chemistry

PRACTICAL ORGANIC CHEMISTRY

Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

KVPY fellow
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SAKSHI SAKSHI
 POC
Practical Organic Chemistry
Qualitative Analysis of Organic Compounds
Liebig’s Test
Liebig’s Method (for determination of C and H)

O.C containing C and H 1. C + CuO ⟶ CO2

2. CO2 + Ca(OH)2 ⟶ CaCO3

CuO 3. Excess H2O + CO2 + CaCO3 ⟶ Ca(HCO3)2

H2O
CO2
Liebig’s Method (for determination of C and H)

O.C containing C and H 1. H + CuO ⟶ H2O

2. CuSO4 + H2O ⟶ CuSO4.5H2O

Lassaigne Test
Lassaigne test

P, S, N, X
1. For N

C + N + Na ⟶ NaCN (Lassaigne extract)

CN- + Fe2+ ⟶ [Fe (CN)6]4-

[Fe (CN)6]4- + Fe3+ + xH2O ⟶Fe4 [Fe (CN)6]3.xH2O

Lassaigne test

Lassaigne test is not given by NH2 - NH2

2. For X

1. The sodium fusion extract is acidified with nitric acid and then treated
with silver nitrate.
2. A white precipitate, soluble in ammonium hydroxide shows the
presence of chlorine.
2. For X

3. A yellowish precipitate, sparingly soluble in ammonium hydroxide

shows the presence of bromine.
4. A yellow precipitate, insoluble in ammonium hydroxide shows the
presence of iodine.
2. For X

Important Points
1. 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.
2. NaCN → HCN
3. Na2S → H2S
3. For S

1. The sodium 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.
3. For S

2. On treating sodium fusion extract with sodium nitroprusside,

appearance of violet colour further indicates the presence of sulphur.

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

If S and N are present together

S + C + N + Na ⟶ NaSCN

SCN- + Fe3+ ⟶ [Fe(SCN)]2+

#No Prussian blue since there are no free cyanide ions

If S and N are present together

*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 + 2Na2S

4. For P

3. The solution is boiled with nitric acid and then treated with ammonium
molybdate. A yellow colouration or precipitate indicates the presence of
phosphorus.
HNO3
Na3PO4 ⟶ H3PO4 + NaNO3
HNO3
H3PO4 + (NH4)MoO4 ⟶ (NH4)PO4.12MoO3↓
Practise Questions
An organic compound ‘A’ is oxidized with Na2O2 followed by boiling
With HNO3. The resultant solution is then treated with ammonium
molybdate to yield a yellow precipitate.
Based on above observation, the element present in the given
compound
[Main April 12, 2019 (I)]
A. Nitrogen
B. Phosphorus
C. Fluorine
D. Sulphur
Tests for Alcohols
 Chemical Tests Alcohol

1. Test For Alcohols :

Sodium Metal

● When Na-metal reacts with alcohol H2(g) evolve

● It occurs in 1º, 2º & 3º alcohols
● Other Functional groups that evolve H, are
R2NH, RSH, RC≡C-H, RCOOH etc.
CAN Test
Test for Alcohols
➔ Ceric Ammonium Nitrate Test (CAN Test) :
Test for Alcohols
➔ Ceric Ammonium Nitrate Test (CAN Test) :

➔ Positive Test: Color changes from yellow to red first then to colorless
solution. (1 min to 12 hrs)
➔ A positive test includes successively the formation and then the
disappearance of the red color.
➔ Very good test for 1o, 2o alcohol, but slow for 3o alcohol
➔ Note: Phenols gives brown or black products.
Jones Oxidation
Jones Oxidation
➔ Chromic anhydride or Chromium Trioxide (CrO3)
➔ A positive test for 10 , and 2o alcohols consists in the changes from an
orange-red color (Cr+6) to green colour (Cr+3) in 2 sec.
➔ 30 alcohols give no visible reaction
Jones Oxidation

➔ Note
➔ Aldehydes give positive result.
Jones Oxidation
Lucas Test
Lucas Test
➔ This test distinguishes 10, 20 & 30 alcohol from each other
➔ It uses, anhydrous ZnCl2 in Conc. HCl (lucas reagent)
Lucas Test

➔ 30 alcohols give White turbidity solution immediately

➔ 20 alcohols give White turbidity solution within 5 to 10 minutes
➔ 10 alcohols does not give white turbidity at normal temperature

Note :- Benzyl alcohols also reacts immediately

Victor Meyer Test
Victor-Meyer Test RBC Test
➔ This test distinguishes 1o, 2o & 3o alcohol
Periodic Acid Test
Periodic Acid (HIO4) Test for Vicinal Diols
Periodic Acid (HIO4) Test for Vicinal Diols
Periodic Acid (HIO4) Test for Vicinal Diols
Periodic Acid (HIO4) Test for Vicinal compounds
Periodic Acid (HIO4) Test for Vicinal
Compounds
 Periodic Acid (HIO4)

➔ This iodic acid is detected with 5% AgNO3 solution - an immediate

precipitation of silver iodate occurs

➔ Olefins, 2o alcohols, 1, 3 - glycols, ketones and aldehydes are not

affected by HIO4 condition
Test for Aldehydes &
Ketones
2,4 DNP Test
Classification Tests for Aldehydes & Ketones
1. 2,4-Dinitrophenyl Hydrazine

➔ Positive Test: Formation of yellow, orange or red ppt

➔ The precipitate may be oily at first and become crystalline on standing
Sodium Bisulphite
Test
Classification of Tests for Aldehydes & Ketones
4. Sodium Bisulphite (NAHSO3)

➔ Positive Test: By aldehydes and methyl ketone

Iodoform Test
Classification of Tests for Aldehydes & Ketones
5. Iodoform Test (for Methyl Ketones)
Classification of Tests for Aldehydes & Ketones
5. Iodoform Test (for Methyl Ketones)

➔ Positive Test: Yellow ppt for methyl ketones

➔ Disadvantages: Some compounds that can be easily oxidized to methyl
ketones give also positive results
➔ The principal types of compounds that give a positive test:
Practise Questions
Consider the following reaction :

JEE Main 2020

A is

JEE Main 2020

A.

B.

C.

D.
[Main Sep. 02, 2020 (II)]
[Main Sep. 02, 2020 (II)]
 Distinction b/w
Aldehydes Ketones
Test that give positive results with Aldehydes and
Negative result with Ketones

(i) Tollens Reagents Ag(NH3)2OH

● Positive Test : Formation of silver mirror (Ag(s)) or colloidal (granular)

Gray or black Ag precipitate
Test that give positive results with Aldehydes and
Negative result with Ketones

(ii) Benedict's solution

● Positive Test : yellow or yellowish green/reddish ppt.

● All aldehydes give positive result except aromatic aldehydes (negative)
Test that give positive results with Aldehydes and
Negative result with Ketones

(ii) Benedict's solution

Test that give positive results with Aldehydes and
Negative result with Ketones

(ii) Benedict's solution

Test that give positive results with Aldehydes and
Negative result with Ketones

(ii) Fehling solution : shown by aldehydes and ∝ hydroxy ketones

 Test for
Unsaturation
 Tests for Unsaturated “Alkenes & Alkynes”

1. Bromine in CCl4
Tests for Unsaturated “Alkenes & Alkynes”

1. Bromine in CCl4

● Positive Test : Bromine color discharged evolution without of gas (HBr)

● Alkenes & alkynes give positive results
● If HBr is evolved, it indicates phenols, enols & enolizable compounds
Classification Tests for Unsaturated “Alkenes & Alkynes”

2. Baeyer Test (KMnO4 aqueous)

Classification Tests for Unsaturated “Alkenes & Alkynes”

2. Baeyer Test (KMnO4 aqueous)

Positive Test: Purple color discharges, and brown color ppt (MnO,) appears

Note : Aldehydes and alcohols also give positive result

 Test for
Alkyl Halides
Tests for Alkyl Halides
(i) Ethanolic Silver Nitrate Solution
➔ The reaction of alkyl halide with silver nitrate yields a silver halide
precipitate
Tests for Alkyl Halides
➔ Positive Test: formation of ppt indicates 2o and 3° RX
➔ 1° RX, Ar-X, and vinyl halides give negative Result.
➔ Note: allylic and benzylic RX give positive result
➔ AgCl (white); AgBr (pale yellow); AgI (yellow)
Tests for Alkyl Halides
(ii) Sodium Iodide in Acetone Test

➔ The Nal test can be used to test for the presence of bromine or
chlorine.
➔ Sodium halide (NaX) precipitates from the solution.
Tests for Alkyl Halides
➔ Positive Test: precipitate forms
➔ Indications : 1°, 2° RX, allylic and benzylic halides.
➔ Not good for ArX, vinyl halides ,HCCl3,and 3° RX.
Practise Questions
Which one of the following is likely to give a precipitate with
AgNO3 solution ?

A. CH2 = CH - Cl [Main April 12,2019 (II)]

B. CCl4
C. CHCl3
D. (CH3)3CCl
 Test for
Amines and salts
Test for Amines and Amine Salts
Nitrous Acid

➔ Reaction of amines with nitrous acid (HONO) classifies the amine not only
as 1°, 2°, or 3°, but also as aliphatic or aromatic.
Test for Amines and Amine Salts
Nitrous Acid
➔ The diazonium salt of the primary aromatic amine reacts with sodium 2-
Naphthol to produce a red-orange azo dye.
Test for Amines and Amine Salts
Nitrous Acid

➔ 2° amines undergo a reaction with nitrous acid to form N-nitrosamine,

which are usually yellow solids.
Test for Amines and Amine Salts
Nitrous Acid

➔ 3° aliphatic amines do not react with nitrous acid, but they form a
soluble salt. The reaction mixture gives an immediate positive test on
the starch-iodide paper for nitrous acid.
Test for Amines and Amine Salts
Nitrous Acid

➔ 3o aromatic amines react with nitrous acid to form the orange-colored

hydrochloride salt of the C-nitrosamine. Treating the solution with base
liberates the blue or green C-nitrosamine.
Test for Amines and Amine Salts
(iii) Hinsberg Test
➔ Based on the reaction of the amine with benzenesulfonyl chloride
(Hinsberg reagent), it can be used to separate 1º, 2º, and 3º amines.

1° amines: give solution that produce ppt after addition of HCl

Test for Amines and Amine Salts
(iii) Hinsberg Test

➔ 2° amines: give ppt - acidification of the solution does not dissolve the
sulfonamide (i.e., the PPT is not soluble in NaOH or HCl)
Test for Amines and Amine Salts
(iii) Hinsberg Test
➔ 3º amines: undergo reaction with benzenesulfonyl chloride to produce
quaternary ammonium sulfonate salts, which yield sodium sulfonate
and insoluble 3° amines in basic solution.
➔ Acidification of the reaction mixture results in the formation of sulfonic
acids and soluble amine salts.
Test for Amines and Amine Salts
(v) Libermann's nitroso test :

➔ It is used as a test for secondary amines. Secondary amines(aliphatic as

well as aromatic) reacts with nitrous acid to form N-nitrosamines.

➔ Nitrosamines are water soluble yellow oils and when warmed with
phenol and few drops of conc.sulphuric acid, produce a green colour
solution which turns blue on adding alkali. This reaction is called
Libermann's nitroso reaction.
➔ Tertiary amine do not react with nitrous acid.
Test for Amines and Amine Salts
(v) Liebermann's nitroso test :
Test for Amines and Amine Salts
Sodium Metal :
➔ The active hydrogen on 1° and 2° amines undergo reaction with sodium
to form salt and liberate hydrogen gas
 Tests for Amino Acids
(i) Ninhydrin Test :
➔ Amino acids react with ninhydrin to give a positive test which is blue or
blue-violet color.
Practise Questions
Consider the following reaction:

[Main Jan. 07, 2020 (I)]

The product ‘X’ is used:

A. In protein estimation as an alternative to ninhydrin

B. In acid base titration as an indicator
C. As food grade colourant
D. In laboratory test for phenols
Test for Phenols
Tests for Phenols
➔ As with alcohols, the acidic hydrogen in phenol can be detected with
sodium

➔ Phenols undergo reaction with yellow ceric ammonium nitrate to

produce brown or black products.

➔ Phenols reduce potassium permanganate solution and undergo

oxidation to quinones.
Tests for Phenols
➔ The manganese is reduced from +7 which gives a purple solution to +4
which is brown.
Tests for Phenols

(i) Bromine water

➔ Positive Test: decolorization of bromine.

➔ This is good for water soluble phenols
Tests for Phenols
● Libermann’s nitroso test

➔ While phenol is reacted with NaNO2 and concentrated H2SO4, it provides

a deep green colour which changes to red on dilution with water. while
generated alkaline along with NaOH, blue colour is restored.
Quantitative Analysis
Dumas Method
Kjeldahl’s Method
Kjeldahl’s Method
Kjeldahl’s Method
Carius Method
Practise Questions
The Kjeldahl method of nitrogen estimation fails for which of the
following reaction products ?
[Main Sep. 03, 2020 (I)]

A. (3) and (4)

B. (1) and (4)
C. (1), (3) and (4)
D. (2) and (3)
Kjeldahl’s method cannot be used to estimate nitrogen for which
of the following compounds ?

A. [Main Jan. 08, 2020 (II)]

B.
C.

D.
Which of the following compounds will be suitable for Kjeldahl’s
Method for nitrogen estimation ?

[Main 2018]
Match the following:

[Main Sep.06, 2020 (II)]

Column-I Column-II
Test/ Method Reagent

(I) Lucas Test (A) C6H5SO2Cl / aq. KOH

(II) Dumans method (B) HNO3/AgNO3
(III) Kjeldahl’s method (C) CuO/CO2
(IV) Hinsberg Test (D) Conc. HCl and ZnCl2
(E) H2SO4
A. (I) (D) , (II) (C) , (III) (B) , (IV) (A)
B. (I) (B) , (II) (D) , (III) (E) , (IV) (A)
C. (I) (D) , (II) (C) , (III) (E) , (IV) (A)
D. (I) (B) , (II) (A) , (III) (C) , (IV) (D)
Practise Questions
A solution of m-chloroaniline, m-chlorophenol and m-chlorobenzoic
acid in ethyl acetate was extracted initially with a saturated
solution of NaHCO3 to give fraction A. the leftover organic phase
was extracted with dilute NaOH solution to give fraction B. The final
organic layer was labelled as fraction C. Fractions A,B and C,
contain respectively:
[Main Jan. 07, 2020 (I)]

A. m-chlorobenzoic acid, m-chloroaniline and m-chlorophenol

B. m-chlorobenzoic acid, m-chlorophenol and m-chloroaniline
C. m-chlorophenol , m-chlorobenzoic acid, and m-chloroaniline
D. m-chloroaniline, m-chlorobenzoic acid and m-chlorophenol
The organic compound that gives following qualitative analysis
is:
A. Dil. HCl insoluble
[Main. April 9, 2019 (I)]
B. NaOH solution soluble
C. Br2/water declourization

A.

B.

C.

D.
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