5.6.1

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Testing Alcohols

We can test alcohols to decide whether they are primary, secondary or tertiary.

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The test

  • We must warm the alcohol and then add acidified potassium dichromate (V).
    • Primary: turns green.
    • Secondary: turns green.
    • Tertiary: nothing happens.
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The problem

  • The issue with this test is that it gives the same result for primary and secondary alcohols.
  • A rough way to differentiate between the two is that, generally, primary alcohols will react faster - the green colour will form quicker.
    • But this is unreliable.
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Overcoming the problem

  • A better way to differentiate is by testing the products of the first test.
  • In the first test, the acidified potassium dichromate (V) oxidises:
    • Primary alcohols to aldehydes.
    • Secondary alcohols to ketones.
  • So we can carry out an aldehyde/ketone test to determine which alcohol was initially present.
    • The aldehyde/ketone test uses either Fehling's solution or Tollen's reagent - it has been covered before.

Aldehyde or Ketone

We can determine whether a chemical is either an aldehyde or a ketone through two possible tests.

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Aldehydes and ketones

  • Aldehydes and ketones have very similar functional groups and so are hard to tell apart.
    • The one feature they have that is different is their oxidising ability.
    • So we can use oxidising agents to identify which is present.
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Oxidising ability

  • Aldehydes can be oxidised further (twice) to carboxylic acids.
    • This is because they still have a C-H bond that can be broken for oxidation.
  • Ketones cannot be further oxidised (only once).
    • You would have to break a C-C bond.
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Fehling's solution

  • Our first test is Fehling’s solution.
    • It contains Cu2+ and is deep blue.
  • When you add an aldehyde, the Cu2+ oxidises the aldehyde and is reduced to Cu+.
    • This causes a colour change from deep blue to brick red.
    • With a ketone, you get no colour change because it can’t be oxidised.
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Tollen's reagent

  • Tollen’s reagent contains the diamine silver 1+ ion: [Ag(NH3)2]+.
    • This is a clear solution.
  • This reagent also oxidises an aldehyde, but will do nothing to a ketone.
    • When it oxidises an aldehyde, it is reduced to solid silver and is said to form a ‘silver mirror’ on the surface of the test tube.
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Overall test results

  • Fehling's solution:
    • Aldehyde: Deep blue → brick red.
    • Ketone: Remains deep blue.
  • Tollen's reagent:
    • Aldehyde: Clear → silver mirror.
    • Ketone: Remains clear.

Jump to other topics

1Physical Chemistry

2Physical Chemistry 2 (A2 Only)

3Inorganic Chemistry

4Inorganic Chemistry 2 (A2 Only)

5Organic Chemistry 1

6Organic Chemistry 2 (A2 Only)

6.1Optical Isomerism (A2 Only)

6.2Aldehydes & Ketones (A2 Only)

6.3Carboxylic Acids & Esters (A2 Only)

6.4Aromatic Chemistry (A2 Only)

6.5Amines (A2 Only)

6.6Polymers (A2 Only)

6.7Biological Organic (A2 Only)

6.8Organic Synthesis (A2 Only)

6.9NMR Spectroscopy (A2 Only)

6.10Chromatography (A2 Only)

6.11A-A* (AO3/4) - Organic 2

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