CHAPTER -05

The D- & F-BLOCK ELEMENTS

Transition Elements
DEFINITION
Transition elements are those d-block elements which has
partially filled (n – 1)d subshell either in their ground state or in
their stable oxidation states.
Therefore Zn, Cd & Hg are d-block elements but not transition
elements.
GENERAL ELECTRONIC CONFIGURATION
𝑛𝑠 0−2 (𝑛 − 1)𝑑1−10
𝐶𝑟 = 4𝑠1 3𝑑5
Exceptions {
𝐶𝑢 = 4𝑠1 3𝑑10 , 𝑃𝑑 = 5𝑠 0 4𝑑10
TRANSITION SERIES
1st 3d series 𝑆𝑐21 − 𝑍𝑛30 9 + 1 = 10
2nd 4d series 𝑌39 − 𝐶𝑑48 9 + 1 = 10
3rd 5d series 𝐿𝑎57 , 𝐻𝑓72 − 𝐻𝑔80 9 + 1 = 10
4th 6d series 𝐴𝑐89 , 𝑈𝑛𝑞104 − 𝑈𝑢𝑏112 9 + 1 = 10
ATOMIC RADIUS
3d series 𝑆𝑐 > 𝑇𝑖 > 𝑉 > 𝐶𝑟 > 𝑀𝑛 ≥ 𝐹𝑒 ≃ 𝐶𝑜 ≃ 𝑁𝑖 ≤ 𝐶𝑢 < 𝑍𝑛
In a group 3d to 4d series increases but 4d and 5d series nearly
same due to poor shielding of f electron. (Lanthanide contraction)
3𝑑 < 4𝑑 ≃ 5𝑑
smallest radius − Ni
e.g: 𝑇𝑖 < 𝑍𝑟 ≃ 𝐻𝑓 |
Largest radius − La

Melting point: s-blockmetals < d-blockmetals

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In a series on increasing number of unpaired 𝑒 – melting point
increases upto 𝐶𝑟 then decreases.

Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn

Half filled d5 Fully filled d10

∴ weak metallic bond ∴ weak metallic bond
Zn > Cd > Hg
Melting point | (data based)
Cu > Ag ≤ Au

E.N. Exception Zn < Cd < Hg

Density: − s – block metals < d – block metals.

3d series
𝑆𝑐 < 𝑇𝑖 < 𝑉 < 𝐶𝑟 < 𝑀𝑛 < 𝐹𝑒 < 𝐶𝑜 ≤ 𝑁𝑖 < 𝐶𝑢 > 𝑍𝑛
Density in a Group: 3d < 4d << 5d
Metallic character: They are solid, hard, ductile, malleable, good
conductor of heat and electricity and exhibit metallic lusture,
high tensile strength. Hg is liquid Electrical conductor.
𝐴𝑔 > 𝐶𝑢 > 𝐴𝑢 > 𝐴𝑙
d-block p-block
OXIDATION STATE
Transition elements exhibit variable oxidation state due to small
energy difference of ns and (n–1)d electrons.
• Sc(+3) and Zn(+2) exhibit only one oxidation state.
• Common oxidation state is +2 & +3
• In 3d series highest oxidation state is +7 (Mn)
• In d-block series highest oxidation state is +8 (Os, Ru)
• In carbonyl compound oxidation state of metals is zero due
to synergic effects.

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 • Their higher oxidation states are more stable in fluoride
and oxides.
• Higher oxidation states in oxides are normally more stable
than fluorides due to capability of oxygen to form multiple
bonds.

eg. stable fluoride in higher oxidation state of Mn is MnF 4

while oxide is Mn2O7

⇒ Mn show maximum number of oxidation state (+2 to +7)

among 3d series.
⇒ Beyond Mn, trihalide are not observe except FeX3 (X = Cl/Br/I)
& CoF3
⇒ V2O3 V2O4 V2O5
basic basic amphoteric
⇒ CrO Cr2O3 CrO3
basic amphoteric acidic
⇒ MnO MnO2 Mn2O7
basic amphoteric acidic
⇒ CuI2 does not exist
1
𝐶𝑢𝐼2 → 𝐶𝑢𝐼 + 𝐼2
2
⇒ In aqueous, Cu+ disproportinated into Cu & Cu+2. In p-block
lower oxidation states of heavier elements are more stable
while in d-block higher oxidation state of heavier elements are
more stable.
eg. In VIB gp Mo(+6) & W(+6) are more stable than Cr(+6)
MAGNETIC PROPERTY
All transition elements are paramagnetic due to presence of
unpaired electrons. They attract when magnetic field is applied.
Magnetic moment of unpaired electron is due to spin and orbital
angular momentum.

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“Spin only” magnetic moment can be calculated by using formula
𝜇 = √𝑛(𝑛 + 2) Bohr magneton. (𝑛 is number of unpaired 𝑒 – .)
If 𝑛 is 1 𝜇 = 1.73 BM
𝑛 is 2 𝜇 = 2.84 BM
𝑛 is 3 𝜇 = 3.87 BM
𝑛 is 4 𝜇 = 4.90 BM
𝑛 is 5 𝜇 = 5.92 BM
Substances that are not attracted by applied magnetic field are
diamegnetic. They have all the electrons paired. d-block element
and ions having d0 and d10 configuration are diamagnetic.
COLOUR
Colour in transition mental ions is associated with d-d transition
of unpaired electron from t2g to eg set of energies. This is achieved
by absorption of light in the visible spectrum, rest of the light is
no longer white.
Colourless – Sc3+, Ti4+, Zn2+ etc
Coloured – Fe3+ yellow, Fe2+ green, Cu2+ blue, Co3+ blue etc
ALLOYS
Solid mixture of metals in a definate ratio (15% difference in
metallic radius)
They are hard and have high melting point.
eg. Brass (Cu + Zn)
Bronze (Cu + Sn) etc.
Hg when mix with other metals from semisolid amalgam except
Fe, Co, Ni, Pt.
Interstitial compound
When less reactive nonmetals of small atomic size eg. H, B, N, C,
trapped in the interstitial space of transition metals, interstitial
compounds are formed, like :- TiC, Mn4N, Fe3H etc.
They are nonstoichiometric compounds.
They have high melting point than metals.
They are chemically inert.
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CATALYTIC PROPERTIES
Most of the d-block compounds act as catalyst due to their
variable oxidation state or complex formation tendency or
adsorption on their surface.
Example:
Contact process = V2O5
Haber process = Fe2O3 + Al2O3 + K2O
Fenton’s reagent = FeSO4 + H2O2
Decomposition of KClO3 = MnO2
Ostwald process = Pt/Rh
Zeigler Natta = TiCl4 + (C2H5)3 Al
Hydrogenation of Alkene = Ni/Pd
Wilkinson’s catalyst = RhCl + PPh3
Important reactions of d-block elements
(a) 𝐶𝑢2+ + 4𝐼 − → 𝐶𝑢2 𝐼2(𝑠) + 𝐼2
(b) 𝐶𝑢𝑆𝑂4 + 𝐾𝐶𝑁 → 𝐾2 𝑆𝑂4 + 𝐶𝑢(𝐶𝑁)2
Excess Unstable
2𝐶𝑢(𝐶𝑁)2 → 2𝐶𝑢𝐶𝑁 + (𝐶𝑁)2
Cyanogen
𝐶𝑢𝐶𝑁 + 3𝐾𝐶𝑁 → 𝐾3 [𝐶𝑢(𝐶𝑁)4 ]
𝐻2 𝑂+𝐶𝑂2
(c) 𝐶𝑢 → 𝐶𝑢𝐶𝑂3 . 𝐶𝑢(𝑂𝐻)2
most air green
Aqua regia
𝐴𝑢 → 𝐻[𝐴𝑢𝐶𝑙4 ] + 𝑁𝑂𝐶𝑙 + 𝐻2 𝑂
(3HCl+HNO3 )
Heating 1
(d) 𝐴𝑔𝑁𝑂3 (𝑠) → 𝐴𝑔 + 𝑁𝑂2 + 2 𝑂2
Heating 1
𝐴𝑔𝐶𝑂3 (𝑠) → 𝐴𝑔 + 𝐶𝑂2 + 2 𝑂2
100°C 720°C
(e) 𝐶𝑢𝑆𝑂4 . 5𝐻2 𝑂 → 𝐶𝑢𝑆𝑂4 . 𝐻2 𝑂 → 𝐶𝑢𝑆𝑂4
light greenish blue Colourless
230°C 1
→ 𝐶𝑢𝑂 + 𝑆𝑂2 + 2 𝑂2
𝑁𝐻2
(f) 𝐻𝑔2 𝐶𝑙2 + 𝑁𝐻4 𝑂𝐻 → 𝐻𝑔 + 𝐻𝑔
Black
𝐶𝑙

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 FeSO4 +H2 SO4
(g) 𝑁𝑂3− /𝑁𝑂2− → [𝐹𝑒(𝐻2 𝑂)5 𝑁𝑂+ ]𝑆𝑂4
Brown ring complex
(h) 𝐴𝑔𝐵𝑟 + 2𝑁𝑎2 𝑆2 𝑂3 → 𝑁𝑎3 [𝐴𝑔(𝑆2 𝑂3 )2 ] + 𝑁𝑎𝐵𝑟
Photographic complex
(i) Chemical volcano:
(𝑁𝐻4 )2 𝐶𝑟2 𝑂7 → 𝑁2 + 4𝐻2 𝑂 + 𝐶𝑟2 𝑂3

Compounds of d-Block Elements

1. Potassium Dichromate (K2Cr2O7)
Ore Ferrochrome or chromite (FeO∙Cr2O3) or (FeCr2O4)
Preparation:
4FeO∙Cr2O3 + 8Na2CO3 + 7O2 ⟶ 8Na2 CrO4 + 2Fe2O3 + 8CO2↑
Yellow

2Na2CrO4 + 2H+ ⟶ Na2 Cr2 O7 + 2Na+ + H2O

Orange

Na2Cr2O7 + 2KCl ⟶ K2Cr2O7 + 2NaCl

Sodium dichromate is more soluble than potassium dichromate.
Chromates and dichromates are interconvertible in aqueous
solution depending upon pH of the solutions.

Properties: Sodium & Potassium dichromates are strong

oxidising agents thus, acidified K2Cr2O7 will oxidise iodides to
iodine, sulphides to sulphur, tin (II) to thn (IV) and iron (II) salts
to iron (III).
Cr2O2−
7 + 14H + 6I ⟶ 2Cr + 7H2O + 3I2
+ − 3+

Cr2O2−
7 + 3H2S + 8H ⟶ 2Cr + 3S + 7H2O
+ 3+

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Cr2O2−
7 + 14H + 3Sn
+ 2+ ⟶ 3Sn4+ + 2Cr3+ + 7H O
2

Uses:
(A) K2Cr2O7 is used as an oxidising agent in volumetric analysis.
(B) It is used in mordant dyes, leather industry, photography (for
hardening of film).
(C) It is used in chromyl chloride test.
(D) It is used in cleaning glassware.
2. Potassium Permanganate (KMnO4)
Ore Pyrolusite (MnO2)
Preparation:
2MnO2 + 4KOH + O2 ⟶ 2K 2 MnO4 + 2H2O
Green
3MnO24 + 4H+ ⟶ 2MnO4 + MnO2 + 2H2O
Commercial preparation
Fused with KOH, oxidised
MnO2 → MnO24
with air or KNO3 Manganate ion
Electrolytic oxidation
MnO24 → MnO4
(alkaline medium) Permanganate ion
(purple)
Properties: KMnO4 acts as strong oxidising agent.
(A) In the presence of dilute H2SO4, KMnO4 is reduced to
manganous salt.
MnO4 + 8H+ + 5e ⟶ Mn2+ + 4H2O
Acidic KMnO4 solution oxidises oxalates to CO2, iron (II) to
iron (III), nitrites to nitrates and iodides to iodine. The half-
reactions of reductants are
5C2O2−4 ⟶ 10CO2 + 10e
5Fe2+ ⟶ 5Fe3+ + 5e
5NO2 + 5H2O ⟶ 5NO3 + 10H+ + 10e
10I ⟶ 5I2 + 10e
To acidify KMnO4, only H2SO4 is used and not HCl or HNO3
because HCl reacts with KMnO4 and produce Cl2 while HNO3,
itself acts as oxidising agent.
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(B) In alkaline medium, KMnO4 is reduced to insoluble MnO2.
MnO− 4 + 3e + 2H2O ⟶ MnO2 + 4OH
−

Alkaline or neutral KMnO4 solution oxidises I to IO3, S2O2− 3 to

2
SO4 , Mn to MnO2, etc.
2+

Aqueous KMnO4 reacts with NH3 to liberate N2 gas.

2KMnO4 + 2NH3 ⟶ 2KOH + 2MnO4 + N2 + 2H2O
Uses KMnO4 is used
(A) In laboratory preparation of Cl2.
(B) As an oxidising agent and disinfectant.
(C) In making Baeyer's reagent.
(D) 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.
Structures:

Inner-Transition (f-Block) Elements

The elements in which the filling of atomic orbitals by electrons
in valence shell take place in f-subshells, two levels inside the
outer subshell, are known as inner-transition elements. They are
also known as f-block elements.
Classification of f-block Elements
They have been classified into two series.
(A) 4f-series (first inner-transition series). The last electron
enters in 4f-orbital. The elements belonging to this series are
also known as lanthanoids.

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(B) 5f-series (second inner-transition series). The last electron
enters in 5f-orbital. The elements belonging to this series are
also known as actinoids.
Lanthanides
The fifteen elements from lanthanum (at number 57) to lutetium
(at. number 71) are known as lanthanoids or rare earths. Their
properties are as follows:
Electronic Configuration
The general electronic configuration of these elements is
[Xe]4f0-145d0-16s2. The lanthanum, electronic configuration
[Xe]4f05d16s2 and lutetium, electronic configuration
[Xe]4f 5d 6s , have no partially filled 4f-orbital in their ground
14 1 2

state, are considered as lanthanoids due to their properties close

to these elements.
Oxidation State
The most common and most stable oxidation state of lanthanides
is +3 but some elements also exhibit +2 and +4 oxidation states
in which they leave behind stable ions, e.g.,
Eu2+ = [Xe]4f7, Yb2+ = [Xe]4f14
Ce4+ = [Xe]4f0, Tb4+ = [Xe]4f7
An aqueous solution of Ce4+ is a good oxidising agent. The Eu 2+
and Yb2+ can exist in aqueous solution and are good reducing
agents. But there are exceptions also, e.g.,
Sm2+ = [Xe]4f6; Tm2+ = [Xe]4f13; Pr4+ = [Xe]4f1
Magnetic Properties
Magnetic properties have spin and orbit contributions. Hence,
magnetic moments are given by the formula,
μ = √4S(S + 1) + L(L + 1)
Where, L = orbital quantum number, S = spin quantum number
All lanthanoid ions with the exception of La3+, Lu3+ and Ce4+, are
paramagnetic in nature. For the first-row transition elements, the
electric fields of the ligands in its environment. Thus, as a first
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approximation the magnetic moment can be calculated using the
simple spin only formula.
μs = √n(n + 2)
Lanthanoid Contraction
Steady decrease in the atomic ionic (Ln3+) radii as the atomic
number of the lanthanoid elements increases is called lanthanoid
contraction. This is because the additional electron goes to 4f-
subshell. These 4f-orbitals being large and diffuse, have poor
shielding effect. The effective nuclear charge increases which
causes the contraction in the size of electron charge cloud. This
contraction in size in quite regular and is known as lanthanoid
contraction.
The f-f transitions are possible due to absorption of light from the
visible region.
Consequences of Lanthanoid Contraction
(A) Covalent character of cations increases.
(B) The electronegativity of trivalent ions increases slightly.
(C) There is decrease in basic strength of oxides and hydroxides
from La to Lu.
(D) There is small increase in standard electrode potential
values.
(E) Sizes of Zr and Hf; Nb and Ta are similar, so they are called
chemical twins.
Colour
The species containing unpaired electrons are coloured and so on
in the case of lanthanoid ions.
Melting and Boiling Points
Lanthanoids have high melting and boiling points but there is no
regular trend.
Density
Lanthanoids have densities varying from 6.67 to 9.7 g cm -3, but
there is no regular trend for these values.
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Electronegativity
For lanthanoids, the electronegativity values are almost same as
that of s-block elements. Lanthanoids form ionic compounds.
Ionisation Energies
The ionisation energy values of lanthanoids are not very high due
to their large size and comparable with those of alkaline earth
metals.
Complex compound
Due to their large ionic size, they have little tendency to form
complexes.
Chemical Reactivity
Due to their low values of ionisation energies, the lanthanoids are
very reactive.
Ln2O3 H2

heated with S with halogens

Ln2S3 ← Ln → LnX3
2773 K
with C

LnN Ln(OH)3 + H2
LnC2
Chemical Reactions of Lanthanoids
Alloys
They form alloy especially with iron e.g., misch metal which
consists of a lanthanoids metal 76 ~ 95%, iron ~ 5% and S, C,
Ca and Al in traces. Mg mixed with 3% misch metal is used for
making jet engine parts.

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Actinoids
The fourteen elements from actinium (at number 89) onwards to
lawrencium (at number 103) are known as actinoids and
constitute the 5f-series. From neptunium to onwards, the
elements are man-made (artificially prepared) and also known as
transuranic elements.
Electronic Configuration
The last electron in such elements enters in the 5f atomic orbital.
Their general electronic configuration is
[Rn]5f0-146d0-77s2
There is not much difference between the energies of 5f and 6d,
so it is difficult to predict whether the electron has entered in 5f
or 6d.
Oxidation State
The common oxidation state is +3 but other oxidation states are
also exhibited by actinoids upto the maximum being +7.
Magnetic Properties
The magnetic moments of actinoid ions are smaller than
theoretical values. It is hard to interpret due to large spin orbit
coupling.
Actinoid Contraction
It is similar to lanthanide contraction due to poor shielding of 5f-
electrons. It is greater than lanthanoid contraction.
Melting and Boiling Points
They have high values for melting and boiling points but there is
no regular trend.
Density
The value of density varies from 7.0 g cm-3 to 20 g cm-3. Again,
there is no regular trend in density.
Reducing Character
They are strong reducing agents as they have high E° values
approximately 2.0 V.
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Reactivity
Actinoids are very reactive in nature and combine with oxygen
and halogens like lanthanoids.
Coloured Ions
Actinoid ions are coloured due to the presence of unpaired
electrons and f-f transitions.
Complex Formation
They have higher tendency to form complex compounds.

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