1.

GROUP 15 ELEMENTS: NITROGEN FAMILY

1.1 General Characteristics & Trends

Valence Configuration: ns²np³

Atomic & Ionic Radii: Increase down the group

Ionisation Enthalpy: Decreases down the group

Electronegativity: Decreases down the group

Metallic Character: Increases (N, P - non-metals; As, Sb - metalloids; Bi - metal)

1.2 Oxidation States & Stability

Common OS: -3, +3, +5

Key Trend: Stability of +5 decreases down the group; Stability of +3 increases (Inert Pair
Effect)

Nitrogen: Exhibits +1, +2, +4, +5

Bismuth: Only well-characterized +5 compound is BiF₅ (strong oxidizing agent)

1.3 Anomalous Behaviour of Nitrogen

Small size, high electronegativity, high ionisation energy

Forms pπ-pπ multiple bonds (N≡N, C≡N)

Maximum covalency = 4 (no d-orbitals)

Weak catenation (N-N single bond weak)

Exists as diatomic gas (N₂); others are solids

1.4 Chemical Properties Overview

HYDRIDE (EH₃) STABILITY: NH₃ > PH₃ > AsH₃ > SbH₃ > BiH₃

HYDRIDE REDUCING NATURE: NH₃ < PH₃ < AsH₃ < SbH₃ < BiH₃

HYDRIDE BASICITY: NH₃ > PH₃ > AsH₃ > SbH₃ ≈ BiH₃

OXIDE ACIDITY (E₂O₃/E₂O₅): Acidic → Amphoteric → Basic

TRIHALIDE COVALENT CHARACTER: NF₃ (covalent); BiF₃ (ionic)

PENTAHALIDE FORMATION: N - none; P, As, Sb, Bi - form EX₅

1.5 Important Compounds & Reactions

A. Ammonia (NH₃)

Preparation (Haber's Process):

N₂(g) + 3H₂(g) ⇌ 2NH₃(g); ΔH = -46.1 kJ/mol
Conditions: High pressure (~200 atm), ~700 K, Fe₂O₃ + K₂O + Al₂O₃ catalyst

Properties:

Lewis base (lone pair donation)

Forms complexes: [Cu(NH₃)₄]²⁺ (deep blue), [Ag(NH₃)₂]⁺

Higher boiling point than PH₃ due to H-bonding

B. Oxides of Nitrogen

OXIDE: Nitrous Oxide

FORMULA: N₂O
OXIDATION STATE: +1
IMPORTANT FEATURE: Neutral, laughing gas

OXIDE: Nitric Oxide

FORMULA: NO
OXIDATION STATE: +2
IMPORTANT FEATURE: Paramagnetic, odd electron

OXIDE: Nitrogen Dioxide

FORMULA: NO₂
OXIDATION STATE: +4
IMPORTANT FEATURE: Brown gas, dimerizes to N₂O₄

OXIDE: Dinitrogen Pentoxide

FORMULA: N₂O₅
OXIDATION STATE: +5
IMPORTANT FEATURE: Solid, anhydride of HNO₃

C. Nitric Acid (HNO₃)

Strong Oxidizing Agent:

Cu + 4HNO₃(conc.) → Cu(NO₃)₂ + 2NO₂ + 2H₂O

3Cu + 8HNO₃(dil.) → 3Cu(NO₃)₂ + 2NO + 4H₂O

Passivation: Al, Cr, Fe become passive in conc. HNO₃

Brown Ring Test: For NO₃⁻ ions; brown complex [Fe(H₂O)₅NO]²⁺

D. Phosphorus Allotropes

White P: P₄ tetrahedral, waxy, toxic, chemiluminescent, soluble in CS₂

Red P: Polymeric, non-poisonous, insoluble in CS₂, used in matchsticks

Black P: Least reactive, conducts electricity

E. Phosphine (PH₃)

Preparation:
Ca₃P₂ + 6H₂O → 3Ca(OH)₂ + 2PH₃
P₄ + 3NaOH + 3H₂O → PH₃ + 3NaH₂PO₂

Properties: Poisonous, weak base, forms PH₄I

F. Phosphorus Halides

PCl₃: PCl₃ + 3H₂O → H₃PO₃ + 3HCl

PCl₅:

Structure: Trigonal bipyramidal (axial bonds longer)

Hydrolysis: PCl₅ + H₂O → POCl₃ + 2HCl → POCl₃ + 3H₂O → H₃PO₄ + 3HCl

Dissociation: PCl₅ ⇌ PCl₃ + Cl₂

G. Oxoacids of Phosphorus

ACID: Hypophosphorous
FORMULA: H₃PO₂
BASICITY: 1 (Monobasic)
OXIDATION STATE: +1
KEY FEATURE: Strong reducing agent (2 P-H bonds)

ACID: Phosphorous
FORMULA: H₃PO₃
BASICITY: 2 (Dibasic)
OXIDATION STATE: +3
KEY FEATURE: -

ACID: Orthophosphoric
FORMULA: H₃PO₄
BASICITY: 3 (Tribasic)
OXIDATION STATE: +5
KEY FEATURE: No reducing property

Disproportionation: 4H₃PO₃ → 3H₃PO₄ + PH₃

2. GROUP 16 ELEMENTS: OXYGEN FAMILY

2.1 General Characteristics & Trends

Valence Configuration: ns²np⁴

Atomic Radius: Increases down the group

Ionisation Energy, Electronegativity: Decrease down the group

Metallic Character: Increases (O, S - non-metals; Se, Te - metalloids; Po - metal)

2.2 Oxidation States & Stability

Common OS: -2, +2, +4, +6

Key Trend: Stability of -2 decreases down the group; Stability of +6 decreases, +4 increases
(Inert Pair Effect)

2.3 Anomalous Behaviour of Oxygen

Small size, high electronegativity

Maximum covalency = 4 (no d-orbitals)

Forms strong H-bonds in H₂O

Exists as O₂ (paramagnetic); others are solids

2.4 Important Compounds

A. Dioxygen (O₂)

Preparation (Lab): 2KClO₃ → 2KCl + 3O₂ (MnO₂ catalyst)

Properties: Paramagnetic, supports combustion

B. Ozone (O₃)

Preparation: 3O₂ → 2O₃ (silent electric discharge; endothermic)

Properties:

Powerful oxidizing agent (O₃ → O₂ + [O])

Structure: Angular (bond angle ~117°), resonance hybrid, equal bond lengths

Ozone Depletion: Catalyzed by CFCs & NO

NO + O₃ → NO₂ + O₂

C. Sulphur Dioxide (SO₂)

Properties:

Acidic oxide: SO₂ + H₂O ⇌ H₂SO₃

Reducing agent:

Decolorizes KMnO₄

2Fe³⁺ + SO₂ + 2H₂O → 2Fe²⁺ + SO₄²⁻ + 4H⁺

Structure: Angular, resonance hybrid

D. Sulphuric Acid (H₂SO₄)

Manufacture (Contact Process):

S + O₂ → SO₂

2SO₂ + O₂ ⇌ 2SO₃ (V₂O₅, 720 K, ~2 bar)

SO₃ + H₂SO₄ → H₂S₂O₇ (Oleum) → H₂S₂O₇ + H₂O → 2H₂SO₄

Properties:

Strong acid: H₂SO₄ → H⁺ + HSO₄⁻ (Kₐ₁ >> 1); HSO₄⁻ ⇌ H⁺ + SO₄²⁻ (Kₐ₂ = 1.2×10⁻²)

Dehydrating agent: C₁₂H₂₂O₁₁ → 12C + 11H₂O

Oxidizing agent (hot & conc.):

Cu + 2H₂SO₄ → CuSO₄ + SO₂ + 2H₂O

C + 2H₂SO₄ → CO₂ + 2SO₂ + 2H₂O

3. GROUP 17 ELEMENTS: HALOGENS

3.1 General Characteristics & Trends

Valence Configuration: ns²np⁵

Atomic Radius: Increases down the group

Ionisation Energy, Electronegativity, Electron Gain Enthalpy: Decrease down the group

Oxidizing Power: F₂ > Cl₂ > Br₂ > I₂

Bond Dissociation Enthalpy: Cl-Cl > Br-Br > F-F > I-I

3.2 Anomalous Behaviour of Fluorine

Small size, highest electronegativity

No d-orbitals, shows only -1 oxidation state

HF is liquid (H-bonding); others are gases

Electron Gain Enthalpy less negative than Cl due to small size

3.3 Chemical Properties

A. Hydrogen Halides (HX)

Acidic Strength: HF < HCl < HBr < HI

Stability: HF > HCl > HBr > HI

HF: Weak acid due to strong H-bonding

B. Reactions with Water

F₂ + 2H₂O → 4H⁺ + 4F⁻ + O₂ (oxidizes water)

X₂ + H₂O → HX + HOX (X = Cl, Br; disproportionation)

I₂ + H₂O: No reaction (non-spontaneous)

C. Chlorine Reactions

With cold dilute NaOH: Cl₂ + 2NaOH → NaCl + NaOCl + H₂O

With hot concentrated NaOH: 3Cl₂ + 6NaOH → 5NaCl + NaClO₃ + 3H₂O

With slaked lime: 2Ca(OH)₂ + 2Cl₂ → Ca(OCl)₂ + CaCl₂ + 2H₂O (Bleaching Powder)

Bleaching Action: Due to oxidation (Cl₂ + H₂O → 2HCl + [O])

D. Interhalogen Compounds

Types: XX', XX'₃, XX'₅, XX'₇ (X = larger halogen)

Preparation: Direct combination of halogens

Properties:

More reactive than halogens (except F₂) due to weaker X-X' bond

Hydrolysis: XX' + H₂O → HX' + HOX

E. Structures (VSEPR Theory)

ClF₃, BrF₃: Bent T-shape (2 lone pairs on central atom)

ClF₅, BrF₅: Square pyramidal (1 lone pair)

IF₇: Pentagonal bipyramidal (0 lone pairs)

4. GROUP 18 ELEMENTS: NOBLE GASES

4.1 General Characteristics

Valence Configuration: ns²np⁶ (He: 1s²)

Ionisation Enthalpy: Very high, decreases down the group

Electron Gain Enthalpy: Large positive values

Reactivity: Least reactive due to stable configuration

4.2 Xenon Compounds (Important for JEE)

Forms compounds only with F and O

A. Xenon Fluorides

Xe + F₂ → XeF₂ (Xe excess)

Xe + 2F₂ → XeF₄ (1:5 ratio)

Xe + 3F₂ → XeF₆ (1:20 ratio)

B. Structures (VSEPR)

XeF₂: Linear (3 lone pairs on Xe)

XeF₄: Square planar (2 lone pairs)

XeF₆: Distorted octahedral (1 lone pair)

C. Hydrolysis Reactions

2XeF₂ + 2H₂O → 2Xe + 4HF + O₂ (Redox reaction)

XeF₆ + 3H₂O → XeO₃ + 6HF

Partial hydrolysis: XeF₆ + H₂O → XeOF₄ + 2HF

D. Oxides & Oxyfluorides

XeO₃: Pyramidal, highly explosive

XeOF₄: Square pyramidal