO4 & HCl is used to
oxidize HCl to Cl2.
17. Why is KMnO4 used in cleaning surgical instruments in hospitals?
Answer: This is because KMnO4 has germicidal properties.
18. Why the properties of third transition series are very similar to second transition
series? (OR) Why second and third series elements show similar size? (OR) Why the
second and third members in each group of the transition elements have very
similar atomic radii?
Answer: Due to lanthanoid contraction the size of atoms of the third series is almost
same as that of the second series. This leads to similar properties.
19. Why the third ionization enthalpy of manganese is unexpectedly high?
Answer: Mn2+ has the configuration [Ar]3d5 which is stable due to the half filled d5
configuration.
20. For the first row of transition metals, the E⁰ values are

E⁰ V Cr Mn Fe Co Ni Cu
(M2+/M) -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34

Explain the irregularity in the E0 value in the above series.

Answer: this is because E⁰ values are sum of sublimation enthalpy, ionization
enthalpy, hydration enthalpy etc. The irregularity is due to irregular variation of
ionization enthalpies and also the sublimation enthalpies.
21. Why is the E⁰ value values for Mn3+/Mn2+ couple is much more positive than for
Cr3+/Cr2+ or Fe3+/Fe2+?
Answer: the large positive E⁰ value for Mn3+/Mn2+ shows that Mn2+ is more stable
than Mn3+. This is due to the 3d5 configuration which is half filled and hence is very
stable.
22. Transition metal fluorides are ionic in nature whereas bromides and chlorides are
usually covalent in nature. Why?
Answer: As electronegativity of halogens decreases in the order F>Cl>Br, the ionic
character of transition metal halides decreases in the order M-F>M-Cl.M-Br. Hence,
fluorides are ionic whereas chlorides and bromides are covalent.
23. The E⁰ values in respect of the electrode of chromium, manganese and iron are
Cr3+/Cr2+=-0.4V, Mn3+/Mn2+ =+.1.5V, Fe3+/Fe2+=+0.8V
On the basis of the above information compare the feasibilities of further oxidation
of their +2 oxidation states.
Answer:
i) -ve value of E⁰ for Cr3+/Cr2+ shows that Cr2+ is least stable.
ii) Greater +ve value for Mn3+/Mn2+ than that for Fe3+/Fe2+ shows that Mn2+ is
more stable than Fe2+.
iii) Hence stability of +2 oxidation state is in the order:
Cr2+<Fe2+ <Mn2+
24. Why is that largest number of oxidation states are exhibited by the elements in the
middle of the first row transition metals?
Answer: The maximum number of oxidation states is shown by the elements in a
transition series which has maximum number of unpaired electrons.
25. What is the effect of pH on the solution of K2Cr2O7 solution?
Answer: In aqueous solution
Cr2O72- + H2O 2 CrO42- + 2H+
Dichromate ion Chromate ion
(orange red) (yellow)
In acidic medium equilibrium shifts backwards and the colour is orange red. In basic
medium equilibrium shifts forward and the solution becomes yellow in colour.
26. How is the variability in the oxidation state of the transition elements different from
that of the non-transition elements?
Answer: The variability of oxidation states of transition metals is due to the
incomplete filling of d-orbitals in such a way that their oxidation states differ by
unity, E.g.,Fe2+ and Fe3+.
In case of non transition elements the oxidation states differ by units of two, e.g.,
Pb2+ and Pb4+.
Moreover, in transition metals the higher oxidation states are more stable for
heavier elements in a group. In p-block elements the lower oxidation states are
more stable for heavier members due to inert pair effect.
27. Why is Cr2+ reducing and Mn3+ oxidizing when both have d4 configuration?
Answer: Cr2+ changes readily to d3 because d3 has half filled teg orbitals and hence
stable. Therefore it is reducing in nature. Whereas Mn3+ changes to Mn2+ which is
more stable due to the half filled d5 configuration.
28. How would you account for the increasing oxidizing power in the series
VO2+ <Cr2O72-<MnO4- ?
Answer: This is due to the increasing stability of the lower species to which they are
reduced.
29. How do you account for the fact that transition metals and their compounds are
found to be good catalyst?
Answer: Because of their ability to exhibit variable oxidation state.
30. In the 3d series of transition elements Zinc has the lowest enthalpy of atomization.
Why?
Answer: In the 3d series zinc does not have any unpaired electrons. Hence, atomic
intermetallic bonding is weakest in zinc.
31. The E⁰ (M2+/M) value for copper is positive (+0.34V).What is possibly reason for
this?
Answer: E⁰ for any metal is related to the sum of the enthalpy of atomization,
enthalpy of ionization and enthalpy of hydration. Copper has high enthalpy of
atomization and low enthalpy of hydration. Hence, E⁰ for copper is positive.
32. How would you account for the irregular variation of ionization enthalpies in first
series of the transition elements?
Answer: Change in the ionization enthapy of the elements is irregular due to
i) Reorganization energy ii) Irregular electronic configuration
33. Why is the highest oxidation state of the metal exhibited in its oxides and fluorides
only?
Answer: Because of the high electro negativity of oxygen and fluorine.
34. Explain why Cu+ ion is not stable in aqueous solution?
Answer: Cu+ is not stable in aqueous state due to the high negative hydration
enthalpy of Cu2+.
35. Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
Answer: This is due to the poor shielding by 5f electrons in the actinoids than by the
4f electrons in the lanthanoids.
36. Why are Mn2+ compounds are more stable than Fe2+ compounds towards oxidation
to their +3 oxidation state?
Answer: Electronic configuration of Mn2+ is 3d5 which is half filled and hence more
stable. Therefore for oxidation to +3 oxidation is very difficult. Whereas Fe2+ is in
3d6 configuration. So further oxidation to +3 state means attaining more stable 3d5
configuration.
37. Transition metals and many of their compounds are paramagnetic in nature. Why?
Answer: Because most of them have unpaired electrons.
38. Transition metals and their compounds act as good catalyst. Why?
Answer: Because they show variable oxidation state.
39. What are interstitial compounds and why are such compounds known for transition
metals?
Answer: Compounds in which small atoms such as H, C B and nitrogen occupy the
empty spaces in large atoms are called interstitial compounds. Since transition
metals have empty space in their lattice they readily form interstitial compounds.
40. For M2+/M and M3+/M2+ syatems, E⁰ values for some metals are as follow:

Cr2+/Cr -0.9 V Cr3+/Cr2+ -0.4V

Mn2+/Mn -1.2V Mn3+/Mn2+ +1.5V
Fe2+/Fe -0.4V Fe3+/Fe2+ +0.8V

Use this data to comment upon

i) The stability of Fe3+ in acid solution as compared to that of Cr3+ and Mn3+
ii) The ease with which iron can be oxidized as compared to the similar process
for either Cr or Mn metals.

Answer:

i) Cr3+/Cr2+ has a negative reduction potential. Hence, Cr3+ cannot be reduced to

Mn3+/Mn2+ has large positive E⁰ value and hence it can be reduced easily . E⁰
value for Fe3+/Fe2+ is also positive but very small. Hence Fe3+ is more stable
than Mn3+ but less stable than Cr3+.
ii) Since Fe has the least negative potential value it will be less readily oxidisied
than Mn and Cr.
41. Predict which of the following will be coloured in aqueous ssolution?
Ti3+, V3+,Sc3+,Mn3+,Fe3+,Co2+ and MnO4-
 Answer: Only those ions will be coloured which have incompletely filled d-
orbitals.Thus, all except Sc3+ are coloured.
MnO4- is coloured not because of d-d- transition but due to charge transfer (from O
to Mn) reducing the oxidation state of Mn from +7 to +6 momentarily.
42. Cobalt(II) is stable in aqueous solution but in presence of a complexing agent
(ligand) it is easily oxidized. Why?
Answer: Cobalt(III) has a greater tendency to form coordination compounds than
cobalt(II). Hence it is easily oxidized in the presence of a ligand.
43. The d1configuration is very unstable in ions. Explain.
Answer: The ions in d1 configuration will have the tendency to lose an electron and
gain d0 configuration. Hence they are unstable in d1 configuration.
44. Why is that the highest oxidation state is exhibited in oxo-anion of a metal?
Answer: This is due to the higher electronegativity of oxygen and also its ability to
form multiple bond with the metal.
45. For transition metals the lowest oxide is basic, the highest acidic inn nature. Explain.
Answer: Because at the lower oxidation state it can donate electrons and hence
behave as base whereas in the higher oxidation state it can only accept electrons
and hence behave as acid.
46. The chemistry of actinoid elements are not as smooth as that of lanthanoids. Give
reason.
Answer: The chemistry of actinoid is highly complicated due to the variable
oxidation state exhibited by them and their radioactive nature.
47. Why do actinoids have more number of oxidation states than lanthanoids?
Answer: Due to the comparable energy level of 7s, 6d and 5f orbitals.
48. Differentiate between actinoids and lanthanoids.

Lanthanoids Actinoids
Shows only one stable oxidation state Variable oxidation state
+3
They are less basic They are more basic
Most of the ions are colourless Most of the ions are
coloured
They are non-radioactive ,except They are radioactive
promethium
Do not form oxocation Form oxocations
49. What happens when chromates are kept in acidic solution?
Answer : They are converted into dichromate
50. Copper(I) compounds are white and diamagnetic while copper(II) compounds are
coloured and paramagnetic and fom coloured compounds. Explain.
 Answer: In copper(I) all orbitals are completely filled and hence coloureless and
diamagnetic whereas copper(II) has 3d9 configuration and hence d-d transition is
possible. So it is coloured and paramagnetic in nature.
51. What do you mean by lanthanoid contraction?
Answer: The regular decrease in the atomic and ionic radii with increase in the
atomic number among the 5d series due to the poor shielding effect of intervening
4f orbitals is called lanthanoid contraction.
52. Explain why size of trivalent lanthanoid cations decrease with increase in the atomic
number.
Answer: because of lanthanoid contraction
53. Why Sm2+, Eu2+ and Yb2+ ions in solutions are good oxidizing agents while an
aqueous solution of Ce4+ is a good oxidizing agent?
Answer: The most stable oxidation state of lanthanoids is +3. Hence, ions in +2
states tend to change to +3 oxidation state by loss of electrons and those in +4 state
tend to change to +3 state by gain of electrons.
54. Of lanthanoides, Cerium (at no 58) forms a tetra positive ion, Ce4+ in aqueous
solution. Why?
Answer: Ce(III) having the configuration 4f15d06s0 can easily lose an electron to
acquire the configuration 4f0 and form Ce(IV).
55. Why Zr and Hf exhibit similar properties? /
Answer: Due to lanthanide contraction, Hf and Zr have similar size.
56.