Pratical Organic Chemistry (13th)

XIII (ALL)
PRACTICAL ORGANIC CHEMISTRY

(A) FUNCTIONAL GROUP ANALYSIS
1. Unsaturation : Alkenes & alkynes:
(a) Bayers test : Cold dil alk. KMnO4 decolourisation test
Purple colour  Colourless + MnO2 (Brown ppt)
(b) Br2 water decolourisation test
Violet colourless of Br2  Colourless
2. Terminal alkynes:
Confirmed by ppt of Acetylide ion with NaNH2 or AgNO3 or Cu2Cl2NH4OH
3. Alkyl halides:
(a) If they are capable of carbocation formation then they will give ppt with AgNO3.
(b) Beilstein’s test : A green colour is imported to the flame if small amount of organic compound is taken on
copper wire.
4. Alcohol:
(a) Cerric ammonium nitrate  Give red colour
(b) Boil with acetic acid & conc. H2SO4  fruity smell

(c) 2-alkanol & ethanol also give Iodoform test  Yellow ppt. of CH3I on reaction with I2+ OH
5. Aldehyde & Ketones:
2,4- Dinitrophenyl hydrazize (or) Braddy’s reagent give yellow, orange or red color with ald. & Ketones
(2,4-DNP)
6. Aldehydes:
(a) Tollen’s test  Silver mirror
(b) Fehling’s test {except benzaldehyde} Red colour
(c) Benedicts test  Red colour
(d) Schiff’s dye colour regeneration test  Pink colour
(e) Gly ppt with HgCl2 .
7. Ketones:
(a) Methyl Ketones give haloform test
(b) -hydroxy Ketones give Tollen’s & Fehling test’s too.
8. Carboxylic acids:
(a) Brisk effervescence with aq. NaHCO3 solution.
(b) HCOOH alone gives silver mirror test with Tollen’s reagent.
(c) Blue litmus  red
(d) Give fruity smell on reaction with alcohols.
9. Phenols:
(a) Violet colouration with neural FeCl3
(b) Liebermann test
(c) White ppt with Br2 water
(d) Brisk effervescence with aq. NaHCO3 is observed in case of Nitrophenols.
10. Primary amines:
(a) Carbylamine reaction  Isonitriles have very distinctive foul odors
(b) Hoffmann mustard oil reaction Oily liquid with mustard like smell.
11. Aromatic 1° amine  diazo test
12. Amide boil with NaOH  NH3
13. Nitrobenzene  Mullikqn Baker test  Treat it with ZnNH4Cl then boil with Tollen’s reagent  Silver
mirror will appear
14. Proteins:
(a) Biuret test : Also used for urea  Alkaline solution of protein treated with a drop of aq CuSO4
when bluish violet colour is obtained
(b) Ninhydrin test : Protein treated with a puridine solution of ninhydrin give colour ranging from deep blue
to violet pink.
DIFFERENTATION TEST
D1. 1°, 2° & 3° alcohols:
(a) Luca’s test : Lucas reagent is conc. HCl + ZnCl2
(b) Victor Meyer’s test (RBC test)
(i) 1° Alcohol  Blood red colour
(ii) 2° Alcohol  Blue
(iii) 3° Alcohol  Colourless
D2. 1°, 2° & 3° amines:
(a) Hinsberg’s reagent
(i) 1° Amine yield a clear solution from which upon acidification an insoluble material separated.
(ii) 2° Amine yield an insoluble compound which is unaffected by acid
(iii) 3° Amine yield insoluble compound
(b) Reaction with HNO2
QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

The elements present inorganic compounds aer carbon and hydrogen. In addition to these, they may
also contain oxygen, nitrogen, sulphur,halogens and phosphorus.
1. Detection of Carbon and Hydrogen
Carbon and hydrogen are detected by heating the compound iwth 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 suphate, which turns blue).
C + 2CuO   2Cu + CO2

2H + CuO   Cu + H2O

CO2 + Ca(OH)2  CaCO3 + H2O
5H2O + CuSO4  CuSO4 . 5H2O
White Blue
2. Detection of Other Elements
Nitrogen, sulphur, halogens and phosphorus present in an organic comopund 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:
Na + + N   NaCN

2Na + S  Na2S

Na + X   NaX

(X = Cl, Br or I)
C, N, S and X come from organic comopund.
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 of 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 nitrogne. Sodium cyanide first
reacts with iron(II) sulphate and forms sodium hexacyanoferate(II). On heating with concentrated sulphuric
acid some iron(II) ions are oxidised to iron(III) ions which react with sodium hexacyanoferrate(II) to
produce iron(III) hexacyanoferrate(II) (ferriferrocyanide) which is Prussian blue in colour.
6CN– + Fe2+  [Fe(CN)6]4–
3[Fe(CN)6]4– + 4Fe3+ xH 2O
 Fe4[Fe(CN)6]3 . xH2O
Prussian blue
(B) Test for Sulphur
(a) The soldium 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.
S2– + Pb2+  PbS
Black
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour further
indicates the presence of sulphur.
S2– + [Fe(CN)5NO]2–  [Fe(CN)5NOS]4–
Violet
In case, nitrogen and sulphur both are present in an organic compuond, sodium thiocyanate is formed. It
gives blood red colour and no Prussian blue since there are no free cyanide ions.
Na + C + N + S  NaSCN
Fe3+ + SCN–  [Fe(SCN)]2+
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.
NaSCN + 2Na  NaCN + Na2S
(C) Test of Halogens
The sodium fustion extract is acidified with nitric acid and then treated with silver nitrate. A white precipi-
tate, 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, insolube in
ammonium hydroxide shows the presence of iodine.
X– + Ag+  AgX
X represents a halogen – Cl, Br or 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 phophate. The solution is boiled with nitric acid and then treated with ammo-
nium molybdate. A yellow colouration or precipitate indicates the presence of phophorus.
Na3PO4 + 3HNO3  H3PO4 + 3NaNO3
H3PO4 + 12(NH4)2MoO4 + 21HNO3  (NH4)3PO4 . 12MoO3 + 21NH4NO3 + 12H2O
Ammonium molybdate Ammonium phophomolybdate
CONCLUSION IS
(A) ELEMENTAL ANALYSIS
Lassaigne method (Detection of elements)

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XIII (ALL)

PRACTICAL ORGANIC CHEMISTRY

QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

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