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Overview of Group 7 Halogens

Feb 19, 2025

AQA Group 7 Halogens Overview

Halogens Overview

  • Halogens are diatomic non-metals
  • Fluorine (F₂): Pale yellow gas
  • Chlorine (Cl₂): Pale green gas
  • Bromine (Br₂): Brown-orange liquid
  • Iodine (I₂): Grey solid/purple gas

Trends in Group 7

  • Boiling Points: Increase down the group due to larger van der Waals forces
  • Electronegativity: Decreases down the group, increased shielding = larger atoms attract electrons less effectively
  • Atomic Radius: Increases down the group, due to increased shielding.

Oxidising Ability/Reactivity of the Halogens

  • Decreases down the group
  • More reactive halogens can displace less reactive halide ions in redox reactions
    • Cl₂ (Strongest Oxidising Agent) can displace Br⁻ and I⁻ ions
    • Br₂ can only displace I⁻ ions
    • I₂ cannot displace any halide

Reducing Ability of Halide Ions

  • Reducing Power Increases down the group.
    • More shells = larger ionic radius = weaker attraction between nucleus and outer electrons
    • Halide ions down the group are more easily oxidised
    • I⁻ (Strongest Reducing Agent)
    • Cl⁻ (Weakest Reducing Agent)

Tests for Halides

Reaction of Halide Salts with Conc H₂SO₄

The increase of reducing power of halide ions down the group is demonstrated by their reactions with H₂SO₄ and how much S is reduced.

Step 1 (Acid-base Reaction):

  • NaX (s) + H₂SO₄ (l) → NaHSO₄ (s) + HX (g)

Step 2 (Redox Reaction/s):

  • Unbalanced equation: H⁺ + X⁻ + H₂SO₄ → X₂ + (S compound) + H₂O

Fluoride and Chloride Ions (F⁻/Cl⁻)

F⁻ & Cl⁻ ions do not have enough reducing power to reduce S in H₂SO₄, so no redox only acid-base reaction.

  • NaF + H₂SO₄ → NaHSO₄ + HF
  • NaCl + H₂SO₄ → NaHSO₄ + HCl

Observation: White steamy HF/HCl Fumes

Bromide Ions (Br⁻)

Br⁻ ions are stronger reducing agents than F⁻ & Cl⁻ ions, so they have a redox reaction.

Step 1: NaBr + H₂SO₄ → NaHSO₄ + HBr

Step 2: 2H⁺ + 2Br⁻ + H₂SO₄ → SO₂ + Br₂ + 2H₂O

  • Oxidation State (S): +6 → +4

Overall equation: 2NaBr + 3H₂SO₄ → 2NaHSO₄ + Br₂ + SO₂ + 2H₂O

Observations: White steamy HBr fumes, Orange Br₂ fumes and SO₂ (colourless, acidic gas)

Iodide Ions (I⁻)

I⁻ ions are the strongest reducing agents, so they have multiple redox reactions.

Step 1: NaI + H₂SO₄ → NaHSO₄ + HI

Step 2: 2H⁺ + 2I⁻ + H₂SO₄ → SO₂ + I₂ + 2H₂O

  • Oxidation State (S): +6 → +4

Step 3: 6H⁺ + 6I⁻ + H₂SO₄ → S + 3I₂ + 4H₂O

  • Oxidation State (S): +6 → 0

Step 4: 8H⁺ + 8I⁻ + H₂SO₄ → H₂S + 4I₂ + 4H₂O

  • Oxidation State (S): +6 → -2

Overall equation: CBA

Observations: White steamy HI fumes, Black solid I₂ & Purple I₂ fumes, SO₂ (colourless, acidic gas), Solid yellow S and H₂S egg smell

Identifying halide ions with acidified AgNO₃

  • Add HNO₃ (to get rid of CO₃²⁻ and OH⁻ impurities)

    • HCl or H₂SO₄ would also form precipitates (can't use)
  • Add AgNO₃ to form Silver Halide precipitates

    • Ag⁺ + X⁻ → AgX (s)

Precipitate Colors:

  • Fluoride (F⁻): Colourless (AgF is soluble)
  • Chloride (Cl⁻): White
  • Bromide (Br⁻): Cream
  • Iodide (I⁻): Yellow

Use ammonia to further distinguish

  • AgCl: Dissolves in dilute NH₃
  • AgBr: Dissolves in concentrated NH₃
  • AgI: Insoluble in concentrated NH₃
  • Equation: AgX (s) + 2NH₃ → [Ag(NH₃)₂]⁺ + X⁻

Uses of Chlorine (Cl₂) and Chlorate (ClO⁻)

Chlorine reacts with water in a disproportionation reaction to form Chloric acid and Hydrochloric acid

  • Cl₂ + H₂O ⇌ HClO + HCl

Water Sterilisation

Chlorate ions (ClO-) kill bacteria, preventing diseases like cholera

  • As HClO reacts with bacteria, equilibrium shifts to replace it

Used to disinfect pools and drinking water

  • Advantages: Destroys microorganisms, long-lasting, reduces algae growth
  • Disadvantages: Chlorine is toxic, potential cancer risk from reaction with organic compounds
  • Benefits generally outweigh risks

In sunlight, Cl₂ in water can react to make HCl, so only little is used (& Cl₂ is toxic anyway)

  • 2Cl₂ + 2H₂O → 4HCl + O₂

Bleach Production

Disproportionation Reaction: Cl₂ reacts with cold, dilute, aqueous NaOH to form NaClO (bleach)

  • Cl₂ + 2NaOH → NaCl + NaClO + H₂O
    • Cl₂ is oxidised and reduced

Uses include water treatment, paper bleaching, and cleaning