Experiment No.

CHARACTERISATION OF ORGANIC COMPOUNDS

It is carried out using following steps in the given order.
[A] Preliminary tests
[B] Nature of the compound
[C] Detection of elements
[D] Functional group tests
[E] Determination of physical constant (m.p. / b.p.)
[F] Results

[A] Preliminary tests

Test Observation Inference

1.0 State Liquid / Solid ………..

2.0 Colour Pale yellow Nitro compounds, anthracene,

anthraquinone etc.

Nitrophenols or nitro
Yellow compounds
Orange yellow Nitroanilines
Buff β- naphthol, α – naphthol
Grey Diphenylamine
Brown or Reddish brown Amines
Colourless solid Aliphatic acids, aromatic acids,
carbohydrates, hydrocarbons,
anilides, amides, urea, thiourea
Colourless liquids present
Aldehydes, ketones, alcohols,
esters, aromatic hydrocarbons
and their simple halogen
derivatives present

3.0 Odour Fishy Tertiary amines

Phenolic Phenols and naphthols

Moth ball Naphthalene

Bitter almond Benzaldehyde, nitrobenzene

Sweet / pleasant

4.0 Burning test or heating on
a porcelain piece
5.0 Beilstein Test
Heating on oxidized Cu wire
6.0 Unsaturation Test
a) Action of KMnO4
1/ 2 drops or 15 mg of
compound + acetone + few
drops of very dilute
KMNO4 solution
b) Action of Br2 water
1/ 2 drops or 15 mg of
compound + acetone / H2O +
few drops of very dilute Br2
solution
[B] Nature of compound
Test
1) Compound + Water, shake
well
Ketones, alcohols, esters,
aromatic / aliphatic
hydrocarbons and their simple
halogen derivatives present
No characteristic odour
Acids, amides, anilides,
aromatic hydrocarbons may be
present
Sooty flame Aromatic compounds, CHCl3,
CCl4 may be present
Non-sooty flame Aliphatic compounds or highly
oxygenated compounds may be
present.
Green flame Halogenated compounds, urea,
thiourea, benzamide may be
present
Non – green flame Halogenated compounds, urea,
thiourea, benzamide may be
absent
Decolorisation Unsaturated or easily
oxidisable compound may be
present
No decolorisation Unsaturated or easily
oxidisable compound may be
absent
Unsaturated compound may be
Decolorisation
present or compound can be
easily brominated
No decolorisation Saturated compound may be
present or cannot be easily
brominated.
Observation Inference
Soluble / miscible Water soluble / miscible
compound present
Insoluble / immiscible Water insoluble / immiscible
compound present
 If compound is water soluble / miscible, perform the following tests with aqueous solution of
compound (AQS)

(1a)Take AQS on watch glass Blue litmus paper turns red Acidic compound may be
and dip wet red and blue present
litmus paper Red litmus paper turns blue Basic compound may be
present
No change in litmus paper Neutral compound may be
present
(1b)AQS + saturated NaHCO3 Effervescence Acid present
solution
No Effervescence Acid absent
(1c)AQS+ Aq. FeCl3 solution Violet colour Phenol present
No violet colour Phenol absent
(1d) If all the tests fail ----- Compound must be water
soluble / miscible neutral.
If compound is water insoluble / immiscible, perform the following tests.

(2)Test for acid

Compound + sat. NaHCO3
soln., shake well
Filter the above solution. Cool
the filtrate + Conc. HCl
dropwise
(3)Test for phenol
Compound + dil. NaOH soln.,
shake well
Filter the above solution. Cool
the filtrate in ice bath + Conc.
HCl dropwise
(4)Test for base
Compound + 1:1 HCl, shake
well
Effervescence due to evolution Acid may be present
of CO2 gas
Reprecipitation / regeneration
Water insoluble acid present
of compound
Soluble / miscible Phenol may be present
Reprecipitation / regeneration Water insoluble phenol present
of compound
Soluble / miscible Base may be present

Filter the above solution. Cool
the filtrate in ice bath + Conc.
NaOH dropwise
(5)If all above tests fail
Reprecipitation / regeneration Water insoluble base present
of compound
…….. Compound must be water
insoluble / immiscible neutral

[C] Detection of Elements

Preparation of Sodium Fusion Extract (FE): Fuse a small piece of dry sodium in a dry hard glass test
tube. Add the given organic compound i.e. 1 – 2 drops of liquid or 6 – 10 mg of solid and heat gently.
Add 5 mg of powdered sucrose. Heat it gently for few seconds and then to redness for 5 minutes till the
smell of burning sucrose. Cool and then add 2-3 drops of methanol with Pasteur pipette. Warm to
remove unreacted methanol and then heat to redness. Cool and add 2-3 cm3 of water. Filter it using
cotton plug at the tip of Pasteur pipette or filter through small funnel. Filtrate is sodium fusion extract
(FE).
NOTE:
Use 1-2drops of FE for each test i.e. for test for nitrogen, sulphur and halogens as in the practical
handbook. Use only 2 drops of other reagent involved.
(1)Test for Nitrogen
1-2 drops of FE + 1-2 drops of Green or blue coloration. Nitrogen present
dil. NaOH + freshly prepared
FeSO4 soln. Green ppt. is
obtained. Boil and cool it. Add
1 -2 drops of conc. H2SO4 till
ppt. dissolves.

(2)Test for sulphur

1-2 drops of FE + acetic acid + Black ppt. Sulphur present
lead acetate

(3)Test for halogens

(3a) In absence of nitrogen
1-2 drops of FE + dil. HNO3, Thick white ppt. Halogens present
boil +AgNO3
(3b) In presence of nitrogen
1-2 drops of FE + dil. H2SO4 Thick white ppt. Halogens present
boil till half volume + dil.
HNO3 +AgNO3
(4)Individual tests for
halogens
(To be performed if halogens Colourless layer Cl present
are present)
1-2 drops of FE + dil. H2SO4 Yellowish / brown layer Br present
boil till half volume. Cool it and
Violet layer I present
add CHCl3 + Cl2 water in excess

Conclusion: The given compound contains ………………… elements and is ………………..

innature.
[D] DETECTION OF FUNCTIONAL GROUPS
Tests for compounds under C, H, (O) Elements:
(1) Carboxylic Acids:
(1a) 1-2 ml of sat. NaHCO3 Effervescence Carboxylic acids present
soln. on watch glass + 1 -2
drops of liquid or 10 mg of
solid
2.Phenols
(2a) Ferric ion test
Compound + few drops of water / ethyl Red, blue, purple or green Phenol present
alcohol to dissolve the compound + 1-2 colour
drops of 2.5 % aq. FeCl3 soln., shake
well
(2b) Indophenol spot test
Reagent: 1 % sodium nitrite in Conc.
H2SO4 Change in colour Phenol present
Compound + 1 drop of above reagent, Violet or reddish yellow or Cresols present
allow to stand for few minutes, dilute reddish pink
with a drop of water →color develops.
Add few drops of 4N NaOH soln. and Green colour α - naphthol
allow it to stand
3. Neutrals
(3a)Aldehyde and Ketone:
(i) 2,4-DNP test
Compound + 7-8 drops of freshly Yellow to red ppt. Aldehyde or Ketone present
prepared Conc. 2,4 – dinitrophenyl
hydrazine, shake well and dilute with
water
(ii) Silver mirror test
Aldehyde present
Tollens agent: 1 ml 5 % aq. AgNO3 + 1 Silver mirror or blackish
drop of 10 % NaOH + Conc. NH3 grey ppt.
dropwise with shaking until ppt
dissolves
Tollens reagent + Compound, shake
and allow it to stand for 10 minutes ( If
no reaction, then warm for few
minutes)

(iii) Bisulphite addition complexes for

Aldehyde present
aldehyde:
Crystalline ppt.
Reagent: Mixture of 1 – 5 cm3 of
ethanol and 6 cm3 of 40 % aq. Soln. of
sodium bisulphite, filter if required
Solution of compound in ethanol (1
mL) + 3 drops of above reagent, mix
(iv) Enolisable ketone Aliphatic ketone present
1 drop of 1 % soln. of m- Violet to red colour
dinitrobenzene in alcohol + 1 drop of
KOH in methanol + 1 drop of
compound, warm CH3CO - group present.
Red or blue colour
(v) Methyl ketone
1 drop of compound + 1 drop of freshly
prepared sodium nitroprusside soln. +
1 drop of 30 % NaOH soln., stand it for
few seconds + 1 drop of glacial acetic
acid.
(3b) Alcohols
(i) 1 – 2 drops of liquid in a fusion tube Effervescence due to Alcohols present
+ a small piece of dry sodium metal evolution of H2 gas
(ii) Ceric ammonium nitrate test
5 drops of Ceric ammonium nitrate Colour changes from Alcohols present
reagent + 1 –2 drops or 5 mg yellow to red.
compound, stir (if alcohol is water (Phenols give brown
insoluble, add 3 – 5 drops of dioxane)
coloured ppt)

(3c) Esters
(i)0.1 ml or 10 mg compound + water / Pink colour disappears Esters present
ethanol just to dissolve it + 1 drop of
phenolphthalein + 0.5 % NaOH till
pink colour develops, heat in water
bath
(3d) Carbohydrates
Molisch test:
10 mg compound + 5 ml water + 2-3 Red ring changing to violet Carbohydrates present
drops of 10 % soln. of α – naphthol in at the junction of two layers
alcohol + add conc. H2SO4 from the
side of test tube
(3e) Hydrocarbons
(i) Crystal of iodine + 2 -3 drops of (i)Brown colour Compound with π –
liquid electrons or n – electrons
(ii) Violet colour like, alkanes, arenes,
aromatic hydro--carbons
present(i.e. – ve test)
(ii) Conc. H2SO4 test:
Alkanes, alkyl halides or
2 drops of cold conc. H2SO4 + 1 drop Insoluble in acid
aromatic hydrocarbons
of compound
present

(iii) Bayer Test for unsaturation:

Discharge of purple colour, Unsaturated hydrocarbons
0.5 ml acetone + 2 drops of liquid or 10 brown ppt of Mn - oxide
present
mg solid + dropwise addition of 1 %
aq. KMnO4.
Tests for compounds under C, H, (O), N Elements:
1. Acids and phenols
Compound + few drops of dil. (i) Compounds dissolve with Nitrophenols may be present
NaOH soln. deepening of colour [Perform -NO2grp. test given
below in (2b) (i) & (ii)]

(ii)Compound dissolves Nitro- or amino- carboxylic

without any change in colour acids present (perform -
NO2grp. test as given below in
(2b) (i) & (ii) and –NH2grp. test
given below under (2a) (i), (ii)
&(iii)
(iii) Insoluble Acids and phenols absent
2.Bases
(2a) Tests for amines ( primary, secondary and tertiary amine)
(i)Compound + 0.5 ml 10 % Blue green colouration or ppt Amines present
CuSO4 soln.

(iii)Azo-dye test
Take three test tubes (tt).
i) Orange – red colouration at Primary amine (-NH2 gr.)
✓ Add compound + 1:1 HCl in
boundary because of orange- present
the first tt.
red dyestuff formed.
✓ Take half a spatula solid
sodium nitrite (NaNO2) + 3-
4 cm3 water in second tt. ii) Yellow oil or yellow solid Secondary amines (>NH)
Prepare clear solution. obtained not turning greenish present
✓ Dissolve1/4thspatula of β- on addition of excess of NaOH
naphthol in 3-4 cm3conc. soln.
NaOHsoln. in the third tt.
✓ Cool all the test tubes in ice iii) Yellow oil or solid turning Tertiary amines present
bath. greenish on addition of excess
✓ Add solution in 2nd test tube of NaOH soln.
in 1st test tube kept in ice
bath. Mix them properly.
✓ Add the contents of the 3rd
test tube in the mixture (1sttt)
(2b) Test for Nitro (- NO2)
group
(i) Ferrous hydroxide test
Red-brown ppt Nitro group present
Dissolve compound in acetone +
0.4 ml of freshly prepared 5 %
aq. Ferrous ammonium sulphate
+ 1 drop of 3 N H2SO4 + 10
drops of 2 N methanolic KOH,
 shake well and allow it to stand
for 5 minutes

(ii) Neutral reduction test

Compound + 5 ml 50 % alcohol Black or grey ppt Nitro group present
+ a grain of NH4Cl solid + a
grain of Zn-dust, heat, cool,
filter (use Pasteur pipette with
cotton plug) add and into it few
drops of Tollen’s reagent

Tollens agent: 1 ml 5 % aq.

AgNO3 + 1 drop of 10 % NaOH
+ Conc. NH3dropwise with
shaking until ppt. dissolves

3. Neutrals
(3a) Test for amides, ammonium salts and nitriles

(i) Hydroxamate test for

amides
Compound + 0.5 ml 1M Reddish purple or reddish Amides present
hydroxylamine hydrochloride + brown colour
propylene glycol soln. heat to
boil for some time. Cool to
room temp. + 1-2 drops 5 % aq.
FeCl3 soln.

(ii) Alkaline hydrolysis

Formation of blue colour Amides, ammonium salts,
Compound + 0.5 ml 20 % NaOH
(aq.)soln. Heat to boil, moisten a nitriles present.
strip of filter paper with 2 drops
of 10% aq. CuSO4 soln. and
place it over the mouth of the
test tube.

(3b) Test for Nitrohydrocarbons

Perform test for nitro (-NO2)
grp. as given in 2b, i.e.
(i) Ferrous hydroxide test
(ii) Neutral reduction test
(iii) Sodium hydroxide colour
test:
Take compound in 1 ml acetone
(i) No colour Mono-nitro compound present
+ 0.2 ml 10 % aq. NaOH
solution, shake well (ii) Bluish purple colour Di-nitro compound present
 NOTE: This test is to be used for (iii) Blood red or green colour Tri-nitro compound present
only aromatic nitro compounds
in order to determine the no. of
nitro groups on the ring. Test
will be positive if compound
contains amino or hydroxyl grp.
(3c) Test for Anilides(C6H5NHCO-)
Take three test tubes (tt).
✓ Add compound + 3-4 drops Orange-red dyestuff Anilides present
of conc. H2SO4 in the first tt.
✓ Take half a spatula solid
sodium nitrite (NaNO2) + 3-
4 cm3 water in second tt.
Prepare clear solution.
✓ Dissolve1/4thspatula of β-
naphthol in 3-4 cm3 conc.
NaOH soln in the third tt.
✓ Cool all the test tubes in ice
bath.
✓ Add solution in 2nd test tube
in 1st test tube kept in ice
bath. Mix them properly.
✓ Add the contents of the 3rd
test tube in the mixture (1sttt)

Tests for compounds under C, H, (O), X Elements (where, - X = - Cl, -Br, or – I):
1-2 drops or 10 mg of (i) White or yellow ppt Aliphatic or alkyl halides
compound + water / alcohol till present
it dissolves + NaOH, boil till
clear homogeneous soln. is (ii) No white or yellow ppt. Nuclear substituted aromatic
obtained, cool and acidify with halogen compound present.
dil. HNO3 + AgNO3 soln.

*In addition to above test, all tests given under C, H, (O) elements page no.___ are to be carried
out to determine the functional group.
Tests for compounds under C, H, (O), N, X Elements (where, - X = - Cl, -Br, or – I):
The compounds under this group consists of halogenated nitrocarboxylic acids, halogenated
nitrophenols, halogenated amines, halogenated amides, halogenated anilides, halogenated amino
carboxylic acids, halogenated aminophenols, halogenated nitro compounds and halogenated azo
compounds.
The individual halogen is identified in the sodium fusion test under Elemental analysis.
All the tests given under C, H, (O), N elements Page no. ____and C,H,(O), X elements page no.___
should be carried out to determine the functional group.

Tests for compounds under C, H, (O), S elements:

The compounds under this group consist mainly of sulphonic acids, thiohydrocarbons, thiophenols etc.
Compound + sat. NaHCO3 soln. Effervescence Sulphonic acid present

Compound + NaOH + lead Black ppt Thioamide present

acetate and heat

Besides the above tests, all other tests given under C,H,(O) elements page no. ____ should also be
carried out to determine the functional group. If all the tests are negative, then the compound must be
thiohydrocarbon.

Tests for compounds under C, H, (O), N, S Elements:

The compounds under this group consist mainly of aminosulphonic acids, thioamides.
All the tests given under C,H,(O),N elements page no. ___ and C,H,(O),S elements page no. ___should
be carried out to determine the functional group.

(E) Physical constant: m.p. / b.p. ______oC

(F) Results
(1) Solubility in water and chemical Nature

(2) Elements

(3) Functional group

(4) Melting / Boiling point