QUESTIONS FROM THE CHAPTER d- & f- BLOCK ELEMENTS:

1. Why are E- values for Mn, Ni and Zn more negative than expected?

Answer:

The metals will quickly lose their electrons and get oxidised. A negative E value means that the oxidised species is more
stable than the reduced species. Here, Mn2+ (3d5) and Zn2+ (3d10) have half-filled and fully filled d orbitals, giving them
stability and, therefore, prefer to stay that way and not get reduced. Ni 2+ (3d8) has very high negative hydration enthalpy,
balanced by first and second ionisation enthalpy.

2. Why is the first ionisation enthalpy of Cr is lower than that of Zn?

Ionisation enthalpy of Cr is less than that of Zn because Cr has a stable configuration. In the case of zinc, the electron
comes out from wholly filled 4s orbital. So, the removal of an electron from zinc requires more energy as compared to
chromium.

3. Transition elements show high melting points. Why?

Answer:

The high melting points of transition metals are due to the involvement of a greater number of electrons of (n-1)d in
addition to the ns electrons involved in strong interatomic metallic bonding.

4. When Cu2+ ion is treated with KI, a white precipitate is formed. Explain the reaction with the help of a chemical
equation.

Answer:

When Cu2+ ion is treated with KI, it produces Cu2I2 white precipitate in the final product.

2Cu2+ + 4I− → Cu2I2 (White ppt.) + I2

(In this reaction, CuI2 is formed, which, being unstable, dissociates into Cu2I2 and I2 ).

5. Ionisation enthalpies of Ce, Pr and Nd are higher than Th, Pa and U. Why?

Answer:

Ce, Pr and Nd are lanthanoids and have an incomplete 4f shell, while Th, Pa and U are actinoids and have an incomplete
5f shell.

When 5f-orbitals begin to be occupied, they will penetrate less into the inner core of electrons. The 5f-electrons will,
therefore, be more effectively shielded from the nuclear charge than the 4f electrons of the corresponding lanthanoids.

Therefore, outer electrons are less firmly held and are available for bonding in the actinoids.
6. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite difficult to separate them. Why?

Answer:

Separation of Zr and Hf is pretty tricky because of lanthanoid contraction. Due to lanthanoid contraction, they have almost
identical sizes (Zr = 160 pm and Hf =159 pm) and, thus, similar chemical properties. That’s why it is tough to separate
them by chemical methods.

7. Although +3 oxidation states is the characteristic oxidation state of lanthanides but cerium shows +4 oxidation
state also. Why?

Answer:

After losing one more electron, Ce3+ acquires a stable 4f0 electronic configuration. Thus, although the +3 oxidation state is
the characteristic oxidation state of lanthanoids, cerium shows a +4 oxidation state.

8. Explain why does colour of KMnO4, disappear when oxalic acid is added to its solution in acidic medium.

Answer:

KMnO4 acts as an oxidising agent. It oxidises oxalic acid to CO2 and changes to Mn2+ ion, which is colourless.

9. When orange solution containing Cr2O72- ion is treated with an alkali, a yellow solution is formed and when
H+ ions are added to yellow solution, an orange solution is obtained. Explain why does this happen?

Answer:

The following reaction takes place when Cr2O72- is treated with an alkali,

(orange) Cr2O72- + OH– → 2CrO42- (yellow)

When the yellow solution is treated with an acid, we get back the orange solution

(yellow) 2CrO42- + 2H+ → Cr2O72– (orange) + H2O

This reaction is reversible under proper conditions.

10. The second and third rows of transition elements resemble each other much more than they resemble the first
row. Explain why?

Answer:

Due to lanthanoid contraction, the atomic radii of the second and third-row transition elements are almost identical. So,
they resemble each other much more than first-row elements.

11. The halides of transition elements become more covalent with increasing oxidation state of the metal. Why?
Answer:

As the oxidation state increases, the size of the ion of the transition element decreases. As per Fajan’s rule, as the size of
metal ions decreases, the covalent character of the bond formed increases. Therefore, the halides of transition elements
become more covalent with the increasing oxidation state of the metal.

12. While filling up of electrons in the atomic orbitals, the 4s orbital is filled before the 3d orbital but reverse happens
during the ionisation of the atom. Explain why?

Answer:

Atomic orbitals are filled in order of increasing energies. Since the energy of 3d orbital is more than 4s orbital, based on
the (n+l) rule, it is filled after 4s orbital. But during ionisation, electrons in the outermost orbital are lost. Since 4s will be
the outermost orbital, in this case, electrons from this orbital will be ionised first.

13. Reactivity of transition elements decreases almost regularly from Sc to Cu. Explain.

Answer:

It is due to the regular increase in ionisation enthalpy.

Long answer questions:

14. When a chromite ore (A) is fused with sodium carbonate in free excess of air and the product is dissolved in
water, a yellow solution of compound (B) is obtained. After treatment of this yellow solution with sulphuric acid,
compound (C) can be crystallised from the solution. When compound (C) is treated with KCI, orange crystals of
compound

(D) crystallise out. Identify A to D and also explain the reactions.

Answer:

Compound A to D are,

A = FeCr2O4 B = Na2CrO4 C = Na2Cr2O7.2H2O D = K2Cr2O7

4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2

2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O

Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

15.(a) Transition metals can act as catalysts because these can change their oxidation state.

How does Fe(III) catalyse the reaction between iodide and persulphate ions?
(b) Mention any three processes where transition metals act as catalysts.

Answer:

(a) The reaction between iodide and persulphate ions.

2I− + S2O82− → I2 + 2SO42−

We can explain this catalytic action as:

2Fe3+ + 2I− → 2Fe2+ + I2

2Fe2+ + S2O82− → 2Fe3+ + 2SO42−

(b) (i) Vanadium (V) oxide in the contact process for the oxidation of SO2 to SO3.

(ii) Finely divided iron in Haber’s process in converting N2 and H2 to NH3.

(iii) MnO2 in preparation of oxygen from KClO3.

16. Answer the following questions:

(i) Which element of the first transition series has the highest second ionisation enthalpy?

(ii) Which element of the first transition series has highest the third ionisation enthalpy?

(iii) Which element of the first transition series has the lowest enthalpy of atomisation?

Answer:

(i) Cu, because the electronic configuration of Cu is 3d10. So, the second electron needs to be removed from the
completely filled d-orbital, which is very difficult.
(ii) Zinc, because of the electronic configuration of Zn = 3d104s2 and Zn2+=3d10, which is fully filled and is very
stable. Removal of the third electron requires very high energy.

(iii) Zinc, as it has completely filled 3d subshell, and no unpaired electron is available for metallic bonding.