Dr.Mohammad Idrees and Dr.Naqui.J.

Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Identification of Organic Compound by Organic Qualitative

Analysis

A Systematic Scheme for the identification of the organic compound is outlined below.

1. Preliminary Test
2. Solubility Test
3. Detection of Extra Elements
4. Detection of Functional Group
5. Determination of physical constant and Identification of the compound.
6. Confirmatory Test.
7. Derivatives preparation and its m.pt determination .

1. Preliminary Test

Test Observation Inferences

i) Solid Carbohydrate, acid , phenol, amine ,
(a) Nature higher hydrocarbon may be present.
ii) Liquid Alcohol , ketone , aldehyde, ester,
phenol, amines may be present.

m- Dinitrobenzene, p- Nitro toluene,

i) Yellow -Solid nitro phenol , nitro aniline.
ii) Yellow -liquid Nitrobenzene.
(b) Colour iii) Brown P – Toluidine , resorcinol.
iv) Blackish α – Naphthol
v) Pink ß – Naphthol
vi) Buff or reddish Aniline, phenol, Aromatic amine.
vii) Colourless Simple acid , alcohol, ester, ketone
aromatic hydrocarbon.

i) Carbolic Phenol, cresol.

ii) Fishy Amine
(c) Odour iii) Sweet pleasant Ester, alcohol and halogen derivatives.
iv) Bitter almonds Nitrobenzene,Benzaldehyde
v) Moth balls Naphthalene
vi) No particular smell Aromatic acid ,amide, carbohydrate.

Aromatic compound or aliphatic

i) Sooty flame compound containing small proportion
(d) Flame Test of hydrogen e.g . CHCI3,CCI4
ii) Non sooty flame Aliphatic compound
iii) Substance chars Carbohydrate, sulphanilic acid.

( f) Test for unsaturation i) Decolourisation of KMnO4 Unsaturated or easily oxidizable

1. KMnO4 test. compound.
Substance + 2 ml of water
shake well + 2 drops of
dilute KMnO4 solution. ii) No decolourisation Saturated compound.

2. Bromine water Test. i) Decolourisation of bromine Unsaturated compound.

Substance + 2 ml of water water.
shake well + 2 drops of ii) Decolourisation with Easily substituted compound.
bromine water. formation of precipitate.
iii) No decolourisation. Saturated compound.
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

2. Solubility Test

(A) Perform the following test only if the substance is soluble /miscible in water
Test Observation Inferences

(a). 0.1gm of substance + 3ml of Substance dissolves Lower member of alcohol, ester
water shake well. ketone, carbohydrate.
Test the solution with litmus i) Blue litmus paper turns red Water soluble acid or phenol present.
paper. ii) Red litmus paper turns blue Water soluble base present
iii) No action on the litmus paper Water soluble neutral present

(b). 0.1gm of substance + Saturated

NaHCO3 solution. Strong
effervescence and substance
dissolves.

To this clear solution add conc. HCl No solid appear Water soluble acid present

(c). 0.1gm of substance + water

shake well, substance dissolves.

To this clear solution add alcoholic

FeCl3 Solution. Blue to violet colour Water soluble phenol present

(B) Perform the following test only if the substance is insoluble / immiscible in water
(a) 0.1gm of substance +3 ml Carboxylic acid present.
Saturated NaHCO3 solution. Strong effervescence
Shake well. The substance
dissolves.
To this clear solution add conc. A solid appear Carboxylic acid confirmed.
HCl drop by drop.

(b) 0.1gm of substance +3 ml dilute

NaOH solution.,Shake well.
The substance dissolves.
To this clear solution add conc.
HCl drop by drop. A solid or emulsion appear Phenol present

(c) 0.1gm of substance +3 ml 1:1

HCl solution. Shake well. The
substance dissolves.
To this clear solution add 20%
NaOH solution drop by drop. A solid appear Base confirmed

(d) If substance is insoluble in

NaHCO3,NaOH, HCl solution. …………. Neutral compound present

3. Detection of Extra Elements

Sodium Fusion Test (Lassaigne’s Test)

1. Take a small piece of dry sodium metal in a fusion tube and heat it gently till the metalmelts or fuses.
2. Add equal quantity of compound to this fused metal [ If he compound is a liquid then add two drops
of it with a capillary]
3. Heat it gently then strongly till it becomes red hot.
4. Plung the red hot tube in 10 ml or ¾ of a test tube of distilled water taken in a porcelain dish,covering it immediately
with an asbestos sheet crush the fusion tube completely.
5. Carry out more fusion in the similar way. Boil the extract for five minutes reduce the volume to about 5 ml and filter.
Perform fpllowing test using this filtrate.
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Detection of Elements

Test Observation Inferences

Test for Nitrogen

1 ml of extract + 2-3 drops of NaOH solution

tomake it alkaline + a few drops of freshly Blue or green colour solution Nitrogen present.
prepared FeSO4solution ,boil for afew or Prussian blue coloration.
minutes ,cool and acidify it with by adding
dil.HCl or dil. H2SO4.

Test for Sulphur

(i) 1 ml of extract +1 ml of 2N Acetic Acid + A black precipitate. Sulphur present.

1 ml of Lead Acetate Solution.

(ii) 1 ml of extract + 1 drop of sodium A violet or purple coloration. Sulphur present.

nitroprusside solution.

(iii) 1 ml of extract + 1 ml of aqueous FeCl3 A blood red coloration Nitrogen and Sulphur are
solution. present.

Test for Halogen

(i) 1 ml of extract +1 ml of dilute HNO3 (boil A thick white precipitate. Halogen present.
well if N and S are present) + 1 ml of 5%
AgNO3 solution.

(ii) If halogen is present carry out the (i) Violet colour Iodine present.
following test:
1ml of extract + 1ml of dilute H2SO4 +0.5ml
of CHCl3 and 0.5ml of chlorine water ,shake (ii) Yellow or brown colour. Bromine present.
well and observe the colour of chloroform
layer.
(iii) Colourless layer Chlorine present.

Classify the given compound on the Basis of Element Present

On the basis of the elements present in the organic compound ,it belongs to one of the four
groups,which may be further divided in subgroups are follows :

Group I : C, H, (O) Group III : C, H, (O),N and S

(i). Carboxylic acids (i). Acids

(ii). Phenol (ii). Neutrals
(iii). Neutrals

Group II : C, H, (O) and N Group IV : C, H, (O) and Halogen

(i). Carboxylic acids (i). Neutrals
(ii). Phenols
(iii). Bases
(iv). Neutrals
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

4. Detection of Functional Groups

Group I : C, H, (O) Carboxylic acids

Test Observation Inferences
(a) 0.1gm of substance +3 ml Saturated Strong effervescence Carboxylic acid present.
NaHCO3 solution. Shake well. The
substance dissolves.
To this clear solution add conc. HCl drop A solid appear Carboxylic acid confirmed.
by drop. [ F.G COOH ]

(b) 0.05 gm of compound + 1ml of water , 1. Buff coloured precipitate Benzoic acid or phthalic acid.
shake well + 1-2 drops of alcoholic ii. Violet coloured precipitate Salicylic acid
FeCl3 solution. iii. Violet coloured precipitate Acetyl salicylic acid
obtain on heating the solution
iv. Yellow coloured precipitate Cinnamic acid
v. Faint reddish coloured Succinic acid
precipitate
vi. Deep yellow coloured solution Citric acid
vii. No change in FeCl3 solution. Oxalic acid
Group I : C, H, (O) Phenol
(a) 0.1gm of substance +3 ml dilute NaOH Compound dissolves completely.
solution. Shake well. Phenol present
To this clear solution add conc. HCl drop A solid or emulsion appear
by drop.

(b).0.01gm of compound + 3ml of water or

alcohol shake well and add a drop of i. Violet Colour Phenol Present
alcoholic or neutral FeCl3 solution. ii. Blue Violet Colour Resorcinol
Iii . White ppt slowly changing to α - napthol
pink, blue or violet
iv. Green Colour ß - napthol

(c). Phthalein test

0.01gm of compound + 0.01gm of phthalic Pink colour Phenol Present
anhydride + 2 drops of conc. H2SO4.Heat Green or bluish green α - napthol
gently until the mixture fuses. Cool and pour ß - napthol
it in a beaker containing 20 ml ogf very Yellowish-green flouresence Resorcinol
dilute NaOH solution.

(d).Liebermann test. Red colouration

0.01gm of compound+1ml of conc. H2SO4 + Bluish greenish coloration [ F.G OH (Phenolic) ]
2 crystal of NaNO2. Heat it gently.
Dilute it with water , add 20% NaOH
solution.
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Group I : C, H, (O) Neutrals

Test Observation Inferences
(a)Teat for Carbohydrates
Molish Test : ( Perform this test only if the
compound is colorless and soluble in water ) A Violet ring appears at the Carbohydrate present
Dissolve 0.5 gm of the compound in 2ml of junction of two layers.
water + 2/3 drops of 10% α-napthol dissolved
in ethyl alcohol, add carefully 1 ml of
conc.H2SO4 along the sides of the test tube.

(b)Test for Aaldehydes and Ketones. Yellow or orange red crystalline Aldehyde or Ketone Present
(i) 0.05 gm of the compound + 3 ml of 2,4 precipitate
dinitrophenyl hydrazine. Shake well.

If this test is positive, perform the following test to distinguish between aldehyde and ketone.

Test for Aldehydes : Viotet colour immediately Aliphatic aldehyde present

(i) Schiff’s Test develops
0.05 gm of the compound + 2/3 ml of
Schiff’s Reagent .Shake well. Pink colour slowly develops Aromatic aldehyde present

(ii) Tollen’s Test OR Silver Mirror test: A silver mirror is formed on the
0.1 gm of the compd +2-3mlTollents reagent inner sides of the test tube
(i.e. Ammonical silver Nitrate solution) +
Heat it on a boiling water bath. Aldehyde present

(iii) Fehling Solution Test Formation of red ppt of Cuprous [ F.G CHO ]
0.1gm of the compd + 1ml Fehling A + 1ml oxide
Fehling B solution .Heat it gently

(iv) Benedict’s test Formation of red ppt

0.1gm of the compd + Benedicts solution + Cuprous oxide
Heat it gently.
Teat for Ketones : Wine Red colour or Orange red Ketone present
0.1gm of compd + 2ml of sodium colour
nitroprusside solution + 2 drops of NaOH CH3-CO- gr gives this test [ F.G C=O ]

(c). Test for Esters

Dissolve 0.1gm or 0.5ml of compound in 1
ml of ethyl alcohol + a drop of Pink colour disappears Ester present
phenolphthalein + 2 drops of very dilute
NaOH solution. Heat on a boiling water bath.
(d).Test for Alcohols
(i). Take a small piece of dry Na metal in a Rapid evolution of H2 Alcohol present
fusion tube and add a few drops of
compound.
(ii). 1ml of acetyl chloride in a dry test tube + Strong effervescence Alcohol present
drops of the compound.
e). Test for Hydrocarbons
0.5ml of compound + 1 ml of iodine in Purple colour of CS2 layer Ether present
carbon disulphide, shake well changes to brown colour

(f). Test for Hydrocarbons If all the above tests fail Hydrocarbon present
0.1gm of compound + 1-2 ml of water, Decolourisation Unsaturated hydrocarbon
shake well + 1-2 drops of very very dilute present
KMnO4 solution. Shake again. No decolourisation Saturated hydrocarbon
present
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Group II : C, H, (O) and N Carboxylic acids

Test Observation Inferences
i) 0.1 gm of the compd + 2/3 ml of sat Strong effervescences and Nitro-Carboxylic acid or
NaHCO3 solution. Shake well . compound dissolves. amino carboxylic acid present
To this clear solution add conc. HCl drop by Solid appears Nitro-Carboxylic acid present
drop No solid appears Amino carboxylic acid present
ii) If nitro carboxylic acid is present, perform
the following test of nitro group –
a) Test for nitro group – 0.2 gm of the compd
+ 2 ml of ethyl alcohol + 0.1 gm of solid Black or grey precipitate Nitro group present.
NH4Cl + 0.1 gm of Zn dust. Boil for 5min
and filter. Filter + Tollen’s Reagent [ F.G NO2 ]

iii) If amino carboxylic acid present ,perform A clear solution is obtained Aromatic primary amino
the following test for amino gr- which when added to a cold group is present
0.5 gm of the compd +3 / 4 ml of 1:1 HCl, solution of alkaline ß-
shake well. Cool and add few drops of 2% napthol give orange red dye [ F.G NH2 ]
NaNO2 solution

Group II : C, H, (O) and N Phenols

i)0.1 gm of the compd + dilute NaOH Compd dissolves producing Nitro phenol or Amino phenol
solution deep yellow or orangecolour is present
Add conc HCl drop by drop Solid reappears Nitrophenol present
No solid reappears Aminophenol present
ii) If nitro phenol present perform the test for Black or grey ppt Nitro group present
–NO2 group as written above.
iii) If Aminophenol present, perform the test Orange red dye Aromatic Primary amino
for –NH2 , group as written above. group present

Group II : C, H, (O) and N Bases

0.5 gm of the compd +3 / 4 ml of 1:1 HCl, Compd dissolves Amines present
shake and filter. Filtrate + 20% NaOH drop Solid reappears or emulsion Amines confirmed
by drop obtained

0.5 gm of the compd +3 / 4 ml of 1:1 HCl, Deep yellow, red or green Aromatic tertiary amino group
shake well. Cool and add few drops of colour (-N-) present
2% NaNO2 solution White or yellow emulsion Aromatic secondary amino
group (-NH-) present
A clear solution is obtained Aromatic primary amino
which when added to a cold group (-NH2 ) present
solution of alkaline ß-
napthol give orange red dye
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Group II : C, H, (O) and N Neutrals

Test Observation Inferences
(1).Test for Diphenylamine
1/2 crystal of compd + 1 ml of conc.H2SO4 +
Conc HNO3. or one drop of dilute NaNO2
solution (If this test is positive,perform group Deep Blue Colour Diphenylamine present
test listed under C,H,(O) and N Basic to
confirm the functional group

(2) Test for Amides

0.2 gm of compound + 3ml of 20% NaOH Evolution of NH3(confirm Amide group present
sol .Boil for 1-2 min.Test the gas evolved - with the smell)

i). Bring a moist red litmus paper over the Red litmus paper turns blue Amide group confirmed
mouth of test tube
o
ii).Dip a glass rod in conc HCl and hold this Dense white fumes of NH4Cl [ F.G C - NH2 ]
over the mouth of the test tube are evolved on the glass rod Amide

(3) Test for Anillide

0.1gm of the compd + 1ml of conc HCl. Boil
for 2 min, cool and add 5 ml of water + a few Anilide Group present
drops of cold NaNO2 sol. And mix well. Orange red dye
Add this solution to a cold solution of [ F.G Ar - NH – CO – R ]
alkaline ß-napthol.
R → -CH3, -C6H5
(4). Test for Nitro group
(a). Mulliken’s Test
0.2 gm of the compd + 2 ml of ethyl alcohol
+ 0.1 gm of solid NH4Cl + 0.1 gm of Zn dust. Black or grey precipitate Nitro group present.
Boil for 5min and filter. Filter + Tollen’s
Reagent [ F.G NO2 ]
(b). Azo-Dye Test
(If primary amino group absent, then only
perform this test)
0.5 gm of the compd + 0.5 gm of Tin metal +
2 ml of conc HCl. Boil or 3 min, cool filter Orange red dye Nitro group present.
and dilute with about 5 ml of water +few
drops of NaNO2. Add this sol to a cold [ F.G NO2 ]
solution of alkaline ß-napthol.
(c). Test for Dinitro compound
0.5 g of the compound + 1-2 ml of acetone,
shake well to dissolve the com pound+ 1-2 Dark purple or Violet colour Dinitro compound present
drops of dilute NaOH solution.

Group III : C, H, (O) and N & S - Acids

This class includes amino sulphonic acid
1) Test for Amino Sulphonic Acid
a) 0.2 gm of the compound + 3 -4 ml of Effervescences and Amino Sulphonic acid present
saturated NaHCO3 solution. compound dissolves

b) Perform test for –NH2 group as above. Orange red dye is formed Aromatic primary amino
group present
Dr.Mohammad Idrees and Dr.Naqui.J.Siddiqui, Assistant Professor, Department of Chemistry, Institute of Science, Nagpur

Group III : C, H, (O) and N & S - Neutral

This class includes Thiourea
Test for Thiourea
Thiourea is soluble in water and neutral to
litmus paper Thiourea is confirmed
0.1 gm of comp + 2ml oof 20% NaOH S
solution, boil ,cool and add a few drops of Black ppt is obtained.
lead acetate solution. [ F.G C - NH2 ]
Thioamide
Group IV : C, H, (O) and Halogen - Neutral
0.2 gm of compd + 2-3 of ml of dilute NaOH White or yellow ppt Aliphatic halide like CHCl3
solution Boil for a few min, cool + dilute ,CCl4 present
HNO3 till acidic + 1ml of AgNO3 solution. Chlorobenzene or bromobenzene
No Precipitate.
present

5. Determination of physical constant and Identification of the compound.

Take organic compound into one end sealed capillary and determine m.pt /B pt

6.Confirmatory Test
Test.
Test Observation Inference

7.Derivatives preparation and its m.pt determination .

Results.
From the above step by step analysis of given organic compound shows
that ,it is

State :
Colour :
Odour :
Aromatic / Aliphatic :
Saturated /unsaturated :
Solubility :
Extra elements :
Functional group :
M.pt/B . pt