A Comprehensive Guide to d-Block

Elements
Transition Elements: Properties, Reactions, and Importance

1. Introduction and Electronic Configuration

The d-block elements occupy the large middle section of the periodic table, specifically groups 3 to
12. These elements are characterized by the filling of inner d-orbitals. They are broadly called
'Transition Elements' because they represent a transition from the electropositive s-block elements to
the electronegative p-block elements.

General Electronic Configuration:

(n-1)d1-10 ns1-2

Key Exceptions:
In the 3d series, Chromium and Copper show anomalous configurations due to the extra stability of
half-filled and fully-filled d-orbitals.

• Chromium (Cr, Z=24): [Ar] 3d5 4s1 (instead of 3d4 4s2)

• Copper (Cu, Z=29): [Ar] 3d10 4s1 (instead of 3d9 4s2)
Elements like Zn, Cd, and Hg are technically not transition elements because they have completely
filled d-orbitals in their ground state as well as in their common oxidation states.
2. General Physical Properties
Transition elements are typical metals. They exhibit high tensile strength, ductility, malleability, high
thermal and electrical conductivity, and metallic luster.

Metallic Character and Bonding:

With the exception of mercury (a liquid), all transition elements have typical metallic structures. The
presence of unpaired d-electrons allows them to form strong metallic bonds and even covalent bonds
through d-orbital overlap. This results in higher hardness and lower volatility compared to s-block
elements.

Melting and Boiling Points:

Transition metals have high melting and boiling points. This is attributed to the involvement of (n-1)d
and ns electrons in metallic bonding. The MP increases toward the middle of each series (maximum
at Cr, Mo, W) and then decreases as pairing of electrons starts.

Enthalpy of Atomization:
They have very high enthalpies of atomization. The maxima occurring at about the middle of each
series indicates that more unpaired electrons result in stronger interatomic bonding.
3. Variation in Atomic and Ionic Radii
General Trend:

In a given series, the atomic radii decrease from Group 3 to the middle of the series. This is due to
the increase in nuclear charge, which is not effectively shielded by the electrons entering the
d-orbitals. Toward the end of the series, however, the radii increase slightly due to electron-electron
repulsion among the d-electrons.

Lanthanide Contraction:
This is a crucial concept for JEE. The radii of the metals of the third (5d) series are virtually the same
as those of the corresponding metals of the second (4d) series. For example, Zr (160 pm) and Hf
(159 pm) have nearly identical sizes.

Reason: The intervention of the 4f-orbitals (before the 5d-series) results in poor shielding, leading to
a massive increase in effective nuclear charge that 'pulls' the outer electrons inward.

Density:
Due to the combined effect of decreasing radii and increasing atomic mass, the density increases
significantly along a series from left to right.
4. Ionization Enthalpy and Oxidation States
Ionization Enthalpy (IE):
IE increases across each series. However, the increase is less abrupt than in s-block elements
because the d-electrons provide some shielding to the outer 4s-electrons. The relative stability of
various oxidation states can be predicted from the Sum of IEs.

Oxidation States:
One of the most striking features of d-block elements is the variety of oxidation states they exhibit.
This is because both (n-1)d and ns electrons have very similar energy levels.

• Sc: Only +3

• Mn: Shows the widest range (+2 to +7)

• Fe: Most common +2 and +3

• Noble metals (Pt, Au): Can exist in high oxidation states in complexes.

In p-block, heavier elements favor lower oxidation states (inert pair effect). In d-block, heavier
elements (4d/5d) often favor higher oxidation states compared to 3d (e.g., W(VI) is more stable than
Cr(VI)).
5. Magnetic Properties and Colour Formation
Magnetic Properties:
Most transition metal ions are paramagnetic because they contain unpaired electrons.
Paramagnetism is measured by the magnetic moment (µ).

µ = √(n(n+2)) Bohr Magnetons (BM)

where 'n' is the number of unpaired electrons. For instance, Mn2+ (3d5) has 5 unpaired electrons,
making it highly paramagnetic.

Formation of Coloured Ions:

Transition metal ions are often coloured in their solid or solution form. This color arises from d-d
transitions.

When light falls on the ion, electrons from lower energy d-orbitals are excited to higher energy
d-orbitals. The energy absorbed corresponds to a specific wavelength in the visible region, and we
see the complementary color.

Note: Sc3+ (3d0) and Zn2+ (3d10) are colourless because no d-d transitions are possible.
6. Complexes, Interstitial Compounds, and Catalysis
Formation of Complex Compounds:
Transition metals form a vast number of complex compounds. This is due to:

1. Small size and high ionic charge.

2. Availability of vacant d-orbitals to accept electron pairs from ligands.

Catalytic Properties:
Many transition metals and their compounds are used as catalysts in industrial processes. This is
because they can adopt multiple oxidation states and provide a large surface area for reactants.

• V2O5 in Contact Process (H2SO4 prep).

• Finely divided Fe in Haber's Process (NH3 prep).

• Ni in hydrogenation of Oils.

Interstitial Compounds:
Transition metals trap small atoms like H, C, or N in their crystal lattices. These compounds are
non-stoichiometric (e.g., TiC, Mn4N, VH0.56). They are very hard and have high melting points.
7. Potassium Dichromate (K2Cr2O7)
Preparation from Chromite Ore:
1. 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
2. 2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O
3. Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

Properties:
Cr2O72- is a powerful oxidizing agent in acidic medium.

Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O

pH Dependency:
Chromate and dichromate are interconvertible depending on pH:

2CrO42- + 2H+ ■ Cr2O72- + H2O

(Yellow in Alkali → Orange in Acid)
8. Potassium Permanganate (KMnO4)
Preparation from Pyrolusite (MnO2):
1. 2MnO2 + 4KOH + O2 → 2K2MnO4 (Green) + 2H2O
2. 3MnO42- + 4H+ → 2MnO4- (Purple) + MnO2 + 2H2O

Oxidizing Properties:
Acidic Medium: MnO4- + 8H+ + 5e- → Mn2+ + 4H2O
Neutral/Faintly Alkaline: MnO4- + 2H2O + 3e- → MnO2 + 4OH-

Structures:
Both chromate and permanganate ions are tetrahedral. Permanganate is purple due to Charge
Transfer (L to M), not d-d transition, as Mn is in +7 state (d0).
9. Importance of Specific d-Block Elements
Iron (Fe):
The most important structural metal. Primary constituent of steel. Biologically, it is central to
Hemoglobin and Myoglobin for oxygen transport.

Copper (Cu):
Used widely in electrical wires due to high conductivity. Also forms important alloys like Brass
(Cu+Zn) and Bronze (Cu+Sn).

Zinc (Zn):
Used in galvanization to prevent rusting of iron. Components of many batteries (Dry cell). Biologically
present in Carbonic Anhydrase enzyme.

Silver (Ag) & Gold (Au):

Coinage metals. High value, used in jewelry and high-end electronics. Silver halides are used in
traditional photography.

Platinum (Pt) & Palladium (Pd):

Excellent catalysts for hydrogenation and used in catalytic converters in automobiles to reduce
emissions.
10. Industrial and Biological Overview
Industrial Processes:
• Titanium dioxide (TiO2) is a major pigment in paints.

• MnO2 is used in dry cell batteries.

• Cr and Ni are used for electroplating to provide a decorative and protective finish.

Biological Significance:
1. Manganese: Involved in photosynthesis (water splitting).

2. Cobalt: Essential part of Vitamin B12 (cyanocobalamin).

3. Molybdenum: Part of nitrogenase enzyme in nitrogen-fixing bacteria.

4. Iron: Heme group in blood.

Summary for JEE Aspirants:

Focus heavily on oxidation states, magnetic moment calculations, and the preparation/titration of
KMnO4 and K2Cr2O7. Lanthanide contraction is a recurring theme in reasoning questions.

End of Notes.