The Role of d-Electrons in Transition Metals and Trends in the d-Block
What Makes Metallic Bonding Unique?
- In metals, valence electrons don’t belong to individual atoms.
- Instead, they form a shared "sea of delocalized electrons" that move freely throughout the metallic lattice.
- These electrons interact with positively charged cations, generating strong electrostatic forces known as metallic bonds.
Metallic bonding
Metallic bonding is a type of chemical bonding that arises from the electrostatic attractive force between conduction electrons (in the form of an electron cloud of delocalized electrons) and positively charged metal ions.
- For most metals, these delocalized electrons originate from the s-orbital of the outermost energy level.
- However, in transition metals, electrons from partially filled d-orbitals also contribute to this electron sea.
- This additional electron density significantly strengthens metallic bonds, setting transition metals apart.
The Impact of d-Electrons on Properties
The delocalized d-electrons in transition metals give rise to several key properties:
Higher Melting Points
- The strength of metallic bonds depends on the density of delocalized electrons and their attraction to the metal cations.
- Transition metals, with their additional d-electrons, form stronger metallic bonds than metals like sodium or magnesium.
- This explains their generally higher melting points.
- Sodium (Na): Melting point = 98°C
- Iron (Fe): Melting point = 1538°C
- When comparing melting points, consider both the number of delocalized electrons and the size of the metal cation.
- Smaller cations with higher electron density form stronger metallic bonds.
High Electrical Conductivity
- The mobility of delocalized electrons makes metals excellent conductors of electricity.
- In transition metals, the greater number of delocalized electrons (from both s- and d-orbitals) enhances this conductivity.
- When a potential difference is applied, these electrons move freely, allowing electric current to flow.
Consider copper (Cu), a transition metal widely used in electrical wiring. Its exceptional conductivity arises from the large number of delocalized electrons, which move easily under an electric field.
Trends in the d-Block
The d-block elements (transition metals) exhibit fascinating trends in their physical properties, but these trends are often more complex than those observed in the s- or p-block elements.
Melting Point Trends Across the d-Block
- You might expect melting points to increase steadily across a period in the d-block as more delocalized electrons strengthen metallic bonds.
- However, this trend is not always straightforward.
- Addition of d-Electrons:
- As we move across a period in the d-block, more d-electrons become delocalized.
- This should strengthen metallic bonds and increase melting points.
- Electron-Electron Repulsion:
- However, adding d-electrons also increases electron-electron repulsion within the d-orbitals.
- This repulsion can partially offset bonding strength, leading to irregularities in the melting point trend.
- Chromium (Cr) and molybdenum (Mo):
- These elements have exceptionally high melting points due to half-filled d-orbitals, which maximize bonding efficiency.
- Zinc (Zn):
- In contrast, zinc has a relatively low melting point for a transition metal because its d-orbitals are completely filled.
- This reduces the number of delocalized electrons available for bonding.
- It’s a common misconception that melting points always increase across a period.
- Remember that irregularities arise due to competing factors, such as electron-electron repulsion.
Comparison with Group 1 and Group 2 Metals
To appreciate the unique properties of transition metals, let’s compare them to group 1 and group 2 metals:
- Group 1 Metals (e.g., Sodium): These metals have only one delocalized s-electron per atom, resulting in weaker metallic bonds and lower melting points.
- Group 2 Metals (e.g., Magnesium): These metals have two delocalized s-electrons, leading to stronger bonds and higher melting points than group 1 metals.
- Transition Metals (e.g., Iron): The combination of s- and d-electrons results in even stronger metallic bonds, giving rise to higher melting points and greater hardness.
- The strength of metallic bonding depends on three factors: ionic charge, ionic radius, and the number of delocalized electrons.
- Transition metals excel in all three, making their bonds particularly strong.
Key Relationship: Bond Strength and Metallic Properties
The strength of metallic bonds and the resulting properties of metals can be summarized using the following relationship:
$$\text{Bond Strength} \propto \frac{\text{Charge of Cation}}{\text{Radius of Cation}}$$
- Higher Charge: Increases the electrostatic attraction between cations and delocalized electrons.
- Smaller Radius: Reduces the distance between cations and electrons, strengthening the bond.
- How do delocalized d-electrons contribute to the high melting points and electrical conductivity of transition metals?
- Can you explain why the melting point trend across the d-block is less evident than in other blocks?


