Semester –III Organic Chemistry Practical

Systematic identification of organic compounds

S. No. Test Observation Inference

1 Preliminary Tests
a. Physical state Liquid
Solid
Crystalline
Amorphous

b. Color Orange o-nitro aniline

Pale yellow p-nitro aniline
Golden yellow m-nitro aniline
Lemon p-nitro toluene
Light pink resorcinol

c. Solubility
Soluble in water Carbohydrate, amide, acids
Soluble in NaOH Carboxylic, sulphonic acids, phenols
Soluble in HCl Aliphatic amines
 S. No. Test Observation Inference

d. Ignition Test
The organic compound is Burns with sooty Aromatic compound
placed on a nickel spatula flame
which is then heated in a Burns with non sooty Aliphatic compound
flame flame
e. Acidic & Basic test An aqueous sln of the Acidic character
(Litmus Test) compound turns blue (Carboxylic, sulphonic acids,
litmus paper to red phenols)

An aqueous sln of the Basic character

compound turns red (1o, 2o amines)
litmus paper to blue
Neutral (aldehyde, ketone, carbohydrate,
No color change amide, nitro comp.)
f. Unsaturation Test Purple color of Comp. may be unsaturated
KMnO4 disappears
i. Bayer’s test
To a solution of the comp. Purple color of Comp. is saturated
add dil.KMnO4 sln. KMnO4 persists

ii. Bromine test Brown color of Comp. is unsaturated

To a solution of the comp. bromine disappears
add Br2 sln.
Brown color of Comp. is saturated
bromine persists
Lassaigne’s Test Sodium Fusion Extract (SFE)

Place 20mg of the solid sample in an ignition tube containing Na metal. Add few mg of sample more.
Heat the lower end of the tube first gently until the sodium has melted and then heat vigorously until
bottom the tube becomes red hot. Immerse (plunge) the red hot tube into 10ml of distilled water taken
in a porcelain dish. Break the ignition tube with glass rod and boil the mixture for few minuets and
filter.

If organic compound contains N special element, then SFE contains sodium cyanide

Na + C + N NaCN

If organic compound contains S special element, then SFE contains sodium sulphide

2Na + S Na2S

If organic compound contains both N & S special elements, then SFE contains sodium thiocyanate

Na + C + N + S NaCNS (NaCNS + 2Na NaCN + Na2S)

If organic compound contains X special element, then SFE contains sodium halide

Na + X NaX
 S. Test Observation Inference
No.
2 Special Element Test
i. Test for nitrogen
To 1ml of SFE add small amount of solid Appearance of Prussian blue Nitrogen conformed
FeSO4. A green precipitate of Fe(OH)2 is color
formed. Boil the mixture gently, cool and
acidify by adding dil.H2SO4.

FeSO4 + 2NaOH Fe(OH)2 + Na2SO4

Fe(OH)2 + 2NaCN Fe(CN)2+ 2NaOH

Fe(CN)2+ 4NaCN Na4[Fe(CN)6]

3Na4[Fe(CN)6] + 2Fe2(SO4)3 Fe4[Fe(CN)6]3 + 6Na2SO4

S. Test Observation Inference

No.
ii.
Test for sulphur
(a) To 1ml of SFE add 3-4 drops of sodium Appearance of Pink to purple Sulphur conformed
nitroprusside sln. color
(b) Acidify 2ml of SFE with dil.CH3COOH
and add 1 ml of lead acetate solution Black precipitate obtained Sulphur conformed

Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS]

Na2S + Pb(CH3COO)2 PbS + 2CH3COONa

 S. Test Observation Inference
No.
iii.
Test for nitrogen & sulphur present
together Appearance of blood red color Presence of both nitrogen &
To 2ml of SFE add dil HCl until acidic and sulphur conformed
then add3-4 drops of freshly prepared FeCl3
sln.

3NaCNS + FeCl3 Fe(CNS)3 + 3NaCl NaCNS + 2Na NaCN + Na2S

S. Test Observation Inference

No.
iv.
Test For Halogens (N and S absent) White precipitate obtained
Acidify 2ml of SFE with conc.HNO3 and which dissolves in NH4OH Chlorine is present
boil. Cool and add 1ml AgNO3 sln Yellowish white precipitate
Test For Halogens (N and S Present) obtained which partially
Acidify 2ml of SFE with dil.HNO3 and boil Bromine is present
dissolves in NH4OH
until half of the volume is evaporated in
order to expel HCN and add 1ml AgNO3 Yellow precipitate obtained
which is insoluble in NH4OH Iodine is present
sln.

NaX + AgNO3 AgX + NaNO3

S. No. Test Observation Inference
v. Test for bromine & iodine Organic layer becomes violet Iodine is confirmed
Acidify 2ml of SFE with conc. HNO3 and boil. color
Cool and add 1ml CCl4 and chlorine water Organic layer becomes brown Bromine is confirmed
excess. Shake the solution. color
Test for Amide
Hydrolysis with alkali:
Place a small amount of compound in a test tube and add 1ml of dil. NaOH solution to it. Heat the
mixture to boiling. Evolution of ammonia takes place which turns red litmus to blue or gives white
fumes with HCl indicating the presence of amide group.

RCONH2 + NaOH RCOONa + NH3

Test for Amine group

Dye test:
Dissolve a small amount of substance in 2ml dil. HCl and cool the mixture to 0 oC. To this add precooled
NaNO2 solution in such small amounts that no brown fumes escape from the solution. Add 1ml of this
solution to a solution of β-naphthol in alkali. The orange red coloured dye indicate the presence of
primary amine..

NH2 N2Cl- N N

ONa
NaOH
+ NaNO2 + HCl
-naphthol
Test for Nitro group
(i) Mulliken’s test:
To a small amount of substance add 2ml of alcohol, small amount of solid ammonium chloride(1ml
CaCl2 solution) and pinch of zinc dust or 1-2 small tin pieces. Boil the mixture for 5 minutes, cool and
filter. To the filtrate add tollen’s reagent. A grey or black precipitate or silver mirror indicates the
presence of nitro group.
RNO2 + 4NH4Cl + 2Zn RNHOH + 2ZnCl2 + 4NH3 + H2O
RNHOH + 2Ag(NH3)2OH RNO + 2Ag + 4NH3 + H2O

(ii) Reduction of nitro group:

To a small amount of substance add 3-4 ml of dil. HCl and a pinch of zinc dust. Boil the mixture about
5min. Cool, filter and in the filtrate perform dye test.
Zn/HCl
RNO2 RNH2

Test for Carboxylic group
Sodium bicarbonate Test:
To 5ml of saturated solution of sodium bicarbonate add a pinch of substance. Evolution of carbon
dioxide with effervescence indicates the carboxylic group.

RCOOH + NaHCO3 RCOONa + H2O + CO2

Test for Carbonyl group
2, 4, dinitrophenyl hydrazine test:
place 1ml of a saturated solution of 2,4 DNP (Brady’s reagent) in a test tube and to this add 20 mg of solid
sample. Shake the test tube vigorously. If no precipitate separate out, heat the test tube on water bath for
1-2 minutes and shake again, a precipitate usually red, orange or yellow indicates the presence of
carbonyl group. NO NO
2 2

R1 R1
O2N NH-NH2 O C O2N NH-N C
R2 R2
Test for aldehyde
i. Tollen’s test:
Add 1ml of alcoholic solution of the sample to 1 ml of ammonical silver nitrate solution (Tollen’s reagent)
in a clean dry test tube. Shake and the warm the solution on a water bath for 5 minutes. Formation of
silver mirror or black precipitate indicates the presence of aldehyde.
AgNO3 + NaOH AgOH + NaNO3

AgOH + NH4OH 2Ag(NH3)2OH

RCHO + 2Ag(NH3)2OH + H2O RCOONH4 + NH3 + 2NH4OH + 2Ag

ii. Fehling’s test:
In a test tube mix 1ml each of Fehling’s A (CuSO4 in water with few drops of acetic acid) and Fehling’s B
(Rochelle salt and NaOH solution) solutions when a deep blue colour appears. To this add 100mg of
substance and boil for 5 minuts. Formation of bright red colour indicates the presence of aldehyde group.
H H

HO C COO-Na+ -2H2O O C COO-Na+ RCHO HOHC COO-Na+

Cu(OH)2 Cu RCOOH + Cu2O +
HO C COO-Na+ O C COO-Na+ 
HOHC COO-Na+
H H
Tartrato-cuprate anion (Blue)
Fehling's sln
Test for Phenolic group
Ferric chloride test:
To 2ml aqueous or alcoholic solution of compound add 5 drops of freshly prepared neutral ferric chloride
solution. Coloured complex of phenol are produced. (Phenol, resorcinol – violet or blue colouration;
Catechol – green colouration; Hydroquinone – transient blue colouration)
OH O O O O

Fe3+

-H+ -Fe2+

O O O

O O O

Test for Carbohydrate

Molisch test:
In a dry test tube, dissolve 50mg of compound in 2ml of water and add 2-3 drops of α-naphthol in ethanol
solution. Hold the test tube at an angle and slowly add 2ml conc H2SO4 along the sides of the test tube.
The development of a reddish violet ring at the junction of the two liquids indicates the presence of
carbohydrate. OH

HO OH
Conc. H2SO4 H+
H H
−naphthol C
HOH2C O CHO CH2OH
HOH2C O
OHHO CHO 5-hydroxymethyl furfural