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How do we distinguish aldehydes from ketones, and what reactions does the carbonyl group undergo?

Aldehydes and ketones, oxidation of aldehydes, reduction with sodium tetrahydridoborate, nucleophilic addition of hydrogen cyanide, and the tests for carbonyl compounds (2,4-DNPH, Tollens' reagent and Fehling's solution).

An OCR H432 module 6 answer on carbonyl compounds: aldehydes and ketones, oxidation of aldehydes, reduction with sodium tetrahydridoborate, nucleophilic addition of hydrogen cyanide, and the 2,4-DNPH, Tollens and Fehling tests.

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  1. What this topic is asking
  2. Aldehydes and ketones
  3. Oxidation and reduction
  4. Nucleophilic addition of hydrogen cyanide
  5. The tests
  6. Examples in context
  7. Try this

What this topic is asking

OCR specification point 6.1.2 wants you to describe aldehydes and ketones, the oxidation of aldehydes (but not ketones), reduction by sodium tetrahydridoborate, the nucleophilic addition of hydrogen cyanide, and the tests that detect a carbonyl group (2,4-DNPH) and distinguish aldehydes from ketones (Tollens' reagent and Fehling's solution). The carbonyl group links alcohols to carboxylic acids.

Aldehydes and ketones

Oxidation and reduction

Nucleophilic addition of hydrogen cyanide

The tests

Examples in context

Example 1. Identifying an unknown in the lab. A practical chemist uses 2,4-DNPH to confirm a carbonyl, then takes the melting point of the orange derivative and compares it with data tables to identify the specific aldehyde or ketone.

Example 2. The blue-to-red Fehling's test in food science. Fehling's solution is used to detect reducing sugars (which contain an aldehyde group); a brick-red precipitate on warming shows the sugar is present, a direct application of aldehyde oxidation.

Try this

Q1. Name the reagent that gives an orange precipitate with both aldehydes and ketones. [1 mark]

  • Cue. 2,4-dinitrophenylhydrazine (2,4-DNPH).

Q2. State the product when butanal is reduced by sodium tetrahydridoborate. [1 mark]

  • Cue. Butan-1-ol (a primary alcohol).

Exam-style practice questions

Practice questions written in the style of OCR exam questions on this dot point, with worked answer explainers. The year tag is the paper they imitate, not the source.

OCR 20204 marksA student has two unlabelled bottles, one containing propanal and one containing propanone. (a) Name a reagent that confirms both contain a carbonyl group, and the observation. (b) Name a reagent that distinguishes them, and the observation with each.
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(a) 2,4-dinitrophenylhydrazine (2,4-DNPH, Brady's reagent); both give an orange (or yellow-orange) precipitate, confirming a carbonyl group (1)(1).

(b) Tollens' reagent (ammoniacal silver nitrate), warmed: propanal (an aldehyde) gives a silver mirror as it is oxidised (1); propanone (a ketone) gives no change because it is not oxidised (1).

Markers reward 2,4-DNPH with the orange precipitate for both, and Tollens' giving a silver mirror with the aldehyde but no reaction with the ketone.

OCR 20224 marksPropanone reacts with hydrogen cyanide. (a) Name the mechanism and the product. (b) Outline the mechanism, showing the curly arrows.
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(a) Nucleophilic addition; the product is 2-hydroxy-2-methylpropanenitrile (a hydroxynitrile) (1).

(b) The cyanide ion (nucleophile) attacks the δ+\delta+ carbonyl carbon (curly arrow from the lone pair on CN\text{CN}^- to the carbon), and the C=O\text{C=O} pi bond breaks onto the oxygen (curly arrow from the double bond to O), forming a negatively charged intermediate (1); the oxygen then accepts a proton (from HCN or water) to give the -OH\text{-OH} group (1)(1).

Markers reward the mechanism name and product, the curly arrow from cyanide to the carbonyl carbon, the breaking of the pi bond onto oxygen, and protonation to the hydroxynitrile.

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