|

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.

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 sodium extract or Lassaigne’s extract test. This is done because organic compounds are covalent compounds. And 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.

Preparation of Sodium extract (Lassaigne’s extract)

Sodium metal is generally stored in kerosene.

  1. A small piece of sodium metal is taken and dried in the fold of blotting paper.
  2. It is kept in a fusion tube or ignition tube and heated gently so that the sodium metal just melts into a shiny globule.
  3. 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.
  4. It is heated, first gently, then strongly, until red-hot and plunged into a porcelain basin containing water.
  5. The fusion tube and content 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 thiocyanide)
Na + X NaX (Sodium halide, where X = Cl, Br, I etc.)

1. 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.

  1. About 1 ml of the sodium extract is taken in a test tube and a few drops of freshly prepared FeSO4 solution are added.
  2. It is boiled, where dirty green ppt. is generally formed.
  3. 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.

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

Test for both Sulphur and Nitrogen

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

Blood red colouration (both N and S present)
Na + C + N + S NaCNS (Sodium thiocyanide)
3 NaCNS + FeCl3 Fe(CNS)3 + 3 NaCl
Ferric thiocyanide (blood red coloured)

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.
Na2S + (CH3COO)2Pb 2 CH3COONa + PbS↓
in the presence of CH3COOH  —  Lead acetate (lead ethanoate)  →  Sodium ethanoate + 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.
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]
Sodium nitroprusside             Sodium sulphonitroprusside

Detection of Halogen

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↑

Because 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.

Chlorine

The formation of white ppt., soluble in ammonia solution (ammonium hydroxide) and reappearing in dilute HNO3, indicates the 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

Bromine

The formation of pale-yellow ppt., slightly soluble in ammonium hydroxide or aq. NH3, indicates the presence of bromine.
AgNO3 + NaBr AgBr↓ + NaNO3 (pale yellow ppt)
AgBr + 2 NH3(aq.) [Ag(NH3)2]Br (Diammine silver bromide — partially soluble)

Iodine

The formation of yellow ppt., insoluble in ammonium hydroxide or NH3 solution, indicates the presence of iodine.
AgNO3 + NaI AgI↓ + NaNO3 (yellow ppt.)
© subarnam.com.np

📥 Download 13.2 Detection of Foreign Elements- Notes

📥 Download 13.2 Detection of Foreign Elements- Important Questions

📥 Download 13.2 Detection of Foreign Elements- MCQs

Similar Posts

Leave a Reply

Your email address will not be published. Required fields are marked *