Advance Chemistry
Advance Chemistry
Advance Chemistry
4
The d- and f-Block
Elements
Recap Notes
General characteristics :
Melting and boiling points High due to strong metallic bonding
Enthalpies of atomisation High due to strong interatomic interactions
Ionisation enthalpies Generally increases from left to right in a series
Oxidation states Variable due to participation of ns and (n – 1)d electrons
Atomic radii Decrease from left to right but become constant when pairing of
electrons takes place
Complex formation Form complexes due to high nuclear charge and small size and
availability of empty d-orbitals to accept lone pair of electrons
donated by ligands.
Coloured compounds Form coloured compounds due to d-d transitions
Magnetic properties Transition metal ions and their compounds are paramagnetic
due to presence of unpaired electrons in the (n – 1)d-orbitals
and it is calculated by using the formula, m = n(n + 2) where, n
is the no. of unpaired electrons.
Catalytic behaviour Due to variable oxidation states and ability to form complexes
Interstitial compounds Due to empty spaces in their lattices, small atoms can be easily
accommodated
Alloy formation Due to similar atomic sizes
Alloy formation They form alloys easily with other metals especially iron.
Tendency to form Lanthanoids do not have much tendency to form complexes due to low
complexes charge density because of their large size. The tendency to form complexes
and their stability increases with increasing atomic number.
92. Assertion : Members of 4d and 5d series Reason : The effective nuclear charge felt by
of transition elements have nearly same atomic (n – 1)d electrons is higher as compared to that
radii. by ns electrons.
Reason : Atomic and ionic radii for transition 94. Assertion : The maximum oxidation state of
chromium in its compounds is +6.
elements are smaller than their corresponding
Reason : Chromium has only six electrons in ns
s-block elements.
and (n – 1)d orbitals.
93. Assertion : In transition elements, ns 95. Assertion : Transition metals are poor
orbital is filled up first and (n – 1)d afterwards, reducing agents.
during ionization ns electrons are lost prior to Reason : Transition metals form numerous
(n – 1)d electrons. alloys with other metals.
16. (i) Which metal in the first transition series oxidation states occurs in the middle of the
(3d-series) exhibits +1 oxidation state most series.
frequently and why? 18. What is lanthanoid contraction and what is
(ii) Which of following cations are coloured in it due to? Write two consequences of lanthanoid
aqueous solutions and why? contraction.
Sc3+, V3+, Ti4+, Mn2+
19. What is meant by ‘disproportionation’? Give
(At. Nos. Sc = 21, V = 23, Ti = 22, Mn = 25)
an example of a disproportionation reaction in
17. How would you account for the following :
aqueous solution.
(i) Cr2+ is reducing in nature while with the
same d-orbital configuration (d4), Mn3+ is an 20. (i) Write two characteristic of the transition
oxidising agent. elements.
(ii) In a transition series of metals, the (ii) Which of the 3d-block elements may not be
metal which exhibits the greatest number of regarded as the transition elements and why?
31. (a) Explain the following : (i) Why is E°(Cu2+/Cu) value exceptionally positive?
The enthalpies of atomization of transition (ii) Why is E°(Mn2+/Mn) value highly negative as
metals are quite high. compared to other elements?
(b) Explain the following observations. (b) Give reason and select one atom/ion which
(i) With the same d-orbital configuration will exhibit asked property :
(d4), Cr2+ is a reducing agent while Mn3+ is an (i) Sc3+ or Cr3+ (exhibit diamagnetic behaviour)
oxidising agent. (ii) Cr or Cu (high melting and boiling point)
(ii) There is hardly any increase in atomic size 34. Give reasons for the following :
with increasing atomic numbers in a series of (i) Mn3+ is a good oxidising agent.
transition metals. (ii) EM2+/M values are not regular for first row
32. (i) Transition metals have very high melting transition metals (3d-series).
and boiling points. Why? (iii) d-block elements exhibit more oxidation
(ii) In d-block element, ionic radii of ions of states than f-block elements.
the same charge decreases progressively with 35. How would you account for the following :
increasing atomic number in a series. Why?
(i) The oxidising power of oxoanions are in the
33. (a) order
E°(M2+/M) Cr Mn Fe Co Ni Cu VO+2 < Cr2O72– < MnO4–
–0.91 –1.18 –0.44 –0.28 –0.25 +0.34 (ii) The third ionization enthalpy of manganese
From the given data of E° values, answer the (Z = 25) is exceptionally high.
following questions : (iii) Cr2+ is a stronger reducing agent than Fe2+.