5.5.3Unit 5. Transition Metals and Organic Nitrogen Chemistry
Aromatic Amines — IAL Edexcel Linear (Chemistry) Revision Notes & Topical Questions
5 min read 5 parts Lesson 33 of 43 Unit quiz
Part 1 of 5Preparation of Phenylamine

1
Nitrobenzene is heated under reflux with tin and concentrated hydrochloric acid.
2
C₆H₅NO₂ + 6[H] → C₆H₅NH₂ + 2H₂O, though in acid the product is held as the salt C₆H₅NH₃⁺.
3
Excess sodium hydroxide is added to liberate the free phenylamine.
4
The amine is then separated by steam distillation or solvent extraction.
Part 2 of 5Basicity
Basicity
Weaker base
- Phenylamine is less basic than ethylamine and ammonia.
Reason
- The nitrogen lone pair overlaps with the delocalised ring, so it is less available to accept a proton.
Alkyl comparison
- In aliphatic amines the electron-donating alkyl groups increase the density on nitrogen.
Reaction with bromine
- Bromine water gives a white precipitate of 2,4,6-tribromophenylamine, showing the ring is activated.
Hydrogen bonding
- Phenylamine is only slightly soluble in water, because the large non-polar ring reduces the effect of hydrogen bonding.
Part 3 of 5Diazotisation and Coupling
Diazotisation
- C₆H₅NH₂ + HNO₂ + HCl → C₆H₅N₂⁺Cl⁻ + 2H₂O, using NaNO₂ and HCl at 0-5 °C.
Why cold
- Above about 10 °C the diazonium ion decomposes to phenol and nitrogen gas.
Coupling
- The diazonium ion reacts with phenol dissolved in alkali, or with another activated arene, to give a coloured azo compound.
Azo group
- The -N=N- link joins two aromatic rings, extending delocalisation so that visible light is absorbed.
Uses
- Azo compounds are important dyes and food colourings.
Safety
- Diazonium salts are unstable and must be used in solution immediately, since the dry solids can be explosive.
Part 4 of 5Worked Example
Question State the reagents and conditions for converting phenylamine into benzenediazonium chloride and give the equation.
- Use sodium nitrite and hydrochloric acid, which together form nitrous acid.
- Keep the temperature between 0 and 5 °C.
Answer C₆H₅NH₂ + HNO₂ + HCl → C₆H₅N₂⁺Cl⁻ + 2H₂O
Part 5 of 5Exam Checklist & Tips
5.5.3 – Key Points for the Exam
- Phenylamine C₆H₅NH₂, an aromatic amine.
- Diazonium ion An ion containing N₂⁺ attached to a benzene ring.
- Azo dye A coloured compound containing -N=N- between aromatic rings.
- Coupling Reaction of a diazonium ion with an activated arene.
Common Mistakes
- Doing diazotisation at room temperature.
- Saying that phenylamine is a stronger base than ammonia.
- Forgetting the NaOH step to obtain the free amine.
- Omitting alkaline conditions in the coupling reaction with phenol.
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