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13.2 Qualitative Analysis of Organic Compounds

13.2 Qualitative Analysis of Organic Compounds

🎯 Learning outcomes

By the end of this chapter, Students should be able to:

  • Detect N, S, and halogens in organic compounds by Lassaigne’s test.
13.2 Qualitative analysis of organic compounds (detection of N, S, and halogens by Lassaigne’s test)
1 Detection of foreign elements

As we know, hydrocarbons and their derivatives are called organic compounds. It means carbon and hydrogen are the essential elements in organic compounds. Many organic compounds include oxygen as well. Besides, a few elements like nitrogen, sulphur, halogens, phosphorus, etc., may be present in organic compounds. These elements are called foreign elements.

Generally, foreign elements are detected via the formation of sodium extract, also called Lassaigne’s extract. The whole process is called the sodium extract or Lassaigne’s extract test. This is done because organic compounds are covalent compounds. Reactions involving covalent bonds are slow and complex. It is difficult to test for the presence of foreign elements as such. So, these are first changed into ionic form by strongly heating them with reactive sodium metal, whose presence could be easily tested.

2 Preparation of Sodium extract (Lassaigne’s extract)

Sodium metal is generally stored in kerosene. A small piece of sodium metal is taken and dried in the fold of blotting paper. Then it is kept in a fusion tube or ignition tube and heated gently so that the sodium metal just melts into a shiny globule. Then, after cooling it slightly, the sample of the organic compound, in which the presence of foreign elements is to be detected, is added in an amount nearly equal to the size of sodium. Then it is heated, first gently, then strongly, until red-hot and plunged into a porcelain basin containing water. The fusion tube and contents are crushed and warmed, then filtered. The filtrate is called sodium extract or Lassaigne’s extract, and it is used to detect foreign elements.

The sodium extract is generally alkaline due to the presence of NaOH formed by the reaction of water with excess sodium.

H₂O + Na → NaOH + H₂ + heat

The following reactions occur during the preparation of Sodium extract if N, S, both N and S, or halogens are present in the organic compound, respectively.

Na + C + N → NaCN Sodium cyanide Na + S → Na₂S Sodium sulphide Na + C + N + S → NaCNS Sodium thiocyanate Na + X → NaX Sodium halide (where X = halogen i.e. Cl, Br, I etc)
3 Detection of Nitrogen

For the detection of nitrogen, the sodium extract must be alkaline. If it is not, it should be made alkaline by adding a small amount of NaOH solution. About 1 ml of the sodium extract is taken in a test tube, and a few drops of freshly prepared FeSO₄ solution are added. Then it is boiled, where dirty green ppt. is generally formed. After cooling in tap water, a few drops of FeCl₃ are added and acidified with dilute HCl. The formation of Prussian blue or green colouration indicates the presence of nitrogen in the given organic compound. The following reactions are involved.

Prussian blue  or  Green  colouration → presence of Nitrogen
Na + C + N → NaCN 2 NaOH + FeSO₄ → Na₂SO₄ + Fe(OH)₂↓ Dirty green ppt Fe(OH)₂ + NaCN → Fe(CN)₂ + 2 NaOH Fe(CN)₂ + 4 NaCN → Na₄[Fe(CN)₆] Sodium ferrocyanide 3 Na₄[Fe(CN)₆] + 4 FeCl₃ → Fe₄[Fe(CN)₆]₃ + 12 NaCl Ferric ferrocyanide — Prussian blue or green coloured

During this test, the formation of blood red colouration indicates the presence of both nitrogen and sulphur in the organic compound. (Test for both sulphur and nitrogen)

Blood red colouration → presence of both Nitrogen and Sulphur
Na + C + N + S → NaCNS Sodium thiocyanate 3 NaCNS + FeCl₃ → Fe(CNS)₃ + 3 NaCl Ferric thiocyanide (blood red coloured)
4 Detection of Sulphur

The presence of sulphur is detected in two ways.

a) Lead acetate test

The sodium extract is acidified with acetic acid and then treated with lead acetate. The formation of black ppt. confirms the presence of sulphur.

Black ppt. → presence of Sulphur
Na₂S + (CH₃COO)₂Pb –CH₃COOH–> 2 CH₃COONa + PbS↓ Lead acetate (Lead ethanoate) Sodium ethanoate (Sodium acetate) black ppt

b) Sodium nitroprusside test

To a small portion of the sodium extract solution, nitroprusside solution is added. The appearance of violet colouration confirms the presence of sulphur in the organic compound.

Violet colouration → presence of Sulphur
Na₂S + Na₂[Fe(CN)₅NO] → Na₄[Fe(CN)₅NOS] Sodium nitroprusside Sodium sulphonitroprusside
5 Detection of Halogens

To detect halogens, the first 1 ml of the sodium extract is boiled with dilute nitric acid to remove cyanide or sulphide if present.

HNO₃(aq.) + NaCN(aq.) → NaNO₃(aq.) + HCN↑ HNO₃(aq.) + Na₂S(aq.) → NaNO₃(aq.) + H₂S↑

If not removed, these ions interfere with the result of the silver nitrate test as

AgNO₃ + NaCN → AgCN↓ + NaNO₃ white ppt AgNO₃ + Na₂S → Ag₂S↓ + NaNO₃ black ppt

After boiling, it is cooled, and then a few drops of AgNO₃ solution are added. The formation of white ppt. soluble in ammonia solution (ammonium hydroxide) and reappearing in dilute HNO₃ indicates the presence of chlorine.

White ppt. soluble in NH₃, reappears in dilute HNO₃ → presence of Chlorine
AgNO₃ + NaCl → AgCl↓ + NaNO₃ white ppt AgCl + 2 NH₃(aq.) → [Ag(NH₃)₂]Cl Diammine silver chloride (soluble complex) Or, AgCl + 2 NH₄OH → [Ag(NH₃)₂]Cl + H₂O [Ag(NH₃)₂]Cl + 2 HNO₃ → AgCl + 2 NH₄NO₃

The formation of pale-yellow ppt. slightly soluble in ammonium hydroxide or aq. NH₃ indicates the presence of bromine.

Pale-yellow ppt. slightly soluble in NH₄OH → presence of Bromine
AgNO₃ + NaBr → AgBr↓ + NaNO₃ pale yellow ppt AgBr + 2 NH₃(aq.) → [Ag(NH₃)₂]Br Diammine silver bromide (partially soluble)

The formation of yellow ppt. insoluble in ammonium hydroxide or NH₃ solution indicates the presence of iodine.

Yellow ppt. insoluble in NH₃ → presence of Iodine
AgNO₃ + NaI → AgI↓ + NaNO₃ yellow ppt.

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📥 Download 13.2 Detection of Foreign Elements- Notes

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📥 Download 13.2 Detection of Foreign Elements- MCQs

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