Systematic Qualitative Identification of Organic Compounds

✓ Sample No. :
✓ Date of Experiment :
✓ Date of submission :
1. Preliminary examinations:
(a) Physical state : Solid/liquid/powder solid/crystalline solid, etc.
(b) Color : --------------------------------------------------------
(c) Odor : --------------------------------------------------------
2. Physical constants:
(a) Melting point : …… C
(b) Boiling point : …… C
3. Solubility test:
To 0.1 g of the sample in a test tube, add portionwise 2 mL of solvent (H2O, 5% HCl, 5% NaOH, etc.),
and shake vigorously. If the sample dissolves completely, record it as soluble. Record the solubility in
different solvents in the tabular form and mention the nature of the sample given.

Solvent Water 5% HCl 5% NaOH 5% NaHCO3 Class

A = Acidic
B = Basic
Solubility + ve / - ve + ve / - ve + ve / - ve + ve / - ve
N = Neutral
Am = Amphoteric

4. Elementary analysis:
Preparation of stock solution:
To start, place a clean and dry piece of sodium into a fusion tube. Heat the lower part of the tube until
the sodium melts. Then, add a small amount of the sample and heat again until the bottom of the tube is
heated to a dull red. While the tube is still red hot, carefully drop it into a mortar that contains about 3-4
mL of distilled water. Use a pestle to break up the tube well and filter the solution. Use the filtrate,
which is also known as the “stock solution”, for the tests described below.
Experiment Observation Inference
(a) Test for nitrogen: Prussian blue precipitate or Nitrogen is
Take 1-2 mL of the stock solution into a test color appears. present.
tube, then add a freshly prepared ferrous
sulfate (FeSO4) solution (~1 mL) and boil for
1 minute. Cool the solution and to it add
conc. H2SO4 (2-3 drops).
Note:
Sodium reacts with organic compounds containing S, N, and halogens giving NaCN, Na2S, and NaX
respectively (X = Cl, Br, I, and F).
Na+C+N = NaCN (Sodium cyanide)
Na+C+N+S = NaSCN (Sodium sulphocyanide/sodium thiocyanide)
2Na+S = Na2S (Sodium sulphide)
2Na+X = NaX (Sodium Halidide)
[Excess of the sodium reacts with water to form sodium hydroxide (NaOH). This sodium hydroxide then
reacts with iron (II) sulfate (FeSO4) to form a precipitate of Fe(OH)2 + (Na2SO4)].
2NaCN+FeSO4 → Na2SO4+ Fe(CN)2
Ferrous cyanide
4NaCN+Fe(CN)2 → Na4[Fe(CN)6]
Sodium ferrocyanide
Some of the ferrous sulfates are oxidized with the oxygen of the air and become ferric sulfate [Fe2(SO4)3]
which reacts with sodium ferrocyanide to give ferric ferrocyanide which is Prussian blue or blue.
3Na4[Fe(CN)6]+2Fe2(SO4)3 → Fe4[Fe(CN)6]3+Na2SO4
Ferric ferrocyanide
(Prussian blue or blue)

Experiment Observation Inference

(b) Test for halogens: A white, curdy ppt. is formed, which is Chlorine is
Acidify the stock solution with soluble in NH3 solution. present
dilute nitric acid (HNO3), A pale-yellow ppt. appears, which is sparingly Bromine is
carefully boil for 6-7 minutes, and soluble in NH3 solution. present
then add silver nitrate solution A yellow ppt. is produced, which is insoluble Iodine is
(AgNO3). in NH3 solution. present

Note:
Heat the stock solution with diluted nitric acid (HNO3) to boiling to remove nitrogen as hydrogen
cyanide (HCN) and sulfur as hydrogen sulfide (H2S) gas. This step is crucial because if nitrogen and
sulfur are present and not eliminated, they can lead to the unwanted formation of a silver cyanide
(AgCN) precipitate during later halogen testing. This removal process ensures that subsequent halogen
tests are accurate and unaffected by the presence of nitrogen and sulfur contaminants.
NaX+ AgNO3 = AgX↓+ NaNO3
AgCl → White curdy ppt.
 AgBr → Pale yellow ppt.
AgI → Yellow ppt.

Experiment Observation Inference

Nature of halogen: White, yellow, etc. Halogen is attached
Dissolve a small amount of the sample in ethanol. ppt. to the side chain.
Then, add an alcoholic silver nitrate solution and
shake the mixture well.

Note:
C6H5CH2X+ AgNO3 = C6H5CH2NO3 + AgX↓

Experiment
Observation Inference
(c) Test for sulfur:
(i) Take ~1 mL of the stock solution into a test A black ppt. is produced. Sulfur is
tube, acidify the solution with diluted acetic acid present
(CH3COOH), and then add the lead acetate solution.
(ii) Take ~1 mL of the stock solution into a test A deep-reddish violet Sulfur is
tube, and then add two drops of sodium coloration is produced. present
nitroprusside solution.
(iii) Test for sulfur and nitrogen together: A blood-red coloration is Both S and
Acidify the stock solution with dil. HCl and then add produced. N are present
5% FeCl3 solution.

Note:
Sodium reacts with organic compounds containing S, N, and halogens giving NaCN, Na2S, and NaX
respectively (X = Cl, Br, I, and F).
Na2S+ (CH3COO)2Pb → PbS↓+2CH3COONa
Lead acetate Black ppt. of Lead sulfide
Sodium nitroprusside reacts with sodium sulfide (Na2S) forming a complex compound that is Deep violet
indicating the presence of sulphur.
Na2S+ Na2[Fe(CN)5NO] → Na4Fe(CN)5.SNO
Sodium nitroprusside Complex
If an organic compound contains both Sulfur (S) and Nitrogen (N) elements together, it reacts with sodium
(Na) during fusion and forms sodium thiocyanate (NaCNS). Furthermore, it reacts with ferric ions (Fe3+)
and turns into a blood-red color, indicating the presence of both sulfur and nitrogen elements in the
compound.
NaCNS+FeCl3 → [Fe(CNS)Cl2]+NaCl
Thiocyanatoiron (III) chloride (blood-red)
3NaCNS+FeCl3→ Fe(CNS)3+3NaCl
Ferric thiocyanate (red)
5. Test for functional groups:
Experiment
Observation Inference
(A) Test for unsaturation:
(i) Dissolve ~0.2 g of the sample in ~2 mL The color of the bromine is Unsaturation
CCl4 and add a 2% solution of bromine in CCl4 discharged. is present
solution dropwise.
(ii) Dissolve ~0.2 g of the sample in acetone or The color of the KMnO4 is Unsaturation
water and add a 2% solution of KMnO4 solution discharged. is present
dropwise.

Note:
R1 C C R2 Br2 R1 CH HC R2
CCl4
H H Br Br
Colorless dibromo
compound

R1 C C R2 KMnO 4 R1 CH HC R2

H H OH OH

Experiment Observation Inference

(B) Test for primary amine (-NH2): An orange-red ppt. or color is -NH2 group
Dissolve or take a small amount of the sample in produced. is present
a dil. HCl and 10% NaNO2 (sodium nitrite)
solution slowly. Transfer a few drops of this
solution to a test tube containing an alkaline β-
naphthol solution.

Note:
+ –
NH2 N NCl

+ HCl + NaNO2 + NaNO2

A diazonium salt
Aniline
– +
Cl N N N N
ONa ONa
+
+ HCl

Sodium 1-(phenyldiazenyl)naphthalen-2-olate
 Experiment
Observation Inference
(C) Test for secondary amine:
(i) Dissolve or take some amount of the sample The formation of oily liquids or -NH- might
in dil. HCl and add an excess amount of 10% solids confirms secondary amine be present
NaNO2 (sodium nitrite) solution. which can be further confirmed
by the Liebermanns nitroso test.
(ii) Liebermanns nitroso test: An intense blue coloration will -NH- is
Extract the above oily liquids or solids with ether be developed, changing to pale present
and wash the extract successively with water, dil. red on dilution with water and
NaOH and water. Evaporate the ether layer on a turning green upon adding an
watch glass. Add 2-3 drops of phenol and heat for excess NaOH solution.
30 seconds. Add 2-3 drops of conc. sulphuric acid
(H2SO4).

Note: NO
NH N
HNO3
HCl

OH
H2SO4 HONO
NO OH

OH H , H2SO4 -
+
HON O OH N OH HSO 4

Blue green

H2 O NaOH
OH N O
Excess
Indophenol, Pale yellow

+ –
Na O N O

Indophenol anion, blue

Experiment Observation Inference

(D) Test for tertiary amine (>NH-): Green crystals form. >NH- group
Dissolve a small amount of the sample in dil. is present
HCl and add a sufficient amount of 10% NaNO2
solution. Solid ppt. obtained is heated with 10%
NaOH.

Note:
The greenish solids which on reduction with Zn and HCl yield the corresponding derivative of p-
diamines. These p-diamines on diazotization give intense color with alkaline β-naphthol.
 Experiment
Observation Inference
(E) Test for substituted amide (-NHCOR):
(i) Boil the sample with 20% NaOH soln for 7- An orange-red color develops on -NHCOR
8 min. and absorb the liberated amine on the filter the filter paper. group is
paper soaked with dil. HCl and 10% NaNO2 soln. present
Then add alkaline β-Naphthol soln to the filter
paper.
(ii) Boil the sample with 20% HCl for 7-8 min. An orange-red color or ppt. -NHCOR
and cool the soln under the tap water. Add 10% develops. group is
NaNO2 soln. Transfer this solution to a test tube present
containing alkaline β-naphthol soln.

Note:
(a)
Heat
NH COR + NaOH NH2 + RCOONa

HCl
NH2 Diazotization Diazocoupling
NaNO2

(b)
Heat
NH COR + HCl NH2 . HCl + RCOOH

NH2 . HCl Diazotization Diazocoupling

NaNO2

Experiment Observation Inference

(F) Test for the nitro group (-NO2): An orange-red ppt. or color -NO2 group
Boil the sample with granulated tin (Sn) and develops. is present
conc. HCl for 7--8 min. and cool the soln in an
ice bath. Dilute the soln (with water) and add
10% NaNO2 soln. Transfer the soln immediately
to a test tube containing alkaline β-naphthol soln.

Note:
Reduction
NO2 + Sn + HCl NH2

HCl
NH2 Diazotization Diazocoupling
NaNO2
 Experiment
(G) Test for simple amide -CONH2 and Observation Inference
simple imide -CONHCO-:
Boil the sample with 20% NaOH in a test tube A red litmus paper -CONH2 (simple amide) or
carefully and test whether the gas coming out of is turned to blue. -CONHCO- (simple imide)
the test tube turns the moistened red litmus paper group is present
blue.
Differentiation between simple amide and simple imide:
Add the sample's saturated solution in absolute A silky white ppt. Imide group is present
alcohol to a saturated solution of KOH in absolute appears
alcohol. No ppt. is Amide group is present
observed

Note:
O H2O
C NH2 + NaOH COONa + NH3

O O

H2O ONa
NH + NaOH + NH3
ONa

O O
O O

abs. alc.
NH + KOH N K

O O
K salt
Phthalimide Silky white ppt.

Experiment
Observation Inference
(H) Test for carbonyl group >CO:
Dissolve a considerable amount of the sample in 2 An orange-red crystalline >CO group is
mL of rectified spirit (apply heat if necessary to aid ppt. is produced present
dissolution). Then, add an excess of 2,4-
dinitrophenylhydrazine (DNPH) solution. Allow
the reaction mixture to stand placing the beaker in
cold water.
Differentiation between aldehydes and ketones:
a) Fehling's solution test: A pink ppt. is formed An aldehyde is
Apply Fehling's solution to the sample (by mixing present
equal volumes of Fehling's solutions A and B), then No pink ppt. is formed A ketone is
heat in a water bath for 4-5 minutes. present
Tollen’s reagent test: A silver mirror forms on An aldehyde is
Place a small quantity of the sample into Tollens' the inside wall of the test present
reagent (prepare the reagent freshly) and observe tube
 the reaction at room temperature. If no reaction Silver mirror is not A ketone is
occurs at room temperature, gently heat the solution formed present
in a hot water bath.
Schiff's reagent test: A pink is formed An aldehyde is
Add a small amount of the sample in 2 mL of present
Schiff's reagent and shake the mixture well. No pink color is formed A ketone is
present

Note: NO2
NO2

O 2N NH N C
O 2N NH NH2 + C O
2,4-Dinitrophenylhydrazone
2,4-Dinitrophenylhydrazine

Differentiation:

(a) RCHO + Cu(OH) 2 + NaOH RCOONa + Cu2O +NaOH + 3H2O

(Brick red)

(b) RCHO + Ag(NH 3)2OH RCOONH4 + Ag +NaOH + H2O + NH3

(Silver mirror)

Experiment Observation Inference

(I) Test for the carboxylic group (-COOH): The sample dissolves with -COOH
Add a small amount of the sample to a cold effervescence of CO2 which turns group is
solution of 5% NaHCO3 or a warmed solution of lime water milky. present
conc. NaHCO3 (sodium bIcarbonate) solution.

Note:
R-COOH + NaHCO3 → R-COONa + CO2↑ + H2O

Experiment
Observation Inference
(J) Test for the phenolic -OH:
(i) Dissolve a small amount of the sample in An intense coloration (purple, Ar-OH group
rectified spirit and then add a 5% FeCl3 solution blue, red, Violet, green, etc.) is is present
to it. observed.
(ii) Schotten-Baumann test: A white ppt. appears. Ar-OH group
Dissolve the sample in approximately 2 mL of a is present
20% NaOH solution, then add an excess of (Aromatic)
benzoyl chloride to it and shake vigorously.

Note:
H 5 C6 O OC6H5
(a) C 6H5OH + 2FeCl3 H 5 C6 O Fe Fe OC6H5

H 5 C6 O OC6H5
Iron complex
 NaOH
(b) C6H5OH + C6H5COCl R-COONa + CO2↑ + H2O

Experiment
Observation Inference
(K) Test for the esters and anhydrides:
(i) Dissolve a small sample of the A pronounced coloration A phenolic sample is
compound in water or rectified spirit, and add (violet, blue, red, purple, orpresent. The
1N of hydrochloric acid (HCl). Then, green color) appears. hydroxamic acid test
introduce 1-2 drops of a 5% solution of ferric described below is
chloride (FeCl3) Soln. not applicable and
should not be carried
out.
(ii) The hydroxamic acid test: Burgundy (French wine) or Ester and anhydride
Mix a small sample of the compound with 2 magenta color will be are present
mL of hydroxylamine hydrochloride in 95% produced. (anhydrides
ethanol and 20% NaOH solution until the generally have high
solution becomes alkaline (as indicated by red melting points).
litmus paper). Boil the mixture for 10 to 12
minutes, then cool it. If the solution turns
cloudy, add another 2 mL of 95% ethanol.
Next, acidify the solution with hydrochloric
acid (HCl) until it becomes acidic (as
indicated by blue litmus paper). Finally, add
2-3 drops of a freshly prepared 5% solution of
ferric chloride (FeCl3).

Note:
O OH NH2 O OH
R C OEt R C NHOH R C NOH
Keto form Enol form
–
OH O
3+
R C NOH + FeCl3 R C NOH Fe
Enol form 3

Experiment Observation Inference

(L) Test for the aromatic hydrocarbon: Orange red needle- Aromatic
Dissolve a small amount of the sample in shaped crystalline ppt. is hydrocarbon is
absolute alcohol and then add a saturated formed. present.
solution of picric acid in absolute alcohol.

Note: OH OH
O 2N NO2 O 2N NO2
+ .

NO2 NO2
Picric acid Anthracene Picrate derivative
A molecular compound
6. Name of the functional group or groups:
Following a thorough analysis, the organic sample is identified to contain elements N/X/and or S and
functional groups such as -NH2, -NO2, and or, COOH, >C=O, etc. The determined melting point, as
observed from the melting point chart, corresponds to that of the compound known as [-----Name of the
Organic Sample].
7. Derivative preparation:
8. Conclusion:
9. Name of the sample:
10. Structure of the sample: