Practical Organic Chemistry

Identification of Functional groups :

(i) All organic compound are grouped into smaller number, each group exhibits similar chemical properties.
(ii) This means that all the compounds of the group must have something common, this common
feature is known as functional group or reactive functional group.
(iii) It is defined as the group which largely determine the properties of a compound e.g., CH3OH
C2H5OH, C3H7OH are all collectively called alcohol as the common reactive group in all is – OH.

Characteristic of functional group :

(i) The physical and chemical properties of compound containing different functional groups are different.
(ii) There exists a homologous series of compound containing each type of functional group. For example,
homologous series of alcohol like CH3OH, CH3CH2OH, CH3CH2OH etc.
(iii) The chemical properties of compound containing same functional group are similar. For example
methyl alcohol [CH3OH] & ethyl alcohol (C2H5OH) have similar chemical properties. Therefore,
(iv) Chemical identification of a class of compounds involues the same type of tests.

Practical Organic Chemistry (POC) :

While looking for the information regarding the functional nature of the compound, we go for the following
lab tests.

Test for acidic/active hydrogen

When any compound release H2 gas after reaction with sodium or potassium or alkali metals or
sodamide then this reflects the presence of acidic hydrogen.
Active H : The H atoms which are attached with more electronegative atoms like O,N,S,X, Csp.
– +
General reaction : Z H + Na Z Na + H2

S.No Reactant Reagent (Na metal) Product

1 R–NH2 Na
⎯⎯→ 1
R -NHNa+ H2
↑

2
2 R–SH Na
⎯⎯ → 1
RSNa+ H2
↑

2
3 R–COOH Na
⎯⎯ → 1
R − COONa + H2 
2
4 PhOH Na
⎯⎯ → 1
PhONa + H 2 
2
5 R—OH Na
⎯⎯ → 1
R— O–Na+ + H2 
2

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6 R—SO3H Na
⎯⎯ → 1
R—SO3–Na+ + H2 
2
7 R—CCH Na
⎯⎯ → 1
R—CC–Na+ + H2 
2
8 R —CH = CH2 Na
⎯⎯ → No reaction.
9 R —CH2—O — ⎯⎯→ Na
No reaction.
CH3
10 HCl Na
⎯⎯ → 1
NaCl + H 2 
2
11 H
Na
⎯⎯ → 
Na
1
+ H2
2

Test for unsaturation

(a) (Br2 + CCl4)
This is used to distinguish between saturated (alkane) and unsaturated (alkene/alkyne) hydrocarbon.

S.No Reactant Reagent Product Observation

1 R–CH2–CH3 (Br2 + CCl4) – No reaction
2 R–CH=CH2 (Br2 + CCl4) R–CH–CH2 Red-brown colour disappears
Br Br
3 R–CCR (Br2 + CCl4) Br Br Red-brown colour disappears
R—C—C—R
Br Br

Note : Benzene does not give this test, whereas phenol and aniline give this test.
(b) Baeyer reagent (Cold dil. alkaline KMnO4 Pink/purple solution)
This is also used to distinguish between saturated (alkane) and unsaturated (alkene/alkyne) compounds.
S.No Reactant Reagent Product Observation
1 R–CH2–CH3 Cold dil. alkaline KMnO4 – No reaction
2 R–CH=CH2 Cold dil. alkaline KMnO4 R–CH–CH2 Purple colour disappears
OH OH
3 R–CCR Cold dil. alkaline KMnO4 R–C–C–R Purple colour disappears
O O

2KMnO4 ⎯→ K2O + 2MnO2 + 3 [O]


Brown solution

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Test for terminal alkyne

S.No Reactant Reagent Product Observation

1 RCCH Tollen’s Reagent [AgNO3 + NH4OH R–CCAg + NH4NO3 White
or {Ag(NH3)2}+ OH–] precipitate
2 RCCH Ammonical cuprous chloride R–C  CCu  + 2NH4Cl Red
(Cu2Cl2 + NH4OH) precipitate

Test for alcohols

(a) Lucas reagent test (Conc. HCl + anhydrous ZnCl2)
It gives white turbidity or cloudiness with alcohols (OH groups attached with sp3 hybridised carbon).
Lucas reagent is also used to distinguish between 1°, 2°, 3° alcohol because 1°, 2°, 3° alcohols react
with different rates.
(i) 1° alcohol R–CH2–OH ⎯⎯⎯⎯⎯⎯⎯⎯ Conc.HCl + anhydrousZnCl2
→ RCH2–Cl
(does not give appreciable reaction or gives white turbidity in 30 min.)
(ii) 2° alcohol R2CH –OH ⎯⎯⎯⎯⎯⎯⎯⎯
Conc.HCl + anhydrousZnCl2
→ R2CH–Cl (gives white turbidity in 5 min.½
(iii) 3° alcohol R3C – OH ⎯⎯⎯⎯⎯⎯⎯⎯→ R3C–Cl (gives white turbidity immediately)
Conc.HCl + anhydrousZnCl2

Phenols and enols do not give Lucas test.

(b) Victor Mayer test
NO2
P+I2 AgNO2 HNO2 base
1° Alcohol : RCH2 – OH RCH2 –I RCH2 – NO2 R–C=N–OH Blood Red colour
N=O
P + I2 AgNO2 HNO2 base
2° Alcohol % R2CH–OH R2CH–I R2CH–NO2 R2C–NO2 Blue colour
P + I2 AgNO2 HNO2 base
3° Alcohol %R3C–OH R3C–I R3C–NO2 no reaction no colour

(c) Cerric Ammonium Nitrate test

Alcohols(1°,2°,3°) give characteristic red colour with cerric ammonium nitrate [(NH4)2Ce(NO3)6]
solution. It is group reagent for alcohols.

Test for phenol or enol

Neutral FeCl3 test :
It forms violet purple complex with phenol or enol (OH groups attached with sp2 carbon).
3–
6 PhOH + FeCl3 PhO 6 Fe + 3HCl + 3H+

(Coloured complex)
It does not give positive test with alcohols.

Test for carbonyl compounds

2, 4-DNP  2,4-Dinitrophenyl hydrazine+½Test :
Carbonyl compounds (all aldehydes and ketones) give yellow–orange precipitate with 2,4–DNP.
It is also known as Brady’s reagent.

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C=O + H2N – NH NO2 C=N – NH NO2

NO2 NO2
2,4–DNP (yellow-orange precipitate of Hydrazone)

Test for aldehydes

(a) Tollen’s reagent [AgNO3 + NH4OH or {Ag(NH3)2}+ OH ] : 

Tollen’s reagent gives silver mirror or Black precipitate with aldehydes.

O
AgNO3 + NH4OH
R–CH = O R – C – O + Ag
silver mirror

Note : HCOOH also gives this test.

(b) Fehling’s solution
It is an alkaline solution of cupric ion complexed with sodium potassium tartrate.
There are two solutions in Fehling solution
Solution (A) : CuSO4 solution
Solution (B) : Alkaline solution of sodium potassiumtartrate.
When these two solutions are mixed we get deep blue coloured solution.
CuSO4 + 2NaOH ⎯→ Cu(OH)2 + Na2SO4
HO – CH – COONa O – CH – COONa
Cu(OH)2+ Cu
HO – CH – COOK
O – CH – COOK
Roschelle salt (Blue coloured compound)
Equal volume of both the solutions are heated with aldehyde to give red brown precipitate of
cuprous oxide (Cu2O) which confirms the presence of aldehyde.
R – CHO + 2CuO RCOOH + Cu2O
Blue Red ppt

RCOO + 2Cu  + 2H2O


RCHO + 2Cu2+ + 3OH
Red ppt
(c) Benedict solution
It also consists of two solutions.
Solution (A) : CuSO4 solution
Solution (B) : Alkaline solution of sodium citrate.
CuSO4 + 2NaOH ⎯→ Cu(OH)2 + Na2SO4
CH2COONa CH2COONa
Cu(OH)2 + HO C COONa HO – Cu – O – C – COONa
CH2–COONa CH2COONa
(Blue colour)

Aldehyde gives positive test with Benedict solution.

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RCH = O + 2Cu2++ 3OH RCOO + 2Cu + 2H2O

 

(blue) (Red ppt.)

(d) Schiff’s reagent

It is dilute solution of rosaniline hydrochloride whose pink colour has been discharged by passing SO2.
Aldehyde restores pink colour when treated with Schiff’s reagent (Magenta solution in H2SO3).
Aromatic aldehydes (Benzaldehyde) do not give Fehling and Benedict tests.
NH
CH3

Schiff reagent

H2N NH2

Iodoform Test
Reagents : I2 + NaOH or NaOI  Where R = H, alkyl, aryl group½
Acetaldehyde, all methyl ketones & ethyl alcohol give Iodoform test.
O O
I2 + NaOH
R – C – CH3 R – C – ONa + CHI3
H+

R–COOH
(Acid of 1 carbon less)
OH O
I2 + NaOH
R – C – CH3 R – C – ONa + CHI3
H+ yellow ppt.
R–COOH
(Acid of 1 carbon less)

Test for acids/esters/amides

(a) Sodium bicarbonate test (NaHCO3)
All the acids which are stronger than H2CO3 give CO2 gas with NaHCO3.
HCl + NaHCO3 ⎯→ NaCl + H2CO3 ⎯→ H2O + CO2 
RCOOH + NaHCO3 ⎯→ RCO2Na + H2CO3 ⎯→ H2O + CO2 

RSO3H + NaHCO3 ⎯→ RSO3Na + H2CO3 ⎯→ H2O + CO2 

OH ONa
NO2 NO2
+ NaHCO3 + H2CO3
H2O + CO2
NO2 NO2

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Note :
If electron withdrawing group (NO2) is present at ortho or para position of phenol then it gives positive
test with sodium bicarbonate.
(b) Litmus test % Acid converts blue litmus into red litmus while base converts red litmus into blue.
(c) Acid amide gives smell of ammonia when heated with alkali.
O O
NaOH
R–C–NH2 R–C–ONa + NH3

(d) Esters are sweet (fruity) smelling liquids.
Esters when react with NaOH & phenolphthalein, pink colour disappears on heating.

RCOOR’ + NaOH + Phenolphthalein (Pink) ⎯⎯ → R COOH + R’ OH (Colourless solution)

Test for amines

(i) NaNO2 + aqueous HCl test % it is used to distinguish between 1º, 2º and 3º amines and also
distinguish between aliphatic and aromatic primary amines.
NaNO2 + aq. HCl
1° Aliphatic amine % R–CH2–NH2 R–CH2–OH + N2 

NaNO2 + aq. HCl +

1° Aromatic amine : Ph–NH2
(0–5°C) Ph–N2Cl diazonium salt)

N=O
NaNO2 + aq. HCl
2° Amine % R – NH – R R – N – R (N -Nitroso amine) yellow oily liquid

NaNO2 + aq. HCl

3° Amine : R3N unstable nitrite

(ii) Carbyl amine test (CHCl3 + KOH)

1° Amine (Aliphatic and Aromatic)
CHCl3 + KOH
R–CH2–NH2 R–CH2–N  C + 3KCl + 3H2O
(unpleasent smell of isocyanide)

Ph – NH2 CHCl3 + KOH

Ph – N  C
* 2° Amines and 3° Amines do not give this test.

(iii) Hofmann mustard oil test

It is a test for 1º amine and aniline. Primary amine reacts with carbon disulphide to form dithioalkyl
carbamic acids which decompose on heating with mercuric chloride (HgCl2) to give alkyl
isothiocyanate having smell like mustard oil.
SH
HgCl2
(a) R – NH2 + S = C = S R – NH – C
 R – N = C = S + HgS + 2HCl
S
Dithioethylcarbamic acid Alkylisothiocyanate

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S
 HgCl2
(b) CH3CH2NH2 + S=C=S CH3CH2NH2 –C –SH 
CH3CH2–N = C=S + HgS + 2HCl

(1º amine) Ethyl isothiocyanate

Similarly aniline gives phenylisothiocyanate.
(i) S=C=S
(c) C6H5NH2 (ii) HgCl2
C6H5N=C=S
Phenylisothiocyanate

* 2° Amines and 3° Amines do not give this test.

(iv) Hinsberg reagent (C6H5SO2Cl)
This is used to distinguish between 1°,2° & 3° amines.
1° Amine % R–NH2 + PhSO2Cl ⎯⎯⎯→
Pyridine
R–NH–SO2–Ph ⎯⎯ ⎯
Base
→ Compound is soluble in base.
2° Amine % R2NH + PhSO2Cl ⎯⎯⎯→
Pyridine
R2N–SO2–Ph ⎯⎯ ⎯
Base
→ Compound is insoluble in base.
3° Amine : R3N + PhSO2Cl ⎯⎯⎯→
Pyridine
No reaction.

Test of nitro group (Mulliken- Barker Test)

Nitroalkane & nitrobenzene gives black ppt on reduction with Zn and ammonium chloride followed by
treating with Tollen’s reagent. This is also called Mulliken’s test.
Zn-NH4Cl AgNO3+NH4OH
(a) R–NO2 ⎯⎯⎯⎯
→ R–NHOH ⎯⎯⎯⎯⎯ 
→ Ag(black ppt)
NO2 NH–OH N=O

AgNO3+NH4OH
(b) + Zn + NH4Cl + H2O + Ag
Black ppt

2. Elements detection:
Detection of carbon and hydrogen
Carbon and hydrogen are detected by heating the compound with copper(II) oxide. Carbon present in
the compound is oxidised to carbon dioxide (tested with lime-water, which develops turbidity) and
hydrogen to water (tested with anhydrous copper sulphate, which turns blue).

C + 2CuO ⎯⎯ → 2Cu + CO2

2H + CuO ⎯⎯ → Cu + H2O

CO2 + Ca(OH)2 ⎯⎯ → CaCO3  + H2O

5H2O + CuSO4 ⎯⎯ → CuSO4.5H2O
White Blue

Detection of other elements

Nitrogen, sulphur, halogens and phosphorus present in an organic compound are detected by
“Lassaigne’s test”. The elements present in the compound are converted from their covalent form to their ionic
form by fusing the organic compound with sodium metal.
Following reactions take place: C, N, S and X come from organic compound.

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Cyanide, sulphide and halide of sodium formed by sodium fusion are extracted from the fused mass by
boiling it with distilled water. This extract is known as sodium fusion extract or Lassaigne solution.
 
Na + C + N ⎯⎯ → NaCN ; 2Na + S ⎯⎯ → Na2S
 
Na + X ⎯⎯ → NaX ; Na + C + N + S ⎯⎯ → NaSCN

(i) Test for nitrogen

The sodium fusion extract is boiled with iron(II) sulphate and then acidified with dilute sulphuric acid.
The formation of Prussian blue or green colour confirms the presence of nitrogen.
Alternatively FeCl3 and dil. HCl may be added.
6NaCN + FeSO4 ⎯→ Na4[Fe(CN)6]
xH2O
Na4[Fe(CN)6] + 4Fe3+ ⎯⎯⎯ → Fe4[Fe(CN)6]3. xH2O
Ferric ferrocyanide (Prussian blue)
(ii) Test for sulphur
(a) 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.
Na2S + (CH3COO)2Pb ⎯→ PbS (Black)
(b) On treating sodium fusion extract with sodium nitroprusside, appearance of a violet colour
indicates the presence of sulphur.
Na2S + Na2[Fe(CN)5 NO] ⎯→ Na4[Fe(CN)5NOS]
Sodium nitroprusside Sodium thionitroprusside (Violet/Purple)
(c) In case, nitrogen and sulphur both are present in an organic compound, then sodium thiocyanate
is formed. It gives blood red colour with neutral FeCl3.
Na + C + N + S ⎯→ NaSCN ; Neutral FeCl3 + NaSCN ⎯→ Fe(SCN)3(Blood red)
(iii) Test for halogens
The sodium fusion extract is acidified with nitric acid and then treated with silver nitrate. A white
precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish precipitate,
sparingly soluble in ammonium hydroxide shows the presence of bromine and a yellow precipitate,
insoluble in ammonium hydroxide shows the presence of iodine.
Note :
The sodium fusion extract is first boiled with concentrated nitric acid to decompose cyanide or sulphide
of sodium formed during Lassaigne’s test. These ions would otherwise interfere with silver nitrate test for
halogens.
NaX + AgNO3 ⎯→ AgX 
(iv) Test for phosphorus
The compound is heated with an oxidising agent (sodium peroxide). The phosphorus present in the
compound is oxidised to phosphate. The solution is boiled with nitric acid and then treated with
ammonium molybdate. A yellow colouration or precipitate indicates the presence of phosphorus.
Na3PO4 + 3HNO3 ⎯→ H3PO4 + 3NaNO3
H3PO4 + 12(NH4)2MoO4 + 21 HNO3 ⎯→ (NH4)3PO4. 12 MoO3 + 21 NH4NO3 + 12H2O
Ammonium Ammonium
Molybdate Phosphomolybdate

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Summary
1. Unsaturation : Alkenes & alkynes:
(a) Bayers test : Cold dil alk. KMnO4 decolourisation test
Purple colour → Colourless + MnO2 (Brown ppt)
(b) Br2 water decolourisation test
Violet colourless of Br2 → Colourless

2. Terminal alkynes:
Confirmed by ppt of Acetylide ion with NaNH2 or AgNO3 or Cu2Cl2NH4OH

3. Alkyl halides:
(a) If they are capable of carbocation formation then they will give ppt with AgNO3.
(b) Beilstein’s test : A green colour is imported to the flame if small amount of organic compound is taken
on copper wire.

4. Alcohol:
(a) Cerric ammonium nitrate → Give red colour
(b) Boil with acetic acid & conc. H2SO4 → fruity smell
–
(c) 2-alkanol & ethanol also give Iodoform test → Yellow ppt. of CH3I on reaction with I2 + OH

5. Aldehyde & Ketones:

2,4- Dinitrophenyl hydrazize (or) Braddy’s reagent give yellow, orange or red color with ald. &
Ketones (2,4-DNP)

6. Aldehydes:
(a) Tollen’s test → Silver mirror
(b) Fehling’s test {except benzaldehyde}→ Red colour
(c) Benedicts test → Red colour
(d) Schiff’s dye colour regeneration test → Pink colour
(e) Gly ppt with HgCl2.

7. Ketones:
(a) Methyl Ketones give haloform test
(b) -hydroxy Ketones give Tollen’s & Fehling test’s too.

8. Carboxylic acids:
(a) Brisk effervescence with aq. NaHCO3 solution.
(b) HCOOH alone gives silver mirror test with Tollen’s reagent.
(c) Blue litmus → red
(d) Give fruity smell on reaction with alcohols.

9. Phenols:
(a) Violet colouration with neural FeCl3
(b) Liebermann test
(c) White ppt with Br2 water
(d) Brisk effervescence with aq. NaHCO3 is observed in case of Nitrophenols.

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10. Primary amines:

(a) Carbylamine reaction → Isonitriles have very distinctive foul odors
(b) Hoffmann mustard oil reaction → Oily liquid with mustard like smell.

11. Aromatic 1° amine → diazo test

12. Amide boil with NaOH → NH3

13. Nitrobenzene → Mullikqn Baker test → Treat it with ZnNH4Cl then boil with Tollen’s reagent → Silver
mirror will appear

(A) ELEMENTAL ANALYSIS

Lassaigne method (Detection of elements)
Element Sodium Extract Confirmed Test Reaction
(S.E.)
Nitrogen Na+C+N ⎯⎯

→ NaCN S.E. + FeSO4 + NaOH, boil Feso4 + 2NaOH ⎯→ Fe(OH)2 + Na2SO4
(S.E.) and cool, + FeCl3 + conc. HCl Fe(OH)2 + 6NaOH ⎯→ Na4[Fe(CN)6] + 2NaOH
Blue or green colour Na4[Fe(CN)6] + FeCl3 ⎯⎯ → Fe4[Fe(CN)6]3 + 3
HCl

NaCl Prussian blue

Sulphur 2Ns + S ⎯⎯
→ Na2S

(i) S.E. + sodium nitro (i) Na2S + Na2[Fe(CN)5NO]
(S.E.) prusside (A) A deep violet ⎯→ Na4[Fe(CN)5NOS]
colour. Deep violet
(ii) S.E. + CH3COOH + (ii)Na2S + (CH3COO)2Pb ⎯⎯⎯
CH3COOH
⎯→ PhS +
(CH3COO)2Pb 2CH3COONa black ppt.
A black ppt.
Halogen Na + Cl ⎯⎯
→ NaCl

S.E. + HNO3 = AgNO3 NaX + AgNO3 ⎯⎯⎯
HNO3
→ AgZ
(S.E.) (i) White ppt. so lub le in aq AgCl + 2NH3(aq) ⎯→ [Ag(NH3)2]Cl
NH3 confirms Cl White ppt soluble
(ii) Yellow ppt partially so lub
le in aq. NH3 confirm br
(iii) Yellow ppt inso lub le in
aq NH3 confirms I
Nitrogen Na + C + N + S As in test for nitrogen; NaCNS + FeCl2 ⎯→ [Fe(CNS)]Cl2 + naCl
and 
→ NaCNS (S.E.)
⎯⎯ instead of greed or blue Blood red colour
Sulphur colour, blood red coloration
together confirms presence of N and S
both

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