Unit 1: CH01 Syllabus Node

Periodicity & Trends Across Period 3

Period 3 element trends from Na to Ar: nuclear charge vs shielding, atomic radius contraction, and structural melting point variations.

1. Classification into Blocks

The Periodic Table is arranged in order of increasing atomic number. Elements are classified into blocks according to the subshell containing the highest energy valence electron:

  • s-block elements: Groups 1 and 2 (valence electrons in \(s\) orbital).
  • p-block elements: Groups 13 to 18 (valence electrons in \(p\) orbitals).
  • d-block elements: Transition elements between Groups 2 and 13.
  • f-block elements: Lanthanoids and actinoids.

3. Melting Point Variations Across Period 3

Melting point reflects the type of bonding and crystal structure possessed by the element:

Melting Point Variations Across Period 3 Elements Period 3 Elements Melting Point (K) 0 500 1000 1500 Na Mg Al Si (Peak) P4 S8 Cl2 Ar Metallic (Na, Mg, Al) Simple Molecular (S8 > P4 > Cl2)

Metallic Elements (Na, Mg, Al)

Melting point increases from Na to Al. Why?

  • Ionic charge increases: \(\text{Na}^+ < \text{Mg}^{2+} < \text{Al}^{3+}\).
  • Number of delocalised valence electrons contributed per atom increases from 1 to 3.
  • Cation radius decreases, bringing delocalised electrons closer to the nucleus.
  • Electrostatic attraction between cations and electrons strengthens.

Macromolecular Silicon (Si)

Silicon has the highest melting point in Period 3 (\(1687\text{ K}\)). Silicon forms a giant macromolecular covalent crystal lattice similar to diamond. Melting silicon requires breaking thousands of strong covalent bonds throughout the 3D network, which requires enormous thermal energy.

Simple Molecular Non-Metals (\(\text{P}_4, \text{S}_8, \text{Cl}_2\)) and Argon

These elements exist as discrete molecules or single atoms held together only by weak London dispersion forces:

  • Sulfur (\(\text{S}_8\)): Contains 8 atoms per molecule (128 electrons). Its large electron cloud produces strong London dispersion forces, giving it a higher melting point than phosphorus.
  • Phosphorus (\(\text{P}_4\)): Contains 4 atoms per molecule (60 electrons), with weaker London dispersion forces than \(\text{S}_8\).
  • Chlorine (\(\text{Cl}_2\)): Diatomic molecule (34 electrons), boiling as a gas at room temperature.
  • Argon (\(\text{Ar}\)): Exists as monatomic atoms (18 electrons) with the weakest London dispersion forces, exhibiting the lowest melting point in Period 3.

4. Period 3 Properties Matrix

Element Symbol Structure Bonding Melting Point (K) Electrical Conductivity
SodiumNaGiant metallicMetallic371Good (1 delocalised e-)
MagnesiumMgGiant metallicMetallic923Good (2 delocalised e-)
AluminiumAlGiant metallicMetallic933Good (3 delocalised e-)
SiliconSiGiant covalentCovalent1687Semiconductor
PhosphorusP4Simple molecularCovalent (London forces)317None
SulfurS8Simple molecularCovalent (London forces)392None
ChlorineCl2Simple molecularCovalent (London forces)172None
ArgonArMonatomicLondon forces only84None

5. Practice Questions

Practice Problem (3 Marks)
Explain why sulfur has a higher melting point than phosphorus.

Mark Scheme:

  • Sulfur exists as \(\text{S}_8\) molecules whereas phosphorus exists as \(\text{P}_4\) molecules. (1 mark)
  • \(\text{S}_8\) molecules are larger and possess more electrons than \(\text{P}_4\) molecules (128 electrons vs 60 electrons). (1 mark)
  • Therefore, London dispersion forces between \(\text{S}_8\) molecules are stronger and require more thermal energy to overcome. (1 mark)