Chemistry

Concise Lecture Notes

P-block Elements

Key topics covered in the Class:

• Type of elements, Electronic configuration, Atomic radius
• Ionisation Energy, Electron affinity, Electronegativity
• Inert pair effect, First atom of the group, Catenation and allotropes
• Structure of oxy acids and oxides
• Back bonding, Bridge Bonding, and physical property trends

Metal , Non-metal , Metalloid , Radioactive element

• Metalloids: Boron, Silicon, Germanium, Arsenic, Antimony, Tellurium, and Polonium mark the
boundary between metals and non-metals.
• Trend: Metallic character increases down the group; Non-metallic character decreases.
• Liquid Expansion: Gallium (Ga), Germanium (Ge), and Bismuth (Bi) expand when freezing from
liquid to solid (similar to water).

Electronic Configuration
• General configuration: 𝑛𝑠 2 𝑛𝑝1−6 .
• Elements are arranged by groups (Group 13 to 18) with filling of p-orbitals.

Atomic Radius
• General Trend: Radius increases down the group as shells are added.
• Exception (Group 13): Gallium (Ga) is smaller than Aluminium (Al) due to poor shielding by d-
electrons.
• Ionic Radii Order: 𝐵 3+ < 𝐴𝑙 3+ < 𝐺𝑎3+ < 𝐼𝑛3+ < 𝑇𝑙 3+ .

Ionisation Energy
• Definition: Energy required to remove an electron. High for Noble gases (He is highest).
• Group 13 Irregularity: 𝐵 > 𝑇𝑙 > 𝐺𝑎 > 𝐴𝑙 > 𝐼𝑛 (Due to lanthanoid and transition contraction).
• Trend: Generally decreases down a group, but Lead (Pb) > Tin (Sn) and Thallium (Tl) >
Indium (In) due to poor shielding.
Electron Affinity
• General Rule: Noble gases have positive electron gain enthalpy (endothermic).
• Halogens: Chlorine (𝐶𝑙) has the most negative (exothermic) electron gain enthalpy, not Fluorine
(due to repulsion in small F atom).
• Order: 𝐶𝑙 > 𝐹 > 𝐵𝑟 > 𝐼.

Electronegativity
• Decreases down the group as atomic size increases.
• Values: F (4.0) is the most electronegative element; Boron (2.0), Aluminium (1.5).

Inert Pair Effect

• Definition: Reluctance of s-electrons (𝑛𝑠 2 ) to participate in bonding due to poor shielding of d
and f electrons.
• Consequence: Stability of lower oxidation states increases down the group (e.g., 𝑇𝑙 +1 is more
stable than 𝑇𝑙 +3).
• Applications: 𝑃𝑏 +4 is a strong oxidizing agent; 𝑆𝑛+2 is a reducing agent.

Stability of oxidation state

• Group 13: +1 stability increases down the group (𝑇𝑙 +1 is most stable).
• Group 14: +2 stability increases down the group (𝑃𝑏 +2 is stable, 𝑃𝑏 +4 is oxidizing).
• Reaction Examples: 𝑃𝑏𝑂2 and 𝑃𝑏𝐶𝑙4 are unstable and act as oxidizers; 𝑆𝑛𝐶𝑙2 acts as a
reducing agent.

2. Identification of oxidising agent and reducing agent

• Compounds with elements in their highest unstable oxidation state (like 𝑃𝑏 +4) act as
Oxidizing Agents (e.g., 𝑃𝑏𝑂2).
• Compounds in lower unstable oxidation states (like 𝑆𝑛+2 ) act as Reducing Agents.

3. Existence and Non- Existence

• Non-Existence: 𝑃𝑏𝐼4 does not exist because 𝑃𝑏 +4 oxidizes 𝐼 − to 𝐼2 .
• Existence: 𝐵𝑖𝐹5 exists because Fluorine is a very strong oxidizing agent capable of
stabilizing Bi(+5).
• Note: 𝑇𝑙𝐼3 is actually 𝑇𝑙 + [𝐼3 ]− .

4. Thermal / Chemical Stability

• Group 14 Halides: Tetrachlorides (𝑀𝐶𝑙4 ) stability decreases down the group (𝑃𝑏𝐶𝑙4
is least stable).
• Dihalides: 𝑀𝐶𝑙2 stability increases down the group (𝑃𝑏𝐶𝑙2 is stable).

First Atom of Group

• Anomalous Behavior: First elements (B, C, N, O, F) differ due to small size, high
electronegativity, and absence of d-orbitals.
• Maximum Covalency: Restricted to 4 (𝑠𝑝3 ) because d-orbitals are unavailable (e.g., [𝐵𝐹6 ]3−
cannot form, but [𝐴𝑙𝐹6 ]3− can).
• Multiple Bonds: Readily form 𝑝𝜋 − 𝑝𝜋 bonds (e.g., 𝐶 = 𝐶, 𝑁 ≡ 𝑁).

Bond Energy
• Single Bond Strength: 𝐶 − 𝐶 > 𝑆𝑖 − 𝑆𝑖; but 𝑁 − 𝑁 < 𝑃 − 𝑃 and 𝑂 − 𝑂 < 𝑆 − 𝑆 due to lone
pair repulsion in small atoms.
• Halogens: Bond energy order is 𝐶𝑙2 > 𝐵𝑟2 > 𝐹2 > 𝐼2 (Fluorine is exceptionally weak due to
repulsion).
Catenation Property
• Definition: Self-linking property of an element to form chains/rings.
• Order: 𝐶 ≫ 𝑆𝑖 > 𝐺𝑒 ≈ 𝑆𝑛. Lead (Pb) does not show catenation.
• Reason: High C-C bond strength facilitates long chains.

Allotropes
• Different physical forms of the same element.
• Carbon: Diamond, Graphite, Fullerenes.
• Phosphorus: White, Red, Black.
• Sulphur: Rhombic, Monoclinic.

Allotropes of carbon
• Diamond: 𝑠𝑝3 hybridized, covalent network solid, hardest natural substance, insulator.
Graphite
• Structure: 𝑠𝑝2 hybridized, planar hexagonal layers held by Van der Waals forces.
• Properties: Soft/slippery (dry lubricant), conductor (free 𝜋 electrons), thermodynamically most
stable allotrope (Δ𝐻𝑓 = 0).

Conductivity
• Graphite: Good electrical conductor along sheets; thermal conductor > diamond.
• Diamond: Electrical insulator; high thermal conductivity.

Fullerenes
• Example: Buckminsterfullerene (𝐶60 ).
• Structure: Cage-like (soccer ball), contains 12 pentagons and 20 hexagons.
• Hybridization: 𝑠𝑝2 . Purest form of carbon (no dangling bonds).

Allotropes of Phosphorus
• White P: Discrete 𝑃4 tetrahedra, highly strained (60° angles), very reactive, glows in dark
(chemiluminescence), poisonous.
• Red P: Polymeric chain of 𝑃4 units, stable, non-poisonous.
• Black P: Thermodynamic most stable form, layered structure.
Allotropes of Sulphur
• Forms: Rhombic (𝛼-S) and Monoclinic (𝛽-S). Both consist of 𝑆8 puckered rings (crown
shape).
• Stability: Rhombic is stable at room temperature; Monoclinic is stable above 369 K.
• Paramagnetism: In vapor phase (𝑆2 ), sulphur is paramagnetic like 𝑂2.

Physical Properties (data based)

• Boiling Point: Generally increases down the group.
• Exception: 𝑁𝐻3 , 𝐻2 𝑂, and 𝐻𝐹 have unexpectedly high boiling points due to Hydrogen Bonding.
• Density: Generally increases from top to bottom.

Compounds of Boron
• Properties: Extremely hard, black solid, high melting point due to strong lattice.
• Isotopes: 10
𝐵 (high neutron absorption, used in nuclear shields) and 11
𝐵.

Oxo-acids
• Nomenclature: * ic acid: Standard state (e.g., 𝐻3 𝑃𝑂4 ). * ous acid: One Oxygen less (e.g.,
𝐻3 𝑃𝑂3). * hypo-ous acid: Two Oxygens less. * per-ic acid: One Oxygen more.
 Oxo-acids
Group-13 Group-14 Group-15 Group-16 Group-17 Group-18

H3BO3 H2CO3 HNO3 H3PO4 H2SO4 HClO4 H4XeO6

HClO3 H4XeO4
H4SiO4 HNO2 H3PO3 H2SO3

HClO2
H2N2O2 H3PO2
HClO
Acids of Nitrogen

Hyponitrous acid

+ [O] – [O]
Nitrous acid
Nitric acid
Peroxy nitric acid

Nitric Anhydride
Acids of Nitrogen
• Forms: 𝐻𝑁𝑂3 (Nitric), 𝐻𝑁𝑂2 (Nitrous), 𝐻2 𝑁2 𝑂2 (Hyponitrous).
• Anhydrides: 𝑁2 𝑂5 for Nitric acid; 𝑁2 𝑂3 for Nitrous acid.

Oxo-acids of Sulphur
• Key Acids: 𝐻2 𝑆𝑂4 (Sulphuric), 𝐻2 𝑆𝑂3 (Sulphurous).
• Peroxy Acids: 𝐻2 𝑆𝑂5 (Caro's acid) and 𝐻2 𝑆2 𝑂8 (Marshall's acid) contain peroxide linkage (-O-
O-).
• Pyro Acids: 𝐻2 𝑆2 𝑂7 (Oleum) contains S-O-S linkage.

Oxo-acids of P
• Basicity: Determined by the number of P-OH groups.
• Reducing Character: Determined by the presence of P-H bonds (e.g., 𝐻3 𝑃𝑂2 is monobasic and
strong reducing agent).
• Structure: All have at least one P=O unit.
Meta Acids : Polymeric in nature / Cyclic structure
• Formed by removing water from "ortho" acids.
• Example: (𝐻𝑃𝑂3 )3 is cyclic trimetaphosphoric acid.

Polythionic Acids
• General formula 𝐻2 𝑆𝑛 𝑂6 (where n = 2, 3, 4...).
• Contain S-S bonds. Oxidation state of terminal Sulfurs is +5, middle Sulfurs is 0.

Nature of Oxides
• Acidic: Non-metal oxides (e.g., 𝐵2 𝑂3, 𝐶𝑂2, 𝑆𝑖𝑂2 , 𝑁2 𝑂5).
• Basic: Metal oxides (𝑇𝑙2 𝑂3 , 𝐵𝑖2 𝑂3).
• Amphoteric: 𝐴𝑙2 𝑂3, 𝐺𝑎2 𝑂3 , 𝑆𝑛𝑂, 𝑃𝑏𝑂, 𝐴𝑠2 𝑂3 .
• Neutral: 𝐶𝑂, 𝑁𝑂, 𝑁2 𝑂.

Order Of Boiling Point

• Hydrides: Boiling point increases with molecular mass (Van der Waals forces).
• Exception: 𝐻2 𝑂 ≫ 𝐻2 𝑇𝑒. .., 𝐻𝐹 > 𝐻𝐼. .., 𝑁𝐻3 > 𝐴𝑠𝐻3 . .. due to H-bonding.
• Graph: Sudden spike for period 2 hydrides (N, O, F).
Hydrogen Containing Compounds
• Thermal Stability: Decreases down the group as bond length increases (𝐻 − 𝐹 > 𝐻 − 𝐼).
• Acidic Strength: Increases down the group (𝐻𝐹 < 𝐻𝐶𝑙 < 𝐻𝐵𝑟 < 𝐻𝐼) because weaker bonds
break easily.
• Reducing Power: Increases down the group (𝐻2 𝑇𝑒 is strongest reducing agent in group 16).

Back Bonding
• Definition: Coordinate 𝜋-bond formed when one atom has a lone pair and the other has an
empty orbital.
• Conditions: Best overlap when atoms are small (2nd period).
• Example: 𝐵𝐹3 . F donates lone pair to empty p-orbital of B. This shortens the B-F bond and
decreases Lewis acidity.

Inorganic Benzene (Aromatic) / CO Molecule

• Borazine (𝐵3 𝑁3 𝐻6 ): Known as "Inorganic Benzene". It is isoelectronic with benzene and
aromatic.
• Trisilylamine: (𝑆𝑖𝐻3 )3 𝑁 is planar due to back bonding (N lone pair → Si empty d-orbital),
making it a weak base compared to trimethylamine.
Lewis acidic character
• Boron Halides: Order is 𝐵𝐹3 < 𝐵𝐶𝑙3 < 𝐵𝐵𝑟3 < 𝐵𝐼3.
• Reason: Back bonding is strongest in 𝐵𝐹3 (2p-2p overlap), satisfying Boron's electron
deficiency. 𝐵𝐼3 has poor overlap (5p-2p), so Boron remains "hungry" for electrons.

Bridge Bonding
• Diborane (𝐵2 𝐻6): Contains two "banana bonds" (3-center-2-electron bonds). Hydrogen acts as a
bridge.
• 𝐴𝑙2 𝐶𝑙6 : Dimer where Chlorine lone pairs form coordinate bonds with Aluminium.

Table for Oxidising Power

• Strength Order: 𝐹2 > 𝑂3 > 𝑆2 𝑂82− > 𝐾𝑀𝑛𝑂4 > 𝐶𝑟2 𝑂72− > 𝐶𝑙2 .
• Fluorine is the strongest oxidizing agent.
• Reaction Logic: A stronger oxidizer displaces a weaker one (e.g., 𝐹2 can displace 𝐶𝑙 − ).