CHEMISTRY THE d- AND f-BLOCK ELEMENTS

THE d- AND f-BLOCK ELEMENTS

Lanthanides and Actinides

Introduction to f-Block Elements

 These elements are also called inner transition elements because the last electron
enters (n−2) f- orbital, i.e. inner to the penultimate energy level and forms a transition
series.
 The general electronic configuration of these elements can be given as
Hence, they have three incomplete shells, viz. (n−2), (n−1) and nth.

Classification of f-block elements

 Lanthanoids:

 They are called Lanthanoids because they come immediately after Lanthanum.
 They are also called 4f-block elements or first inner transition series elements or
lanthanides or lanthanons.

 Actinoids:

 They are called Actinoids because they come immediately after Actinium.
 They are also called 5f-block elements or second inner transition series elements
oractinides or actinons.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

The Lanthanoids:

 Electronic Configuration:

 Lanthanoids have the common electronic configuration of 6s2 and electrons

occupying 4f levelvariably. The electronic configuration of all the tripositive ions are
of the form 4fn (n = 1 −14) with increasing atomic number.
 The electronic configuration of Europium (Z = 63) is 4f7 6s2 and that of Gadolinium
(Z = 64) is 4f7 5d1 6s2. This can be explained on the basis of extra stability of the
half-filled orbitals in theircores.
 The electronic configuration of Ytterbium (Z = 70) is 4f14 6s2 and that of Lutetium
(Z = 71) is 4f14 5d1 6s2. This is also explained on the basis of extra stability of the
filled orbitals in theircores.

 Oxidation states:
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

 The common oxidation state of the lanthanoids is +3.

 The +2 and +4 oxidation states are very less common. These are exhibited by those
elements which attain a stable electronic configuration of f0, f7 or f14 by losing 2 or
4 electrons.
 Here, each element tries to attain the stable oxidation state by losing or gaining
electrons, i.e.
+3. Hence, Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing agents and
aqueoussolutions of Ce4+ and Tb4+ are good oxidising agents.

 Atomic and ionic radii of Lanthanoids:

 In lanthanoids, if the atomic number increases, atomic and ionic radii decrease
from La3+ toLu3+.

Variation of ionic radii of trivalent lanthanoids

 Causes of lanthanoid contraction:

1. When we move from left to right along the lanthanoid series, the nuclear
charge increases by one unit at each neighbouring element. The new electron
is added to the same subshell. So, the attractive force between the electron
and nucleus increases, and hence,the size decreases.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

2. When a new electron is added to the f-subshell, the shielding effect of one
electron by another is not perfect due to the shape of f-orbitals. Such a
shielding cannot balance the effect of increased nuclear charge. Hence,
contraction occurs.

 Consequences of lanthanoid contraction:

(a) Difficulty in separation of lanthanoids:

1. Because of the slight difference in ionic radii of lanthanoids, their chemical

propertiesare similar. This makes separation of lanthanoids more difficult.
2. Also, due to the difference in the size of lanthanoids, properties such as
solubility,complex ion formation and hydration show differences. This helps
separate the individual lanthanoids by the ion exchange method.

(b) Similarity in the size of elements belonging to the same group of the second
and thirdtransition series:
1. The size of elements belonging to the second transition series is always
greater than that of the elements belonging to the same group of the first
transition series. Also, the size of the atom of the third transition series, i.e.
after lanthanum, is nearly the same as that of the atom of the element
belonging to the same group of the second transition series.
2. Similarity in size of the atoms of the elements belonging to the same group
of the 2nd and 3rd transition series is due to the effect of lanthanoid
contraction.

(c) Effect on the basic strength of hydroxides:

Because the size of lanthanoid ions decreases from La3+ to Lu3+, the covalent
character of the hydroxides increases, and hence, the basic strength decreases.
Therefore, La(OH)3 is more basic, while Lu(OH)3 is weakly basic.

 Characteristics of Lanthanoids:

(a) Silvery appearance and softness:

All lanthanoids are silvery white soft metals and tarnish easily in air. As the atomic
numberincreases, their hardness also increases.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

(b) Melting point:

They have a very high-melting point in the range 1000−1200 K except samarium,
which has ahigh melting point of about 1623 K.

(c) Electrical and thermal conductivity:

They have metallic characteristics, and hence, they are good conductors of heat
and electricity.

(d) Density:
They have high densities in the range of 6.77−9.74 gcm −3. Density and other
properties differsmoothly with increasing atomic number except in Eu and Yb.

(e) Colour:
They are silvery white. Most of the trivalent ions are coloured in solid and in
aqueous solution.This is due to f–f transition.

(f) Magnetic behaviour:

All the lanthanoids except La3+ and Lu3+ show paramagnetism. This property is due
to thepresence of unpaired electrons in the incomplete 4f subshell.

(g) Ionisation enthalpies:

The first ionisation enthalpies of lanthanoids are about 600 kJ mol−1 and the second
is about 1200 kJ mol−1. The third ionisation enthalpy is low if it leads to a stable
electronic configuration,
i.e. empty, half-filled or completely filled.

(h) Electropositive character:

They are highly electropositive because they possess low ionisation enthalpy.

(i) Standard electrode potential:

The value of their standard electrode potential, i.e. Eo for half-reaction, M3+ (aq) + 3e-
 M(s), lies in the range −2.2 to −2.4 V. Europium is an exception because its Eo
value is −2.0 V.

(j) Reducing agents:

They easily lose electrons; hence, they are good reducing agents.

(k) Complex formation:

CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Because of their large size and low charge density, they do not have much tendency
to form complexes. This tendency of complex formation increases with increasing
atomic number.

(l) Chemical behaviour:

The first few elements of the series are more reactive like calcium. As the atomic
numberincreases, their behaviour becomes similar to that of aluminium. They show
the followingproperties:

They combine with hydrogen on heating.

They form carbides when heated with carbon.

They form halides when burnt with halogens.

They react with dilute acids to liberate

hydrogen gas.

They form oxides and hydroxides.

 Uses of lanthanoids:

1. It is mainly used in the production of alloy steels to improve the strength of steel. A
well-knownalloy is mischmetal which has the following composition:

 Lanthanoid metal = 95%

(about 50% Ce, 40% La and the rest other

lanthanoids)

 Iron = 5%

 S, C, Ca and Al = traces
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

The mischmetal is mostly used in making a magnesium-based alloy. It is pyrophoric

alloy, i.e.an alloy which emits sparks when struck. It is used in making bullets, shells
and lighter flints.
2. Their oxides are used in the glass industry—for polishing glass and to make optical
glass.
3. Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
4. Ceric sulphate is a well-known oxidising agent used in volumetric analysis.

Actinoids

 Electronic Configuration:

 All the actinoids have common 7s2 configuration, and filling of the 5f and 6d
subshells isvariable.
 The 14 electrons are being added to 5f, except in thorium (Z = 90), but this
filling of the 5f subshell continues further after thorium till 5f orbitals are complete
at Z = 103.
 Irregularities in the electronic configurations of actinoids are concerned with the
stabilities of f0,f7 and f14 configurations.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

 Although the 4f and 5f orbitals have similar shapes, 5f is less deeply buried than
4f. Hence, 5felectrons can participate in bonding.

 Oxidation state:
 The common oxidation state of all actinoids is +3.
 Actinoids also possess the oxidation state of +4. Some of them show higher
oxidation state. The oxidation state gradually increases from the extreme left to the
middle of the series and then decreases.
 The compounds of actinoids with +3 and +4 oxidation states undergo hydrolysis.

 Ionic radii and actinoid contraction:

 Like lanthanoids, actinoids also show contraction due to the poor shielding
effect of the 5f-electrons.
 So, the radii of the atoms or ions of actinoids decrease gradually along the series.
 This contraction is greater from element to element in a series because 5f orbitals
extend in thespace beyond 6s and 6p orbitals.

 Characteristics of Actinoids:

(a) Silvery appearance:

Actinoids are metals with silvery appearance.

(b) Structural variability:

They have much more regularities in their metallic radii; hence, they show
great structuralvariability.

(c) Colour:
They are silvery white metals. Their cations are generally coloured. The colour of
these cationsdepends on the number of 5f-electrons.
The cations containing zero 5f electrons or seven 5f electrons are colourless.
The cationscontaining 2−6 5f electrons are coloured.
This colour mainly arises because of f–f transition.

(d) Melting and boiling points:

Actinoids have high melting and boiling points. They do not show any gradual
change even withincreasing atomic number.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

(e) Density:
With the exception of thorium and americium, all actinoids have high densities.
(f) Ionisation enthalpies:
They have low ionisation enthalpies than lanthanoids. This is because 5f is less
penetrating than 4f and hence is more effective in shielding from nuclear charge.

(g) Electropositive character:

They are highly electropositive.

(h) Magnetic behaviour:

They are strongly paramagnetic. The change in magnetic susceptibility of actinoids
with increasing number of unpaired electrons is the same as lanthanoids, but the
values are higher for actinoids.

(i) Reducing agents:

All the actinoids are strong reducing agents.

(j) Radioactivity:
All the actinoids are radioactive. The first few members of the series have long half-
lives. The remaining have half lives ranging from very few days to few minutes.

(k) Chemical behaviour:

They are highly reactive in the crushed form. They show the following properties:

 Uses of actinoids:
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Uses of thorium Uses of uranium Uses of plutonium

• It is used in atomic • It is used as nuclear • It is used as a fuel for

reactors and in fuel. atomic reactors.
treatment of cancer. • Its salts are used in • It is also used for
• Its salts are used in glass, textile, ceramic making bombs.
making incandescent industries and in
gas mantles. medicines.

Comparison of Lanthanoids and Actinoids

 Similarities:

Actinoids show
actinoid
Both show Both are Both exhibit
contraction and
common electropositive magnetic and
lanthanoids
oxidation state and very spectral show
of +3. reactive. properties.
lanthanoid
contraction.

 Differences:

Mind map : learning made simple Chapter - 8
• Helps in production of iron and steels.
• Position : Between s–and p–blocks • TiO in pigment industry
• Electronic configuration : (n –1)d1–10ns1–2 • MnO2 in dry battery cells.
• Physical properties : Show typical metallic properties, melting and • As catalysts in industry.
boiling point are high; High enthalpies of atomization • Ni complexes useful in the polymerization of • Electronic : configuration [Rn]5f 1–14 6d0–2 7s2
• Decrease in radius with increasing atomic number. Lanthanoid alkynes and other organic compounds such as benzene.
• Ionic sizes : Gradual decrease along the series
contraction is due to imperfect shielding of one e– by another • Ag Br in photographic industry.
in same set of orbitals. • Oxidation states : Most common is +3. They
• Ionisation enthalpies : Increases from left to right show ON of +4, +5, +6 and +7.
• Oxidation states : Variable ;higher ON stable • General characteristics :
–Silvery in appearance
• Trends in M2+/M E° : E° for Mn, Ni and Zn are more negative than
expected. –Display variety of structures
–Highly reactive metals
• Trends in M3+/M2+ E° : variable
–Irregularities in metallic radii,
• Chemical reactivity and E° values : Variable; Ti2+, V2+ and Cr2+
are strong reducing agents.
d– Block
tran greater than in Lanthanoids.
siti
o –Magnetic properties more
• Magnetic properties : Diamagnetism and paramagnetism. Magnetic ne
moment increases with increasing atomic number. lem complex than lanthanoids.
en
• Formation of coloured ions : Form coloured compounds due to d – d t s
transitions

gr
ou
• Formation of complex compounds : Form a large number of complex

p
compounds

s3
• Catalytic properties : Due to variable oxidation states and ability to

–12
form complexes.
• Forms interstitial compounds : Non - stoichiometric and are neither The d– And • Electronic configuration
ionic nor covalent.
F– Block 4f1–14 5d0–1 6s2
• Alloy formation : Due to similar atomic sizes. • Atomic and ionic sizes
Elements
Decreases from La to Lu
• Oxidation states
Most common is +3. Some elements
exhibit +2 and +4.
• General characteristics
• Potassium dichromate K 2Cr2O7
•Silvery while soft metals and tarnish
Preparation : 4FeCr2O4 + 8Na2CO3 + 7O2 →8Na2CrO4 + 2Fe 2O3 +8CO2 rapidly in air.
+ + 2–
2Na2CrO4 + 2H → Na2Cr2O7 + 2Na + H2O •Hardness increases with increasing
O pm O O
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl 9
17 atomic number.
126°
Properties : Cr2 O27 − + 14H+ + 6e– → 2Cr3+ + 7H2O O Cr Cr O •Metallic structure and good conductors
16
3p
O m O Ln2O3 of heat and electricity.
Oxidises iodides to iodine, H2S to S, SO32 − to SO24 − , NO−2 to NO−3
H2
•Variable density
•Trivalent Lanthanoid ions are coloured.
burn
ds

• Ionisation Enthalpies : Low third ionisation

s in
aci

• Potassium permanganate KMnO 4 Ln2S3 hea enthalpies

th

O2

ted
wi

Preparation : 2MnO2 + 4KOH + O2 → 2KMnO4 + 2H 2O

wit
hS • Good reducing agents.
O LnX3
+
3 MnO2 − + 4H+ → 2 MnO− + MnO + 2H O
4 4 2 2 Ln gens
hN with hal
+ it
2Mn2+ + 5S2O3 + 8H2O → 2 MnO−4 + 10 SO24 − + 16H dw
w

Mn
73 K

ate
ith

Properties : Intense colour, weak temperature dependent he

H2

paramagnetism O O
O

LnN
+ O
MnO−4 + 8H + 5e – → Mn2+ + 4H 2O
with C 27

Ln(OH)3+H2
Oxidizes I– to I2, Fe 2+ to Fe3+, C2 O24 − to CO 2, S2– to S, SO32 − to SO24 −,
NO−2 to NO−3
LnC2
SCIENCE THE D AND F BLOCK ELEMENTS

Important Questions
Multiple Choice questions-
Question 1. Which transition metal can show highest oxidation state?

(a) Sc

(b) Ti

(c) Os

(d) In

Question 2. Which of the following is not an actinoid?

(a) Thorium

(b) Californium

(c) Uranium

(d) Terbium

Question 3. Which of the following would be diamagnetic?

(a) Cu2+

(b) Ni2+

(c) Cd2+

(d) Ti3+

Question 4. Misch metal is an alloy of

(a) La

(b) Th

(c) Ac

(d) none of these

Question 5. Maximum magnetic moment is shown by

(a) 3d8
SCIENCE THE D AND F BLOCK ELEMENTS

(b) 3d7

(c) 3d9

(d) 3d5

Question 6. Maximum oxidation number of manganese is in

(a) K2MnO4

(b) MnO2

(c) KMnO4

(d) Mn2O4

Question 7. Electronic configuration of Fez+ ion is

(a) [Ar] 4s23d4

(b) [Ar] 4s13d5

(c) [Ar] 3d6

(d) [Ar] 3d8

Question 8. Electronic configuration of Cr (Z = 24) is

(a) 3d4 4s2

(b) 3d6 4s0

(c) 3d5 4s1

(d) none of these

Question 9. Increasing order of paramagnetism is

(a) Cu2+ CO2+, Mn2+, Ni2+

(b) CO2+, Cu2+, Mn2+, Ni2+

(c) Cu2+, Ni2+, CO2+, Mn2+

(d) Mn2+, CO2+, Ni2+, Cu2+

Question 10. Copper sulphate dissolves in excess of KCN to give:

SCIENCE THE D AND F BLOCK ELEMENTS

(a) [CU(CN)4]3-

(b) [CU(CN)4]2-

(c) CuCN

(d) [Cu(CN2].

Very Short Questions-

1. Zinc, cadmium and mercury are not considered as transition metals. Why?
2. Write the general configuration of d- block elements.
3. What are the factors that decide the ionization potential?
4. What are interstitial compounds. Give two examples
5. What is the ore of ?
6. What is the effect of adding a base to potassium dichromate?
7. Draw the structure of chromate and dichromate ions?
8. Draw the structure of manganate and permanganate ions?
9. Complete and balance: -

1.

2.

3.

4.

5.

6.

10. Name the two series of f-block.

11. The chemistry of actinoids is more complicated than lanthanoids. Why?
12.What is the general valance configuration of f-block elements?
13. What is the most common oxidation state of lanthanoids and actinoids?
14. Actinoid contraction is more than lanthanoid contraction. Give reason.
15. What is the composition of mischmetal? Give its one use.
SCIENCE THE D AND F BLOCK ELEMENTS

16. Actinoids show larger number of oxidation states than lanthanoids. Why?
Short Questions-
1. Give an explanation for the catalytic properties shown by transition metals.
2. Write some characteristics of interstitial compounds.
3. Describe the steps of preparation of ?
4. Give some of the uses of ?
5. What happens when
(a) A lanthanoid reacts with dill- acid
(b) A lanthanoid reacts with water.
6. Transition metals generally form coloured ions. Why? Which of the following will be
coloured?
7. Explain the steps of preparation of potassium dichromate?
8. What is the lanthanoid contraction? What are its causes and consequences?
Long Questions-
1.Give reasons-
(i) Transition metals have high melting points.
(ii) Second and third transition series have similar radii.
(iii) Second ionization is difficult from Cu and Cr whereas it is easy for Zn.
(iv) Most of the transition elements are paramagnetic.
(v) Transition elements form alloys.

2. Silver atom has completely filled d orbitals in its ground state. How can you say
that it is a transition element?
3. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the
lowest, i.e., . Why?
4. Which of the 3d series of the transition metals exhibits the largest number of oxidation
states and why?
5. The value for copper is positive (+0.34V). What is possibly the reason for
this? (Hint: consider its high and low )
6. How would you account for the irregular variation of ionization enthalpies (first and
second) in the first series of the transition elements?
7. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
8. Which is a stronger reducing agent or and why?
Assertion and Reason Questions-
1. In these questions, a statement of assertion followed by a statement of reason is given. Choose
the correct answer out of the following choices.
SCIENCE THE D AND F BLOCK ELEMENTS

a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.

Assertion: Co (IV) is known but Ni (IV) is not.

Reason: Ni (IV) has d6 electronic configuration.

2. In these questions, a statement of assertion followed by a statement of reason is given. Choose

the correct answer out of the following choices.

a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.

Assertion: Transition metals form substitutional alloys.

Reason: Alloys are made to develop some useful properties which are absent in the constituent
elements.

Case Study Questions-

1. Read the passage given below and answer the following questions:

The f-block elements are those in which the differentiating electron enters the (n -2)f orbital.
There are two series of F-block elements corresponding to filling of 4f and 5f-orbitals. The
series of 4f-orbitals is called lanthanides. Lanthanides show different oxidation states
depending upon stability of f0, f7 and F14 configurations, though the most conunon oxidation
states is +3. There is a regular decrease in size oflanthanides ions with increase in atomic
number which is known as lanthanide contraction.

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) The atomic numbers of three lanthanide elements X, Y and Z are 65, 68 and 70
respectively, their Ln3+ electronic configuration is:

a) 4f8, 4f11, 4f13

SCIENCE THE D AND F BLOCK ELEMENTS

b) 4f11, 4f8, 4f13

c) 4f0, 4f2, 4f11
d) 4f3, 4f7, 4f9

(ii) Lanthanide contraction is observed in:

a) Gd
b) At
c) Xe
d) Te

(iii) Which of the following is not the configuration of lanthanoid?

a) [Xe]4f106s2
b) [Xe]4f15d16s2
c) [Xe]4d145d106s2
d) [Xe]4f75d16s2

(iv) Name a member of the lanthanoid series which is well known to exhibit +4 oxidation
state.

a) Cerium (Z = 58)
b) Europium (Z = 63)
c) Lanthanum (Z = 57)
d) Gadolinium (Z = 64

(v) Identify the incorrect statement among the following.

a) Lanthanoid contraction is the accumulation of successive shrinkages.

b) The different radii of Zr and Hf due to consequence of the lanthanoid contraction.
c) Shielding power of 4f electrons is quite weak.
d) There is a decrease in the radii of the atoms or ions as one proceeds from La to Lu.

2. Read the passage given below and answer the following questions:

The transition elements have incompletely filled d-subshells in their ground state or in any of
their oxidation states. The transition elements occupy position in betweens- and p-blocks in
groups 3-12 of the Periodic table. Starting from fourth period, transition elements consists of
four complete series : Sc to Zn, Y to Cd and La, Hf to Hg and Ac, Rf to Cn. In general, the
electronic configuration of outer orbitals of these elements is (n - 1)d 1-10 n1-2. The electronic
configurations of outer orbitals of Zn, Cd, Hg and Cn are represented by the general formula (n -
1)d10ns2. All the transition elements have typical metallic properties such as high tensile
strength, ductility, malleability. Except mercury, which is liquid at room temperature, other
SCIENCE THE D AND F BLOCK ELEMENTS

transition elements have typical metallic structures. The transition metals and their compounds
also exhibit catalytic property and paramagnetic behaviour. Transition metal also forms alloys.
An alloy is a blend of metals prepared by mixing the components. Alloys may be homogeneous
solid solutions in which the atoms of one metal are distributed randomly among the atoms
of the other.

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Which of the following characteristics of transition metals is associated with higher
catalytic activity?

a) High enthalpy of atomisation.

b) Variable oxidation states.
c) Paramagnetic behaviour.
d) Colour of hydrated ions.

(ii) Transition elements form alloys easily because they have.

a) Same atomic number.

b) Same electronic configuration.
c) Nearly same atomic size.
d) Same oxidation states.

(iii) The electronic configuration of tantalum (Ta) is:

a) [Xe]4f05d16s2
b) [Xe]4f145d26s2
c) [Xe]4f145d36s2
d) [Xe]4f145d46s2

(iv) Which one of the following outer orbital configurations may exhibit the largest number
of oxidation states?

a) 3d54s1
b) 3d54s2
c) 3d24s2
d) 3d34s2

(v) The correct statement(s) among the following is/ are:

I. All d and f-block elements are metals.

II. All d and f-block elements form coloured ions.
III. All d and f-block elements are paramagnetic.
SCIENCE THE D AND F BLOCK ELEMENTS

a) (I) only
b) (I) and (II) only
c) (II) and (III) only
d) (I), (II) and (III)

MCQ Answers-
1. Answer: (c) Os

2. Answer: (d) Terbium

3. Answer: (c) Cd2+

4. Answer: (a) La

5. Answer: (d) 3d5

6. Answer: (c) KMnO4

7. Answer: (c) [Ar] 3d6

8. Answer: (c) 3d5 4s1

9. Answer: (c) Cu2+, Ni2+, CO2+, Mn2+

10.Answer: (a) [CU(CN)4]3-

Very Short Answers-

Ans 1. Zinc, cadmium and mercury have fully filled configuration. Therefore, they are
not considered as transition metal.

Ans 2. General electronic configuration of d- block elements is .

Ans 3. The ionization potential values are governed by various ionization enthalpy
values, bond enthalpy values and hydration enthalpy values.

Ans 4. Compounds formed by trapping small atoms like H, C, or N inside the crystal
lattices of metals eg. TiC, etc.

Ans 5. Potassium dichromate chromite ore Potassium Permanganate

pyrolusite.

Ans 6. When a base is added to orange coloured potassium dichromate its colour
SCIENCE THE D AND F BLOCK ELEMENTS

changes to yellow due to formation of potassium chromate.

Ans 7.

Ans 8.

Ans 9.
1.
2.
3.
4.
5.
6.

Ans 10. The two series are-

i) 4f series or Lanthanoids
ii) 5f series or actinoids.

Ans 11. The complications in the actinoid series is due to

i) Existence of a wide range of oxidation states.
ii) Their radioactivity.

Ans 12. The general electronic configuration of f-block elements is

SCIENCE THE D AND F BLOCK ELEMENTS

Ans 13. The common oxidation states of

(1) 4f series is +3
(2) 5f series is +3, +4, +5, +6 & +7

Ans 14. The actinoid contraction is more than Lanthanoid contraction as the shielding
Power of 5f orbitals is poorer than 4f orbitals.

Ans 15. Mischmetal is an alloy of a Lanthanoid metal and iron and traces of S, C, Ca & Al.
It is used in Magnesium based alloy to produce bullets, shell and lighter Flint.

Ans 16. Actinoids can show many oxidation states as in actinoids 5f orbitals are filled
which are not as buried as Lanthanoids and can also participate in bonding to a greater
extent besides 6d and 7s electrons.
Short Answers-
Ans 1. Catalytic properties shown by transition metals can be explained due to
(i) Presence of variable valency and ability of elements to form complexes.
(ii) Surface of metals where the reaction can occur.

Ans 2. Some characteristics of interstitial compounds are

(i) They have high melting points.
(ii) They are very hard.
(iii) They retain metallic lustre.
(iv) They are chemically inert.

Ans 3. Potassium Permanganate is prepared in two steps:

Step 1: Fusion of with KOH and oxidizing agent to give dark green .

Step 2: Disproportionation of manganate ions to give permanganate ions.

Ans 4. Uses of potassium permanganate –

(a) As an oxidizing agent.
(b) For bleaching of wool, cotton & silk.
(c) For decolourisation of oils.

Ans 5. (i) When a Lanthanoid reacts with dilute- acid, it liberates hydrogen gas.
SCIENCE THE D AND F BLOCK ELEMENTS

(ii) When a Lanthanoid reacts with water, it forms hydroxide.

Ans 6. Transition metals form coloured ions due to d-d transition. Coloured ions will be
those which have unpaired electrons.
Colourless
Coloured
Coloured
Colourless
Coloured.

Ans 7. Preparation of potassium dichromate takes place in three steps.

Step 1: Fusion of chromite ore with sodium or potassium carbonate in free excess of air.

Step 2: Conversion of Sodium Chromate to Sodium Dichromate by acidifying it.

Step 3: Conversion of sodium dichromate to potassium dichromate by reaching it with KCl.

Ans 8. Lanthanoid contractions – The cumulative effect of the regular decrease in size or radii
of Lanthanoid with increase in atomic number is called Lanthanoid contraction.
Causes – The shape of f orbitals is diffused. They have poor shielding effect due to which the
effective nuclear charge increase with increase in atomic number. This causes a decrease in
atomic radii
Consequences – Due to Lanthanoid contraction-
1. Radii of the members of the third transition series is similar to those of second transition
series.
2. It becomes difficult to separate Lanthanoids.

Long Answers-
Ans.(i) In transition metals besides ns electrons, (n-1)d electrons can also participate in
bonding making stronger metallic bonds. This increases their melting points.
(ii) Due to lanthanoid contraction, there is a decrease in size of 5d series. This makes
their sizes same as sizes of elements of 4d series.
(iii) In Cr the electronic configuration is and for Cu, it is . In these after first
ionization, which removes the electron from 4s, second ionization requires disturbance
in half filled or fully filled configuration which requires high enthalpy whereas the
configuration of Zn is . Here after second ionization, the configuration of Zn is
completely filled. Therefore, second ionization is easier for Zn but difficult for Cr and Cu.
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(iv) Para magnetism in transition elements arises due to presence of one or more
unpaired electrons in atomic orbitals.
(v) Due to similarity in their sizes, transition metals can take each others position in
their crystal lattice. Therefore they are able to form alloys.
Ans. Ag has a completely filled 4d orbital in its ground state. Now, silver displays
two oxidation states (+1 and +2). In the +1-oxidation state, an electron is removed from
the s-orbital. However, in the +2-oxidation state, an electron is removed from the d-
orbital. Thus, the d-orbital now becomes incomplete . Hence, it is a transition
element.
Ans. The extent of metallic bonding an element undergoes decides the enthalpy of
atomization. The more extensive the metallic bonding of an element, the more will be its
enthalpy of atomization. In all transition metals (except Zn, electronic
configuration: ), there are some unpaired electrons that account for their stronger
metallic bonding. Due to the absence of these unpaired electrons, the inter-atomic
electronic bonding is the weakest in Zn and as a result, it has the least enthalpy of
atomization.
Ans. Mn (Z = 25) = Mn has the maximum number of unpaired electrons present in
the d-subshell (5 electrons). Hence, Mn exhibits the largest number of oxidation states,
ranging from +2 to +7.
Ans. The value of a metal depends on the energy changes involved in the
following:
1. Sublimation: The energy required for converting one mole of an atom from the solid
state to the gaseous state.

2. Ionization: The energy required to take out electrons from one mole of atoms in the
gaseous state.

3. Hydration: The energy released when one mole of ions are hydrated.

Now, copper has a high energy of atomization and low hydration energy. Hence,
the value for copper is positive.
Ans. Ionization enthalpies are found to increase in the given series due to a continuous
filling of the inner d-orbitals. The irregular variations of ionization enthalpies can be
attributed to the extra stability of configurations such as . Since these states are
exceptionally stable, their ionization enthalpies are very high.
In case of first ionization energy, Cr has low ionization energy. This is because after
losing one electron, it attains the stable configuration . On the other hand, Zn has
exceptionally high first ionization energy as an electron has to be removed from stable
SCIENCE THE D AND F BLOCK ELEMENTS

and fully-filled orbitals .

Second ionization energies are higher than the first since it becomes difficult to remove
an electron when an electron has already been taken out. Also, elements like Cr and Cu
have exceptionally high second ionization energies as after losing the first electron, they
have attained the stable configuration ( and ). Hence, taking out one
electron more from this stable configuration will require a lot of energy.

Ans. Both oxide and fluoride ions are highly electronegative and have a very small size.
Due to these properties, they are able to oxidize the metal to its highest oxidation state.
Ans. The following reactions are involved when and act as reducing agents.

The value is – 0.41 V and is +0.77 V. This means that can be easily
oxidized to , but does not get oxidized to easily. Therefore, is a better
reducing agent that Fe3+.

Assertion and Reason Answers-

1. (d) Assertion is wrong statement but reason is correct statement.

Explanation:

Both Co and Ni have (IV) oxidation state. Ni (IV) has 3d 6 electronic configuration.

Metals Outer electronic configuration Oxi. states

Co 3d74s2 +2, +3, +4
Ni 3d84s2 +2, +3, +4

2. (b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.

Explanation:

Transition metals form substitutional alloys since they have nearly the same size, they can substitute
one another in the crystal lattice.

Case Study Answers-

1. Answer :

(i) (a) 4f8, 4f11, 4f13

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Explanation:

Terbium (65), 4f8; Dysprosium (Dy), 4f9; Ytterbium (Yb), 4f13.

(ii) (a) Gd

(iii) (c) [Xe]4d145d106s2

(iv) (a) Cerium (Z = 58)

(v) (b) The different radii of Zr and Hf due to consequence of the lanthanoid contraction.

Explanation:

The almost identical radii of Zr (160pm) and Hf (159pm), a consequence of lanthanoid

contraction.

2. Answer :

(i) (b) Variable oxidation states.

Explanation:

The transition metals and their compounds are known for their catalytic activity. This
activity is ascribed to their ability to adopt multiple oxidation states to form complexes.

(ii) (c) Nearly same atomic size.

Explanation:

Because of similar radii and other characteristics of transition metals, alloys are readily
formed by these metals.

(iii) (c) [Xe]4f145d36s2

(iv) (b) 3d54s2

Explanation:

Greater the number of valence electrons, more will be the number of oxidation states
exhibited by the element.

(v) (a) (i) only

Explanation:
SCIENCE THE D AND F BLOCK ELEMENTS

All the d-block elements are metals, they exhibit most properties of metals like lustre,
malleability, ductility, high density, high melting and boiling point, hardness, conduction of
heat and electricity, etc. All the f-block elements are also metals but they are not good
conductors of heat and electricity.