8.9 Qualitative Analysis of Organic Compounds

QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

The elements present in organic compounds are carbon and hydrogen. In addition to these, they may also contain oxygen, nitrogen, sulphur, halogens and phosphorus.

Detection of Carbon and Hydrogen

Carbon and hydrogen are detected by heating the compound with copper(II) oxide. Carbon present in the compound is oxidised to carbon dioxide (tested with lime-water, which develops turbidity) and hydrogen to water (tested with anhydrous copper sulphate, which turns blue).

\(
\begin{aligned}
& \mathrm{C}+2 \mathrm{CuO} \xrightarrow{\Delta} 2 \mathrm{Cu}+\mathrm{CO}_2 \\
& 2 \mathrm{H}+\mathrm{CuO} \xrightarrow{\Delta} \mathrm{Cu}+\mathrm{H}_2 \mathrm{O}
\end{aligned}
\)
\(
\mathrm{CO}_2+\mathrm{Ca}(\mathrm{OH})_2 \longrightarrow \mathrm{CaCO}_3 \downarrow+\mathrm{H}_2 \mathrm{O}
\)
\(
5 \mathrm{H}_2 \mathrm{O}+\underset{\text { White }}{\mathrm{CuSO}_4} \longrightarrow \underset{\text { Blue }}
{\mathrm{CuSO}_4 \cdot 5 \mathrm{H}_2 \mathrm{O}}
\)

Detection of Other Elements

Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by “Lassaigne’s test”. The elements present in the compound are converted from covalent form into the ionic form by fusing the compound with sodium metal. Following reactions take place:

\(
\mathrm{Na}+\mathrm{C}+\mathrm{N} \xrightarrow{\Delta} \mathrm{NaCN}
\)
\(
2 \mathrm{Na}+\mathrm{S} \stackrel{\Delta}{\longrightarrow} \mathrm{Na}_2 \mathrm{~S}
\)
\(
\mathrm{Na}+\mathrm{X}\xrightarrow{\Delta} \mathrm{NaX}
\)
\(
\quad \quad \quad \quad \quad \quad (\mathrm{X}=\mathrm{Cl}, \mathrm{Br} \text { or } \mathrm{I})
\)
C, N, S and X come from organic compound.
Cyanide, sulphide and halide of sodium so formed on sodium fusion are extracted from the fused mass by boiling it with distilled water. This extract is known as sodium fusion extract.

(A) Test for Nitrogen

The sodium fusion extract is boiled with iron(II) sulphate and then acidified with concentrated sulphuric acid. The formation of Prussian blue colour confirms the presence of nitrogen. Sodium cyanide first reacts with iron(II) sulphate and forms sodium hexacyanidoferrate(II). On heating with concentrated sulphuric acid some iron(II) ions are oxidised to iron(III) ions which react with sodium hexacyanidoferrate(II) to produce iron(III) hexacyanidoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.

\(
6 \mathrm{CN}^{-}+\mathrm{Fe}^{2+} \rightarrow\left[\mathrm{Fe}(\mathrm{CN})_6\right]^{4-}
\)
\(
3\left[\mathrm{Fe}(\mathrm{CN})_6\right]^{4-}+4 \mathrm{Fe}^{3+}\xrightarrow{\mathrm{xH}_2 \mathrm{O}}\mathrm{Fe}_4\left[\mathrm{Fe}(\mathrm{CN})_6\right]_3 \cdot \mathrm{xH}_2 \mathrm{O}
\)
\(
\quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \text { Prussian blue }
\)

(B) Test for Sulphur

(a) The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A black precipitate of lead sulphide indicates the presence of sulphur.
\(
\mathrm{S}^{2-}+\mathrm{Pb}^{2+} \longrightarrow \mathrm{PbS}
\)
\(
\quad \quad \quad \quad \quad \quad \quad \text { Black }
\)
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour further indicates the presence of sulphur.
\(
\mathrm{S}^{2-}+\left[\mathrm{Fe}(\mathrm{CN})_5 \mathrm{NO}\right]^{2-}\longrightarrow \quad\left[\mathrm{Fe}(\mathrm{CN})_5 \mathrm{NOS}\right]^{4-}
\)
\(
\quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \text { Violet }
\)
In case, nitrogen and sulphur both are present in an organic compound, sodium thiocyanate is formed. It gives blood red colour and no Prussian blue since there are no free cyanide ions.
\(
\mathrm{Na}+\mathrm{C}+\mathrm{N}+\mathrm{S} \longrightarrow \quad \mathrm{NaSCN}
\)
\(
\mathrm{Fe}^{3+}+\mathrm{SCN}^{-} \quad \longrightarrow \quad[\mathrm{Fe}(\mathrm{SCN})]^{2+}
\)
\(
\quad \quad \quad \quad \quad \quad \quad \quad \quad \quad \text { Blood red }
\)
If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield cyanide and sulphide. These ions give their usual tests.
\(
\mathrm{NaSCN}+2 \mathrm{Na} \longrightarrow \mathrm{NaCN}+\mathrm{Na}_2 \mathrm{~S}
\)

(C) Test for Halogens

The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate. A white precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish precipitate, sparingly soluble in ammonium hydroxide shows the presence of bromine and a yellow precipitate, insoluble in ammonium hydroxide shows the presence of iodine.
\(
\mathrm{X}^{-}+\mathrm{Ag}^{+} \longrightarrow \mathrm{AgX}
\)
\(\mathrm{X}\) represents a halogen \(-\mathrm{Cl}, \mathrm{Br}\) or \(\mathrm{I}\).
If nitrogen or sulphur is also present in the compound, the sodium fusion extract is first boiled with concentrated nitric acid to decompose cyanide or sulphide of sodium formed during Lassaigne’s test. These ions would otherwise interfere with silver nitrate test for halogens.

(D) Test for Phosphorus

The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated with ammonium molybdate. A yellow colouration or precipitate indicates the presence of phosphorus.
\(
\mathrm{Na}_3 \mathrm{PO}_4+3 \mathrm{HNO}_3 \longrightarrow \mathrm{H}_3 \mathrm{PO}_4+3 \mathrm{NaNO}_3
\)
\(
\mathrm{H}_3 \mathrm{PO}_4+12\left(\mathrm{NH}_4\right)_2 \mathrm{MoO}_4+21 \mathrm{HNO}_3 \longrightarrow \left(\mathrm{NH}_4\right)_3 \mathrm{PO}_4 \cdot 12 \mathrm{MoO}_3+21 \mathrm{NH}_4 \mathrm{NO}_3+12 \mathrm{H}_2 \mathrm{O}
\)
\(
\quad \quad \quad \quad \quad \text { Ammonium molybdate } \quad \quad \quad \quad \text { Ammonium phosphomolybdate }
\)