The d and f-block Elements

General electronic configuration (n-1) d 1-10 ns 1-2.

d- Block elements are collectively known as Transition Elements because

properties of these elements vary in between s-Block and p-Block elements.

Transition elements- Transition elements may be defined as the elements whose

atoms or ions contain partially filled d-orbitals in the atomic state or ionic state
with most common oxidation state.

Group 12 elements i.e. Zn, Cd, Hg have completely filled (n-1) d-orbital in atomic
& ionic state & thus these elements are not transition Elements.

Sl Elements At. No Electronic configuration

No.
1 Scandium (sc) 21 1s2 2s2 2p6 3s2 3p6 3d1 4s2 or [Ar] 3d14s2
2 Titanium (Ti) 22 1s2 2s2 2p6 3s2 3p6 3d2 4s2 or [Ar] 3d24s2
3 Vanadium (V) 23 1s2 2s2 2p6 3s2 3p6 3d3 4s2 or [Ar] 3d34s2
4 Chromium (Cr) 24 1s2 2s2 2p6 3s2 3p6 3d5 4s1 or [Ar] 3d54s1
5 Manganese (Mn) 25 1s2 2s2 2p6 3s2 3p6 3d5 4s2 or Ar] 3d54s2
6 Iron (Fe) 26 1s2 2s2 2p6 3s2 3p6 3d6 4s2 or [Ar] 3d64s2
7 Cobalt (Co) 27 1s2 2s2 2p6 3s2 3p6 3d7 4s2 or [Ar] 3d74s2
8 Nickel (Ni) 28 1s2 2s2 2p6 3s2 3p6 3d8 4s2 or [Ar] 3d84s2
9 Copper (Cu) 29 1s2 2s2 2p6 3s2 3p6 3d10 4s1 or [Ar] 3d104s1
10 Zinc (Zn) 30 1s2 2s2 2p6 3s2 3p6 3d10 4s2 or [Ar]3d104s2

Atomic radii
In the beginning of the series, atomic radius decreases because, nuclear force of
attraction is greater than screening effect.
In the middle of the series, atomic radius remains constant, because, nuclear
force of attraction counter balances the screening effect.
Towards the end of the series, the atomic radii increases, because, Screening
effect becomes greater than attractive forces.

Oxidation of 3d transition elements.

Transition elements show variable oxidation state, because, the energies of 3d
orbitals and 4s orbitals are very close and hence both 3d and 4s electrons are
available for bond formation.
+1 and +2 oxidation state involves the participation of 4s electrons where as
higher oxidation states such +3, +4, +5, etc. involves participation of 3d orbitals
for the bond formation.
Example: Outer electronic configuration of scandium is 3d1 4s2. Scandium shows
+2 oxidation state when it uses 4s electrons. And it shows +3 oxidation state
when it uses 3d electrons.

Sl. Elements At. No Electronic Oxidation State

N configuration
 o
.
1 Scandium (Sc) 21 [Ar] 3d14s2 +2, +3
2 Titanium (Ti) 22 [Ar] 3d24s2 +2, +3, +4
3 Vanadium (V) 23 [Ar] 3d34s2 +2, +3, +4, +5
4 Chromium (Cr) 24 [Ar] 3d54s1 +2, +3, +4, +5, +6
5 Manganese (Mn) 25 [Ar] 3d54s2 +2, +3, +4, +5, +6, +7
6 Iron (Fe) 26 [Ar] 3d64s2 +2, +3, +4, +5
7 Cobalt (Co) 27 [Ar] 3d74s2 +2, +3, +4
8 Nickel (Ni) 28 [Ar] 3d84s2 +2, +3
9 Copper (Cu) 29 [Ar] 3d104s1 +1, +2
10 Zinc (Zn) 30 [Ar]3d104s2 +2

Manganese exhibits maximum oxidation state of +7 in compound KMnO4

Magnetic Properties
Most of 3d transition series elements paramagnetic in nature. Because they
contain unpaired electrons in d atomic orbitals. but zinc is diamagnetic because
it do not contains unpaired electrons in d orbitals.

The magnetic moment is given by,

μ= n ( n + 2) BM

Where n = number of unpaired electrons

Unit for magnetic moment is Bohr Magneton or BM.

Formation of coloured compounds

The colour of transition metals or metal ions is due the presence of unpaired
electrons in d orbitals which undergoes d-d transition.
When visible light is passed through a solution of transition metal compound, it
absorbs a particular frequency of radiation and transmits the remaining colours
in the form of complementary colour.

Zinc does not form coloured compounds because it does not contain unpaired
electrons in d orbitals.

Sc+3 salts are colourless because, Sc+3 do not contain unpaired electrons in d
orbitals.
Cr+3 salts are coloured because, Cr+3 salts contain unpaired electrons in d
orbitals.
Cu2+ ions are coloured because, Cu+2 salts contain unpaired electrons in d
orbitals.

Catalytic properties
i. Presence of vacant d orbitals
ii. Ability to show variable oxidation state.
iii. They have tendency to form complexes.

Formation of complex compounds

i. Presence of vacant d orbitals
ii. Ability to show variable oxidation state.
iii. They have tendency to form complexes.
Examples: K4(Fe(CN)6], K3(Fe(CN)6], [Cu(NH3)4]SO4

Intestinal compounds
When smaller atoms like H, C, or N are trapped inside the crystal lattices of
transition metals, intestinal compounds are formed.
Characteristics of interstitial compounds
i. They have high melting points, higher than those of pure metals.
ii. They are very hard and they retain metallic conductivity.

Alloy Formation
An alloy is a homogeneous mixture of one or more metals.
Examples: Brass (copper-zinc)
Bronze (copper-tin).

Potassium dichromate
Manufacture of potassium dichromate from chromite ore
Step 1: Roasting – Conversion of chromite ore into sodium chromate.
4 FeO.Cr2O3 + 8Na2CO3 + 7O2 2 Fe2O3 + 8 Na2CrO4 + 8 CO2
Step 2 : Conversion of sodium chromate into sodium dichromate
2 Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Step 3 : Conversion of sodium dichromate into potassium dichromate
Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl

Properties
Action of Alkali:
2CrO4 2– + H2O
Cr2O7 2– + 2 OH-
Orange red Yellow

+ Cr2O7 2– + H2O
2CrO4 2– + 2H
Yellow Orange red

Oxidising properties:
i. It oxidises iodide to iodine
Cr2O7 2– + 14H+ + 6I- 2 Cr3+ + 7H2O + 3I2

ii. It oxidises suphides to sulphur

Cr2O7 2– + 8H+ + 3H2S 2Cr3+ + 7H2O + 3S

iii. It oxidises Stannous (Sn(II)) to stannic (Sn(IV))

Cr2O7 2– + 14H+ + 3Sn2+ 2Cr3+ + 7H2O + 3Sn4+
iv. It oxidises ferrous (Fe(II)) to ferric (Fe(III))
 Cr2O7 2– + 14H+ + 6Fe2+ 2 Cr3+ + 7H2O + 6Fe3+

Manufacture of potassium permanganate from Pyrolusite.

When MnO2 is fused with potassium hydroxide and oxidising agent KNO3, dark
green K2MnO4 is formed. This undergoes disproportionate reaction in neutral or
acidic solution to form potassium permanganate.
2MnO2 + 4KOH + O2 2 K2MnO4 + 2 H2O

+
2 K2MnO4 + 4 H 2 KMnO4 + MnO2 + 2 H2O + 4 H+

Commercial preparation

Potassium permanganate is commercially prepared by the fusion of MnO2

followed by the electrolytic oxidation of manganate.
MnO2 is fused with KOH and then oxidised with KNO3 to get manganate. The
alkaline solution of manganate is electrolytically oxidized to get permanganate.

Fused with KOH,

oxidising agent KNO3
2 MnO2 MnO4-2

Electrolytic oxidation
in alkaline solution
MnO4-2 MnO4-

Chemical Properties
i. Action Heat
513K
2KMnO4 K2MnO4 + MnO2 + O2

Oxidising properties
In Acidic medium
a. It oxidises iodide to iodine
2MnO4– + 16H+ +10 I – 2Mn+2 + 8H2O + 5I2

b. It oxidises ferrous (Fe(II)) Green to ferric (Fe(III))nyellow

MnO4– + 8H+ +5Fe2+ Mn+2 + 4H2O + 5Fe3+

c. It oxidises oxalic acid to oxalate

2MnO4– + 16H+ + 5C2O42- 2Mn+2 + 8H2O + 10CO2

d. It oxidises hydrogen sulphide to sulphur

2MnO4– + 16H+ + 5H2S 2Mn+2 + 8H2O + 5S

e. It oxides sulphite to sulphate
2MnO4– + 6 H+ +5SO3 –2 2Mn+2 + 3H2O + 5SO4 –2
f. It oxidises nitrite to nitrate
2MnO4– + 6 H+ +5NO2 – 2Mn+2 + 3H2O + 5NO3 –

In Neutral or faintly alkaline medium

a. It oxidises iodide to idate

2MnO4 – +H2O + I- 2MnO2 + 2OH- + IO3-

b. It oxidises thiosulphate to sulphate
8MnO4 – + 3S2O3-2 + H2O 8MnO2 + 6SO4-2 + 2OH-

c. It oxidises Manganous salt to MnO2

2MnO4 – +2H2O +3Mn+2 5 MnO2 + 4 H+

Inner Transition elements (f- block elements)

General electronic configuration of f-block elements:

[Noble gas] (n-2) f1-14 (n-1)d0-1 ns2

f block elements consists of two series

Lanthanoids: Lanthanum, and following 14 elements i.e., Cerium (58) to
Lutetium (71) are called lanthanoids.
General electronic configuration of Lanthanoids: [Noble gas] 4f1-14 5d 0-1 6s2

Atomic Radii
The gradual decrease in atomic and ionic radii from lanthanum to lutetium is
called lanthanoid contraction.
The decrease in size is due to poor shielding effect from f electrons in the the
second inner shell.

Consequence of lanthanoid contraction: Zirconium (160 pm) and Hoffnium (159

pm), shows similar properties because of lanthanoid contraction.

Oxidation State
Common Oxidation state of lanthanoids is +3.
Cerium exhibits +4 oxidation state. Because, Ce+4 has noble gas electronic
configuration.
Ce+4 is good oxidising agent, Because Ce+4 readily undergoes reduction to form
common oxidation state +3.
Chemical properties:
 2 Ln + 6HCl 2 LnCl3 + 3H2

2 Ln + 3H2 2 LnH3

2 Ln + 3X2 2 LnX3

4 Ln + 3O2 2 Ln2O3

2 Ln + 6H2O 2 Ln(OH)3 + 3H2

2 Ln + 3S 2 Ln2S3

2 Ln + N2 2 LnN

Mischmetal
It is an important alloy, which contains 95% lanthanide metal and 5% Fe along
with traces of S, C, Ca and Al. It is used in Mg-based alloy to produce bullets,
shells and lighter flint.

Actinoids: Actinium (89), and following 14 elements i.e Thorium (90) to

Lawrencium (103) are called actinoids.
General configuration of Actinoids: [Noble gas] 5f1-14 6d 0-1 7s2
Common Oxidation state of Actinoids is +3.

Actinoid contraction is greater from element to element than lanthanoid

contraction due to Poor shielding effect of 5f orbitals.
Questions carrying ONE marks each

1. What is lanthanide contraction? Mention the cause for it. ( May 2017)
Ans. The gradual decrease in atomic and ionic radii from lanthanum to
lutetium is called lanthanoid contraction.
Due to the imperfect shielding of one electron by another in the same set of
orbitals.

2. Zr and Hf have almost identical radii ( March 2016 ) ( July 2014 )

Ans. Due to Lanthanoid contraction.

3. a. Actinoids generally show variable oxidation states. ( March 2016, July

2014, June 2015 )
b. Lanthonoids are less reactive than actinoids. (March 2016)
Ans. a. because energies of 5f, 6d and 7s orbitals are almost same.

4. What is lanthanoid contraction? Write the general oxidation states of

actinoids. ( June 2016)
Ans. The gradual decrease in atomic and ionic radii from lanthanum to
lutetium is called Lanthanoid contraction.
The general oxidation states of actinoids is +3.

5. What is Lanthanoid contraction? Mention one of its consequences. (

March 2014 )
Ans. The gradual decrease in atomic and ionic radii from lanthanum to
lutetium is called Lanthanoid contraction.
Radii of members of 3rd transition series are similar to 2nd transition series.

6. Give reasons; Cerium exhibits +4 oxidation state ( June 2015 )

Ans. Because, Ce+4 has noble gas electronic configuration.

7. What is the formula of the products formed when a Lanthanoid (Ln) reacts
with (i) Halogen(x). (ii) Nitrogen?
Ans. i. LnX3 i. LnN

8. Give reasons: Actinoid contraction is greater from element to element

than lanthanoid contraction.
Ans. Poor shielding effect of 5f orbitals.

9. Give reason:
a. Mn exhibits the higher oxidation state of +7 among 3d series transition
elements.
b. Cu+ is paramagnetic and Cu2+ is diamagnetic.
Ans. Because both 4s and 3d electrons involved in the formation of bond.
b. Cu+ do not have unpaired electrons whereas Cu2+ has one unpaired electron.

10. Give reason: “Transition metals generally form coloured compounds”.

Ans. The colour of transition metals or metal ions is due the presence of
unpaired electrons in d orbitals and d-d transition.
When visible light is passed through a solution of transition metal compound,
 it absorbs a particular frequency of radiation and transmits the remaining
colours in the form of complementary colour.

11. Give reason:

a. Most of the transition metals have high melting point and boiling
point.
b. Second ionization enthalpy of copper is exceptionally high.
Ans. Because of stronger interatomic bonding, transition elements have high
melting and boiling points.
b. because of stable 3d10 electronic configuration.

12. Write the general electronic configuration of 3d series of transition

elements.
Ans. 3d1-10 4s1-2

13. Write the general electronic configuration of f-block elements.

Ans. [Noble gas] (n-2) f1-14 (n-1)d0-1 ns2

Questions Carrying three marks each

14. i. Calculate the spin-only magnetic moment of Fe2+. [Atomic number of

iron = 26].
ii. Which element of 3d series exhibits maximum oxidation state? (
March 2017 )
Ans.
i. For Fe+2 n = 4
μ = n ( n + 2) = 4 ( 4 + 2) = √24 = 4.89 BM
ii. Manganese or Mn

15. How is KMnQ4 [Potassium permanganate] is prepared from MnO2? Write

equations. ( March 2017, June 2016 )
Or
Explain the preparation of KMnQ4 [Potassium permanganate] from
MnO2? ( March 2016 )
Or
Describe the manufacture of potassium permanganate from Pyrolusite.
Or
How is potassium permanganate prepared? Give equations.
Ans. When MnO2 is fused with potassium hydroxide and oxidising agent
KNO3, dark green K2MnO4 is formed. This undergoes disproportionate
reaction in neutral or acidic solution to form potassium permanganate.
2MnO2 + 4KOH + O2 2 K2MnO4 + 2 H2O

+
2 K2MnO4 + 4 H 2 KMnO4 + MnO2 + 2 H2O + 4 H+

16. a. 3d series elements exhibit variable oxidation states. Why? ( June

2015)
Ans. Because energies of 3d orbitals and 4s orbitals are very close and hence
both 3d and 4s electrons are available for bond formation.
 b. Calculate the magnetic moment of Mn+2 ion. ( June 2015)
Ans. For Mn+2 n = 5
μ = n ( n + 2) = 5 ( 5 + 2) = √35 = 5.9 BM

17. Describe the manufacture of potassium dichromate from chromite ore. (

June 2015)
or
Write the balanced chemical reaction in the manufacture of Potassium
dichromate from chromite ore. ( March 2016 )
or
How is potassium dichromate prepared from chromite ore?
Ans.
Step 1: Roasting – Conversion of chromite ore into sodium chromate.
4 FeO.Cr2O3 + 8Na2CO3 + 2 Fe2O3 + 8 Na2CrO4 + 8 CO2
Step 2 : Conversion of sodium chromate into sodium dichromate
2Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O
Step 3 : Conversion of sodium dichromate into potassium dichromate.
Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl

18. a. Calculate the spin only magnetic moment of Fe+2 . ( March 2016 )
Ans. For Fe+2 n = 4
μ = n ( n + 2) = 4 ( 4 + 2) = √24 = 4.89 BM

b. Why Sc+3 salts are colourless where as Cr+3 salts are coloured. ( March
2016 )
Ans. Sc+3 do not contain unpaired electrons in d orbitals where a Cr+3 salts
contain unpaired electrons in d orbitals.

19. Cu2+ ions are coloured but Zn+2 ions are colourless. Give reason ( June
2016 )
Ans.
a. Zn+2 do not contain unpaired electrons in d orbitals where a Cu+2 salts
contain unpaired electrons in d orbitals.

20. Write the formula to calculate spin only magnetic moment. ( March
2016 )
Ans. μ = n ( n + 2)

21. a. Give reason: Sc+3 salts are colourless where as V+3 salts are coloured.
b. What are intestinal compounds ? ( March 2016 )
Ans.
a. Sc+3 do not contain unpaired electrons in d orbitals where a V+3 salts
contain unpaired electrons in d orbitals.

b. Interstitial compounds are those which are formed When lighter elements
such as Carbon, Hydrogen or Nitrogen gets trapped inside the crystal lattices
of transition metals.
22. Name the metal of 1st row transition series that
a. has maximum number of unpaired electrons in its ground state.
b. has zero spin only magnetic moment in its +2 oxidation state.
c. Exhibits maximum number of oxidation states.
Ans.
a. Chromium.
b. Zinc.
c. Manganese.

23. a. What is the gas liberated when.

i. Crystals of potassium permanganate is heated to 513 K?
ii. Acidified potassium permanganate is treated with oxalate ion at 333
K.
b. Complete the following equation:

2 MnO4 – + 3 Mn +2 + 2 H2O ______ + 4 H+

Ans.
i. Oxygen.
ii. Carbon dioxide.

b. 2 MnO4 – + 3 Mn +2 + 2 H2O 5 MnO2 + 4 H+

24. a. Write ionic equations for the reaction of dichromate ions with (i)
Hydroxy ions. (ii) Fe+2 ions in acidic medium.
b. In which one of the above two reactions will the oxidation number of
chromium remains unchanged.
Ans.
i.
Cr2O7 2– + 2 OH- 2–
2CrO4 + H2O
Cr2O7 2– + 14 H+ + 6 Fe2+ 2 Cr3+ + 7 H2O + 6 Fe3+
ii.
b. reaction with hydroxyl ions.

25. a. What are intestinal compounds? Write any one characteristics.

b. Out of the following elements, identify the element which does not
exhibit variable oxidation states.: Cr, Co, Zn.
Ans.
a. When smaller atoms like H, C, or N are trapped inside the crystal lattices of
transition metals, intestinal compounds are formed.
i. They have high melting points, higher than those of pure metals.
ii. They are very hard and they retain metallic conductivity.
b. Zinc.

26. i. What happens when H2S is passed into potassium dichromate in acidic
medium? Give the equation.
ii. What is the composition of chromite ore?
Ans.

Cr2O7 2- + 8 H+ + 3 H2S 2Cr3+ + 7 H2O + 3S

 ii. FeO.Cr2O3

27. a. Transition metals and their compounds are used as catalysts. Give two
reasons.
b. Write the outer electronic configuration of chromium (atomic number
= 24)
Ans.
i. presence of vacant d orbitals and ability to show variable oxidation state.
iii. they have tendency to form complexes.
b. 1s2 2s2 2p6 3s2 3p6 3d5 4s1 or [Ar] 3d54s1

28. a. Calculate the magnetic moment of Cr+3 .

b. Which is more stable Fe+3 or Fe+2.
Ans.
a. For Cr+3 n = 3
μ = n ( n + 2) = 3 ( 3 + 2) = √15 = 3.89 BM
b. Fe+3 is more stable.

29. Give reason:

i. Transition elements exhibit variable oxidation state.
ii. Ti+4 ion is colourless.
iii. Cu+ is diamagnetic.
Ans.
i. Because energies of 3d orbitals and 4s orbitals are very close and hence
both 3d and 4s electrons are available for bond formation.
ii. Ti+4 ion is colourless because, Ti+4 do not contain unpaired electrons.
iii. Cu+ is diamagnetic Cu+ do not contain unpaired electrons.

30. a. Compare any two properties of lanthonoids and actinoids.

b. Give reason Zr and Hf exhibits similar properties.
Ans.
i. Both Show common oxidation state +3
ii. Both are electropositive and very reactive.
iii. Both exhibit magnetic and spectral property.
b. Zirconium and Hoffmium shows similar properties because of lanthanoid
contraction.

31. Give reason:

a. Transition metals exhibits higher enthalpies of atomization.
b. Cr2+ is stronger reducing agent than Fe+2.
c. The Highest oxidation state exhibited by oxoanions of metal.
Ans.
a. because of strong interatomic force of attractions.
b. / is lesser than /
c. due to combination of metal with oxygen is highly electronegative and
oxidising agent.
32. a. Name an important which contains some of the lanthanoid metal and
mention its use.
b. Name the common oxidation state of Actinoids.
Ans.
 a. Misch metal contains 95% of Lanthanoid and 5% iron and trces of S, C, Ca
and Al.
b. +3.

33. Complete the following equation

i. Cr2O7 2– + 14 H+ + 6
ii. 8 MnO4 – + 3 S2O3-1 + ______ +
b. Give reason: Zinc is treated as transition metal.
Ans.
i. Cr2O7 2– + 14H+ + 6Fe2+ 2 Cr3+ + 7 H2O + 6 Fe3+

ii. 8MnO4 – + 3S2O3-2 + H2O 8MnO2 + 6SO4-2 + 2OH-

b. because Zinc has completely filled d orbitals.

34. Give reason:

a. Actinoids show more number of oxidation states than lanthonoids.
b. The atomic radii of Zirconium and Hoffnium are very close to each
other.
c. Ce+4 is good oxidising agent.
Ans.
a. Because energies of 5f, 6d and 7s orbitals are almost same.
b. Because of lanthanoid contraction.
c. Because Ce+4 has a tendency to get more oxidation state +3