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4. THE d- AND f-BLOCK ELEMENTS

QUICK REVISION POINTS:
1. d-block elements
(a) DEFINITION: A 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. Zinc, cadmium and
mercury of group 12 have full d10 configuration in their ground state as well as in
their common oxidation states and hence, are not regarded as transition metals. Their
Outer electronic configuration is (n -1) d1-10 ns 1-2
(b) MELTING AND BOILING POINTS: High MP & BP which is due to their strong metallic
bond (strong interatomic bonding ) due to unpaired electrons in (n-1) d orbitals.In any
row the melting points of these metals rise to a maximum at d5 except for anomalous
values of Mn and Tc.
(c) ENTHALPIES OF ATOMIZATION: High enthalpies of atomization Because of large
number of unpaired electrons in their atoms they have stronger interatomic
interaction (metal-metal bonding). The metals of the second and third series have
greater enthalpies of atomisation than the corresponding elements of the first series
due to occurrence of much more frequent metal – metal bonding.
(d) VARIATION IN ATOMIC AND IONIC SIZES : In general, ions of the same charge in a
given series show progressive decrease in radius with increasing atomic number The
atomic radii decreases from group 3 to 6 because of increase in effective nuclear
charge gradually, The atomic radii of group 7,8,9 &10 elements is almost same
because Screening effect counter balances increased effective nuclear charge, Group
11 &12 elements have bigger size due to increase inter-electronic repulsion as result
electron cloud expands and size increases. Members of second(4d) and the third (5d)
series in each group of transition elements have similar radii and shows similar
properties because lanthanoid contraction essentially compensates for the expected
increase in atomic size with increasing atomic number.
(e) DENSITY: The decrease in metallic radius coupled with increase in atomic mass
results in a general increase in the density of these elements. Thus, from titanium
(22) to copper ( 29) the significant increase in the density may be noted.
(f) VARIATION IN IONISATION ENTHALPIES OF TRANSITION METALS: There is an
increase in ionisation enthalpy along each series of the transition elements from left
to right due to an increase in nuclear charge which accompanies the filling of the
inner d orbitals. Irregular variation of ionisation enthalpies is mainly attributed to
varying degree of stability of different 3d-configurations (e.g., d0, d5, d10 are
exceptionally stable).
(g) OXIDATION STATES: The transition elements show variable oxidation state due to
small energy difference between (n-1) d & ns orbital as a result both (n-1) d & ns
electrons take part in bond formation. The highest oxidation state of an element is
equal to number of unpaired e- present in (n-1) d & ns orbital.
(h) MAGNETIC PROPERTIES : Most of the transition metal ions are paramagnetic. due
to the presence of unpaired electrons in d-orbitals. Magnetic moment is given by

Where, n = number of unpaired electrons and BM = Bohr magneton (unit of magnetic

moment).

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 (i) FORMATION OF COLOURED IONS: Due to the presence of unpaired electrons in d-
orbitals of the transition metal ions & because of d– d transitions occurring in a
transition metal ions by the absorption of visible light.
(j) FORMATION OF COMPLEX COMPOUNDS :- Due to smaller sizes of the metal ions,
their high ionic charges and the availability of d orbitals for bond formation.
(k) CATALYTIC PROPERTIES: Due to Variable oxidation states & Large surface area.
(l) FORMATION OF INTERSTITIAL COMPOUNDS: Transition elements form interstitial
compounds because size of C, N, O, and B is similar to size of interstitial voids of
transition metals.
(m) ALLOY FORMATION: As the atomic sizes are very similar, one metal can replace
the other metal from its lattice and form a solid solution which is the alloy.
(n) STANDARD ELECTRODE POTENTIALS: Transition elements have lower negative
value of Standard Electrode Potentials due to high ionization potential, high heat of
sublimation & low enthalpy of hydration. The E0 (M2+/M) values are not regular which
can be explained from the irregular variation of ionization enthalpies and also the
sublimation enthalpies which are relatively much less for manganese and vanadium.
(o) Oxide of transition metals in lower oxidation states are generally basic while those
in the higher oxidation states are acidic. Acidic character increases with increase in
oxidation state is due to decrease in size of metal ion and increase in effective nuclear
charge.e.g. MnO (basic), Mn3O4 (amphoteric), Mn2O7 (acidic).
2. LANTHANOIDS
(a) The 14 elements after Lanthanum having atomic number 58 to 71 are collectively
known as Lanthanoids. The general electronic configuration of these elements is [Xe]
4f1-14, 5d0-1,6s2.
(b) LANTHANOID CONTRACTION (ATOMIC AND IONIC SIZES): The overall decrease in
atomic and ionic radii from lanthanum to lutetium is due to poor shielding of 4f
electrons is known as lanthanoid contraction. Due to lanthanoid contraction:-
(a)basic character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3,
(b) Sizes of 4d and 5d metal pairs like Zr and Hf; Nb and Ta are almost similar.
(c) OXIDATION STATES: Most common oxidation state of these elements is +3,
However, occasionally +2 (Eu+2 and Yb+2)and +4 ions (Ce+4 and Tb+4) in solution or in
solid compounds are also obtained.
(d) COLOUR FORMATION :Many trivalent lanthanoid ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may be attributed to the
presence of unpaired electrons in f subshell.
(e) MAGNETIC BEHAVIOUR: The lanthanoid ions other than the f 0 type (La3+ and Ce4+)
and the f 14 type (Yb2+ and Lu3+) are all paramagnetic.
(f) USES : A well-known alloy is mischmetall which consists of a lanthanoid metal(~ 95%)
and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall is used in
Mg-based alloy to produce bullets, shell and lighter flint.
3. ACTINOIDS
(a) The 14 elements after Actinium having atomic number 90 to 113 are collectively
known as Actinoids
(b) The actinoids are radioactive elements These facts render their study more
difficult.
(c) Electronic Configurations: The general electronic configuration of these elements
is [Rn] 5f1-14, 6d0-1,7s2

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 (d) Ionic Sizes(Actinoid contraction): The overall decrease in atomic and ionic radii
across the series due to poor shielding of 5f electrons is known as Actinoid
contraction
(e) The actinoid contraction is, however, greater from element to element in this series
resulting from poor shielding by 5f electrons.
(f) Oxidation States: The actinoids show in general +3 oxidation state. The actinoids
exhibit a larger number of oxidation states, which is in part attributed to the fact
that the 5f, 6d and 7s levels are of comparable energies. The elements, in the first
half of the series frequently exhibit higher oxidation states. For example, the
maximum oxidation state increases from +4 in Th to +5, +6 and +7respectively in
Pa, U and Np but decreases in succeeding elements.
(g) The actinoids are highly reactive metals, especially when finely divided.
(h) The magnetic properties of the actinoids are more complex than those of the
lanthanoids. Although the variation in the magnetic susceptibility of the actinoids
with the number of unpaired 5 f electrons is roughly parallel to the corresponding
results for the lanthanoids
4. POTASSIUM DICHROMATE (K2Cr2O7)
(a) Preparation: - It takes place in three steps-
1. 4FeCr2O4+ 8Na2CO3 +7O2 ⎯ ⎯→ 8Na2CrO4(yellow solution)+ 2Fe2O3 +8CO2
2. 2Na2CrO4 + 2H ⎯ +
⎯→ Na2Cr2O7(orange sodium) + 2 Na+ + H2O
3. Na2Cr2O7 + 2 KCl ⎯ ⎯→ K2Cr2O7(Orange crystals)+ 2 NaCl
(b) The chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solution. 2 CrO42– + 2H+→Cr2O72– + H2O
Cr2O72– + 2 OH-→2CrO42– + H2O
(c) Potassium dichromate in acidic solution act as oxidizing agent.
• Cr2O72–+ 6I–+ 14H+→ 2Cr+3+ 3I2 + 7H2O
• Cr2O72–+ 3H2S+ 8H+→2Cr+3+ 3S+ 7H2O
• Cr2O72–+ 3Sn2++ 14H+→2Cr+3+ 3Sn4++ 7H2O
• Cr2O72–+ 6Fe2++ 14H+→2Cr+3+ 6Fe3+ + 7H2O
(d) Structure of chromates and dichromates

(e) Uses: Potassium dichromate is a very important chemical used in leather industry
and as an oxidant for preparation of many azo compounds. Potassium dichromate
is used as a primary standard in volumetric analysis.
5. POTASSIUM PERMANGNATE [KMnO4]
a) Preparation: -- It takes place in two steps:-
• 2MnO2 + 4 KOH + O2 ⎯ ⎯→ 2 K2MnO4 (Dark green)+ 2H2O
• 3 MnO4 +4H ⎯
2- +
⎯→ 2MnO4-(Purple)+MnO2 +2H2O [Disproportionation]
b) Properties of KMnO4
• Potassium permanganate are isostructural with those of KClO4.
• When heated KMnO4 decomposes at 513 K.
• 2KMnO4 ⎯⎯ ⎯→ K2MnO4 + MnO2 + O2
Heat , 

• KMnO4 act as Oxidising agent in acidic, alkaline & neutral medium.

• MnO4– + 8H+ + 5e– ⎯ ⎯→ Mn2+ + 4H2O (Acidic)
• 2MnO4– + 16H+ + 5C2O42 ⎯ ⎯→ 2Mn2+ + 8H2O +10CO2
• MnO4– + 8H+ + 5Fe2+ ⎯ ⎯→ Mn2+ + 4H2O + 5Fe3+
• 2MnO4– + 16H+ + 10I– ⎯ ⎯→ 2Mn 2+ + 8H2O +5I2

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 • 5NO2- +2MnO4–+ 6H+ ⎯ ⎯→ 2Mn 2+ + 3H2O +5NO3-
• 5SO32-+2MnO4– + 6H+ ⎯ ⎯→ 2Mn 2+ + 3H2O +5SO42-
• oxidising reactions of KMnO4 In neutral or faintly alkaline solutions.
• 2MnO4–+ H2O + I– ⎯ ⎯→ 2MnO2 + 2OH- + IO3–
• 8 MnO4– +3 S2O32- + H2O ⎯ ⎯→ 8MnO2 + 2OH- +6 SO42-
• 2 MnO4–+3Mn+2+ 2H2O ⎯ ⎯→ 5MnO2+ 4H+
6. Permanganate titrations in presence of hydrochloric acid are unsatisfactory since
hydrochloric acid is oxidised to chlorine.
7. Uses: Besides its use in analytical chemistry, potassium permanganate is used as
a favourite oxidant in preparative organic chemistry. Its uses for the bleaching of
wool, cotton, silk and other textile fibres and for the decolourisation of oils are also
dependent on its strong oxidising power.
8. Structure of Permanganate & Manganate:

MULTIPLE CHOICE QUESTIONS (1 MARKS)

1. In which of the following pairs, both the ions are coloured in aqueous solutions?
[Atomic no of Sc = 21, Ti = 22, Ni = 28, Co = 27, Cu = 29]
(a) Sc3+, Ti+3 (b) Sc3+, Co2+ (c) Ni2+, Cu+ (d) Ni2+, Ti3+
2. Which of the following is most stable in aqueous solution?
(a) Mn3+ (b) Cr3+ (c) V3+ (d) Ti3+
3. KMnO4 is not acidified by HCl instead of H2SO4 because
(a) H2SO4 is stronger acid than HCl
(b) HCl is oxidised to Cl2 by KMnO4
(c) H2SO4 is dibasic acid
(d) rate of reaction is faster in presence of H2SO4
4. Manav poured some potassium chromate solution in test tube for qualitative
analysis. The yellow colour of potassium chromate soon turned orange in colour.
Manav realised that this happened because the test tube was not clean and
contained a few drops of some liquid. Which of the following were the liquid drops
most likely to be.
(a) Drops of water (b) methyl orange solution (c ) NaOH solution (d) HCl solution
5. Generally, transition elements form coloured salts due to the presence of unpaired
electrons. Which of the following compounds will be coloured in solid state?
(a) Ag2SO4 (b) CuF2 (c) ZnF2 (d) Cu2Cl2
6. When KMnO4. solution is added to oxalic acid solution, the decolourisation is slow
in the beginning but becomes instantaneous after some time because
(a) CO2 is formed as the product. (b) Reaction is exothermic.
(c) MnO4– catalyses the reaction. (d) Mn2+ acts as auto catalyst.
7. Which of the following are d-block elements but not regarded as transition
elements?
(a) Cu, Ag, Au (b) Zn, Cd, Hg (c) Fe, Co, Ni (d) Ru, Rh, Pd
8. Transition elements form alloys easily because they have
(a) Same atomic number (b) Same electronic configuration
(c) Nearly same atomic size (d) None of the above.
9. Which of the following ion has magnetic moment value of 5.9?
(a) Mn2+ (b) Fe2+ (c) Ni2+ (d) Cu2+
10. Which of the following lanthanoids show +2 oxidation state besides the
characteristic oxidation state +3 of lanthanoids?
(a) Ce (b) Eu (c) Tb (d) Dy.

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