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 d 5 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 seriesdue 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 expectedincrease 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).
 (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
 (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 (K2Cr2 O7)
(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+ 3Sn 4++ 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)+ 2H 2O
 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   K 2MnO 4 + MnO2 + O2
Heat ,

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

 MnO4– + 8H+ + 5e–   Mn 2+ + 4H2O (Acidic)
 2MnO4– + 16H+ + 5C2O42   2Mn 2+ + 8H2O +10CO2
 MnO4– + 8H+ + 5Fe2+   Mn2+ + 4H2O + 5Fe3+
 2MnO4– + 16H+ + 10I–   2Mn 2+ + 8H2O +5I2
 5NO2- +2MnO4–+ 6H+   2Mn 2+ + 3H2O +5NO3-
 5SO3 +2MnO4 + 6H 
2- – +  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.

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.

11. Assertion(A) : Magnetic moment values of actinides are lesser than the
theoretically predicted values.
Reason(R) : Actinide elements are strongly paramagnetic.
12. Assertion(A) : KMnO4 act as an oxidising agent in acidic, basic or neutral
medium.
Reason(R) : KMnO4 oxidises ferrous sulphate to ferric sulphate.
13. Assertion(A) : Of the 3d4species Cr2+ is strongly reducing and Mn 3+ is strongly
oxidising.
Reason(R) : Cr+3 state is stable due to half-filled t2g set, Mn+2 is stable due to
half- filled d orbitals
14. Assertion(A) :In the series Sc to Zn the enthalpy of atomisation of Zinc is the
lowest.
Reason(R): Zinc has greater number of unpaired electrons
15. Assertion(A) :Magnetic moment of Mn2+ is less than that of Cr2+.
Reason(R): Magnetic moment depends on the number of unpaired electrons.
VERY SHORT ANSWER TYPE QUESTIONS( 1 MARK)
16. Which element has highest melting point in 3d series ?
17. Out of Cu2Cl2 and CuCl2 which is more stable in aqueous solution.
18. Which element of the first transition series don’t exhibit variable oxidation states?
19. Name an oxo anion having oxidation number of metal (3d series) equal to its
groupnumber.
20. Name two elements of 3d series which show anomalous electronic configuration.
21. Identify the Transition metal of 3d series that acts as a strong reducing agent in +2
oxidation state in aqueous solution.
22. Name a member of lanthanoid series which is well-known to show +4 oxidation
state.
23. Among the elements of 3d series which element is soft?
24. Arrange the following in increasing order of acidic character: CrO3,CrO, Cr2O3
25. Complete the following equation :
3MnO42- +4H+
VERY SHORT ANSWER TYPE QUESTIONS (2 MARKS)
26. Name an important alloy which contains some of the lanthanoid metals. Mention
its uses.
27. Among Elements of 3d transition series: Write the element
(a) Which is not regarded as transition element.
(b) Which shows maximum number of oxidation states.
(c) Which forms stable divalent(M2+) ion
(d) Which shows only +3 state?
28. What is Lanthanoid contraction? Give its cause. What are its Consequences?
29. When pyrolusite ore MnO2 is fused of with KOH in presence of air,a green
coloured compound (A) is obtained which undergoes disproportionation reaction
in acidic medium to give purple coloured compound (B).
(i) Write the formulae of (A) & (B).
(ii) What happens when compound (B) is heated.
30. When chromite ore FeCr2O4 is fused with NaOH or (Na2CO3) in presence of air, a
yellow coloured compound (A) obtained which on acidification with dilute
 sulphuric acid gives a compound (B). Compound (B) on reaction with KCl forms
an orange coloured crystalline compound (C).
(a) Write the formulae of (A), (B) & (C).
(b) Write one use of compound (C).
SHORT ANSWER TYPE QUESTIONS (3 MARKS)
31. Explain giving a suitable reason for each of the following
(a) Metal –metal bonding is more frequent for the 4d & 5d series of
transition metals than that for the 3d series.
(b) Cu+ salts are colourless while Cu2+ salts are Coloured
(c) Mn2+ exhibits maximum Para magnetism
32. Account for the following
(a) Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite
difficult to separate them.
(b) There is in general increase in density of element from titanium to copper.
(c ) Most of the transition metals and their compounds act as good catalysts.
33. Explain the following observations.
(a) Mn Shows the highest oxidation state of +7 among 3d series elements
(b) Mn Shows the highest oxidation state of +7 with oxygen but with fluorine it
shows the highest oxidation state of +4.
(c )MnO is basic while Mn2O7 is acidic in nature.
34. Account for the following
(a) Cu+ ion is not stable in aqueous solutions.
(b) The d1 configuration is very unstable in ions.
(c )Eo value for the Mn 2+/Mn much more than expected.
35. Assign reasons for the following.
(a) Scandium is a transition element but Zinc is not.
(b) Silver atom has completely filled d orbital (4d10) in its ground state, yet it is
transition element.
(c )In the series Sc(Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is the
lowest.
LONG ANSWER TYPE QUESTIONS (5 MARKS)
36. Give Reasons for the following
(i) Ce4+ in aqueous solution is a good oxidising agent.
(ii) Actinoids contraction is greater from element to element than lanthanoid
contraction.
(iii) The actinoids exhibit a larger number of oxidation states than the
corresponding lanthanoids.
(iv) La3+ and Lu3+do not show any colour in solutions.
(v) Chemistry of all the lanthanoids are quite similar.
37. Complete & balance the following reactions: -
a) Cr2O72–+ Fe2++ H+→
b) MnO4– + H+ + C2O42-  
c) KMnO4  
Heat , 
d) MnO4– + H2O+ I-  
e) Cr2O72– + OH-→