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SYSTEMATIC PROCEDURE FOR IDENTIFICATION OF THE FUNCTIONAL

GROUP OF AN ORGANIC COMPOUND


S. No. Experiment 1 Physical Characteristics: a) State b) Colour c) Odour 2
Solubility: a) Cold Water (Test the aqueous solution with
Blue and Red Litmus Papers) Observation Solid/liquid
Colourless/ _ _ _ _ _ colour Pleasant/ phenolic/ aniline like/
oil of bitter almond/ characteristic Soluble Blue Litmus turned to Red
Red Litmus turned to Blue Inference

Acidic Basic Presence of Carboxylic Acid b) NaHCO3 (10%)


Soluble with effervescence Group Presence of Acidic Substance c) NaOH (10%)
Soluble (Acids and Phenols) Presence of Basic Substances d) dil HCl (10%)
Soluble (Amines) Note: 1) If Water Soluble, do not test with
NaHCO3, NaOH and dil HCl. Use Litmus Paper
2) If the Compound is insoluble in water and the other reagents, it is NEUTRAL

e) Ether (Note: Insoluble in water, acid and alkali)

Hydrocarbons, nitrohydro carbons, alkyl or aryl halides, Soluble


esters and ethers. Higher molecular weight alcohols, aldehydes and ketones
Insoluble in Ether but soluble May be Carbohydrates or in water Urea
a) Burns with a sooty flame Aromatic Aliphatic Carbohydrates, etc

3.

Flame Test: Glass rod is dipped in the compound and subjected to flame

b) Burns with nonsooty flame c) Charring

4.

Test for Unsaturation: a) Baeyer’s Test: Compound is added to aq. KMnO4


solution b) Compound is added to Bromine in CCl4 (2%)

a) Decolourisation of KMnO4 with brown ppt. b) Decolourisation of Br2


without evolution of HBr The compound decolourises both the reagents
The compound does not decolourise the two reagents (OR)
The colour of one reagent is discharged and the colour of the other is not

Unsaturated Saturated

Saturated

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 1
Br Br C C + Br 2
(Brown)

C C
(Clear)

(Vicinal Dibromide)

OHOH

C C

+ KMnO 4
(Purple)

C C

+ MnO 2
(Brown)

(Glycol)

5.

Lassaigne’s Test for Extra Elements: (Nitrogen and Halogens) A small piece of
Sodium metal (Freshly cut) is placed in an ignition tube and the tube
is heated
strongly. Small quantity of the compound (one or two crystals if solid or one or t
wo drops if liquid) is added and the tube heated strongly. The red hot
tube is plunged into 10.0ml of distilled water contained in a mortar
and is crushed with pestle and the solution filtered. The filterate
is called Sodium Fusion Extract. S. No. Experiment Observation Inference
a) Test for Nitrogen: (in the form of NaCN in the Extract)
To small quantity of the extract If the colour of the solution after
few crystals of Mohr’s salt are adding dil H2SO4 is intense blue
Nitrogen Present (Prussian Blue) added and boiled. To this solution dil H2SO4
is added to get clear solution

Na+C+N®NaCN 6NaCN + FeSO ®Na [Fe(CN) ] + Na SO 4 4 6 2 4 Na [Fe(CN)


]+ 2Fe (SO4) ® Fe [Fe(CN) ] + 6Na SO 4 6 2 3 4 6 3 2 4
(Prussian Blue Clour)
b) Test for Halogens: The Sodium Fusion Extract is
acidified with dil HNO3, boiled, cooled and AgNO3 solution is added
a)White Precipitate soluble in NH4OH b) Cream coloured Precipitate ,
sparing soluble in NH4OH c) Yellow Precipitate insoluble in NH4OH
Chlorine Present Bromine Present Iodine Present

Na+Cl/Br/I ®NaCl/NaBr/NaI NaX + AgNO ® AgX (ppt) + NaNO 3 3


c) Test for Sulphur: The Black precipitate of PbS is
extract is acidified with acetic obtained acid and Pb(CH3COO)2 solution
Sulphur is Present

2Na+S®Na2S
Pb(CH3COO)2 + Na2S ® PbS + 2 CH3COONa

(ALL THE ABOVE TEST ARE COMPULSORY FOR ANY GIVEN COMPOUND)

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 2
Tests for Functional Group Identification S. No. Experiment Observation
Inference Carboxylic Acids: (Acidic, Soluble in NaHCO3 and NaOH) CO2
gas is evolved Carboxylic acid group present 1 Add 1 ml of saturated NaHCO3
solution to one drop of liquid or small amount of solid
one drop of liquid or small amount of solid is dissolved in
Fruity Odour is observed 5ml of ethyl alcohol and 2drops
Carboxylic acid group is present (due to the formation of esters of conc. H2SO4
are added and which are sweet smelling) the mixture is poured in to 25ml
of dil Na2CO3 and stirred well
(Carboxylic Acids do not have any characteristic tests other than its solubility in
NaHCO3 with
effervescence and NaOH. To know whether the acid is simple acid or phenolic acid te
st with FeCl3) Phenols: (Acidic, Insoluble in NaHCO3 2 but soluble in NaOH)
a) Test with FeCl3 A prominent Colour change The compound is dissolved in
other than the yellow colour of Phenolic hydroxyl group present
1ml of alcohol or suspended in FeCl3 obtained water and one or two drops of
(Usually blue or violet – some dilute FeCl3 added cases red or green)
b) Liebermann’s Nitroso Test Compound is added few crystals
of NaNO2 , warmed very A deep blue or deep green gently for 20 seconds and
colouration developed slowly Phenolic hydroxyl group present
allowed to cool and twice the volume of Conc. H2SO4 added
(Note: Only some Phenols give and rotate the test tube slowly to
this test as mentioned above) mix Dilute the contents cautiously
The solution turns red with water Now add an excess of NaOH
The green or blue colouration Solution reappears
(Note: Phenols where Para Position is vacant only will give Liberman’s Niroso
Test) 3 Alcohols: a) Ceric ammonium nitrate test: To the aqueous solution of
Alcoholic hydroxyl group Red colour observed the compound. Add few drops
present of ceric ammonium nitrate b) Xanthate test: to the
aqueous solution add pellets of Yellow precipitate formed
Alcoholic group present KOH, heat, cool and then add
1.0ml of ether followed by 23 drops of CS2 0 Non insoluble layer separates at
1 Alcohol 0 0 c) Distinction between 1 , 2 once 0 and 3 alcohols:
To 2 ml of the 0 Cloudiness appears after 45 2 Alcohol compound
8ml of Lucas reagent minutes added and shake 0 Solution remains clear 3
Alcohol

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 3
S. No. Experiment Observation 4 Carbohydrates:
(Soluble in Water, Neutral, Aliphatic and NonNitrogenous) a) Molisch’s Test:
The compound is dissolved in water and 23 drops of 1%
A deep violet coloration is alcoholic solution of anaphthol
produced where the two liquids and then carefully pour 2 ml of meet conc. H2SO4
down the side of the test tube so that it forms a heavy layer at the bottom
b) Action of H2SO4: The The compound immediately compound is warmed with 1 ml
blackens. As the temperature of Conc. H2SO4 on a small
raises, CO2 , CO and SO2 are flame evolved c) To a small amount of the
compound, Fehling’s Reagent is Red precipitate of CuO2 is
added and heated on a water obtained bath 5 Carbonyl Compounds:
(Neutral Compounds) a) Test with Borsch’s Reagent: Few drops of the compound is
dissolved in methanol and a few Yellow or Orange coloured drops of 2,4-
dinitrophenyl Precipitate is formed hydrazine reagent are added
(gently heat and cool if necessary)

Inference

Carbohydrate present

Carbohydrate present

Reducing sugar

May be aldehyde or ketone

R H or R' O + H NHN 2 O N 2
b) Tollen’s Test: In a clean test tube 23 ml of AgNO3 solution is taken and 23
drops of NaOH soln. added. To this dil. Ammonia added drop
by drop until the precipitated silver oxide is almost
redissolved, then few drops of A silver mirror is formed the compound added the
mixture is gently warmed on a water bath with vigorous shaking from time to time

NO 2

R NHN H or R' O N 2 NO 2

Aldehyde group present

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 4
S. No.

Experiment c) Fehling’s Test: To 1 ml of the compound 1 ml of 10% Na2CO3


solution and a few drops of Fehling;s solution are added and mixture is boiled
gently for 1 minute d) Schiff’s Test The compound is added to the
decolourised Schiff’s Reagent.

Observation

Inference Aldehyde group present

The solution usually turns green (Aliphatic aldehydes reduce


and on standing a fine yellow or Fehling’s solution rapidly,
red precipitate of cuprous oxide Benzaldehyde slowly and slowly separates out
Salicylaldehyde does not reduce it)

The Schiff reagent is the reaction product of Fuchsine


(pararosanilin) and sodium bisulfite

A characteristic magenta or purple colour develops

Aldehyde group present

Tests for Ketones:

(Ketones do not give Tollen’s, Fehling’s and Schiff’s test)

a) Aliphatic ketones containing CH3CO–


group restore the colour very slowly to Schiff’s reagent.
Other ketones have no reaction. b)
Ketones containg the CH3CO– group give the Iodoform test and a red colouration with
alkaline sodium nitroprusside and a violet colouration with m-
dinitrobenzene and sodium hydroxide Esters: (Neutral) a) Hydroximic Acid Test:
To a few drops of the ester 0.2g of hydroxylamine hydrochloride
and 5 ml of 10% NaOH solution are added and gently boiled for 1-
2 minutes. The mixture is A violet or deep redbrown Ester group present
cooled and acidified with HCl, colour develops immediately
cooled again and the a few drops of FeCl3 solution are added
b) Hydrolysis to Acid: 2 ml of the compound is taken
in a 50 mol RB flask fitted with reflux watercondenser and 20
ml of 10% aq. NaOH soln. and refluxed for 2030 minutes till a
Solid acid derivative is obtained Ester group present
homogeneous clear solution is obtained. The mixture is cooled
and acidified with HCl (Note: For Phenolic Esters do not perform hydroxymic acid
test )

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 5
S. No. Experiment Observation
Primary Amines: (Soluble in HCl, Basic, Nitrogenous) 7
a) Isocyanide Reaction / Carbylamine Test: A foul odour of isocyanide
To 0.2g of the substance a few (carbylamine) is produced
drops of chloroform and 23 ml Note: of ethanolic NaOH soln are
(Cool the tube and carefully add added, mixed well and warmed
an excess of conc. HCl to gently deodorise by converting the
isocyanide to amine) b) Diazotisation Test: 0.2g of the compound is
dissolved in 1 ml of conc. HCl and diluted with 3 ml of H2O,
cooled in ice and a few drops of sodium nitrite soln. are added.
This cold diazonium solution is A brilliant red dye is produced
added to a cold solution of bNaphthol in excess of 10% NaOH solution
Secondary Amines: (Soluble in HCl, Basic, Nitrogenous)
A little compound is dissolved A deep blue or deep green
in 3 ml of dil. HCl and sodium colouration developed slowly.
nitrite soln with cooling is added On dilution the solution turns
gradually with shaking until the red yellow oily ppt. of Nitrosoamine
On adding excess NaOH the obtained green or blue colouration reappears
Libermann’s test: To small quantity of Nitrosoamine add 1 or 2 drops
of Phenol and continue the test as in 2b given previously
Tertiary Amines: (Soluble in HCl, Basic, Nitrogenous) a)pNitroso derivative test
0.2g of the compound is dissolved in 3 ml of dil. HCl, it
is chilled in ice and then 2 ml of A reddish solution obtained but
20% sodium nitrite soln added no oil separates. Allow to stand
carefully drop by drop. for 5 min. in the cold. Then NaOH solution is added
b) Potassium Ferrocyanide Test: The compound is dissolved in
dil HCl and aq. Solution of K4Fe(CN)6 is added to it
A green colour is obtained.

Inference

Primary amine Present

Primary amine is confirmed

Secondary Amine Confirmed

Tertiary amine Present

Bulky white precipitate is obtained

Tertiary Amine Confirmed

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 6
S. No. Experiment Observation Inference
Nitro Compounds: (Neutral, Nitrogenous) 8
a) The compound is taken in a boiling tube and 5 ml of conc. HCl and several pieces
of Tin added to it.
The mixture is warmed and shaken continuously to break up the oily drops of the nit
ro compound. To the residue conduct tests for Primary Amines
b) Mulliken and Barker’s reaction: The compound is added and to 10.0 ml of 50% alco
hol and 0.5 g
of Zn dust and 0.5 g of NH4Cl/ CaCl2. The mixture is boiled for 5 minutes and filt
ered. i) The filtrate is added Tollen’s Black Precipitate or Silver
Nitro group present reagent (A+B) mirror is formed RNO2 + 4H ® RNHOH + H O 2

RNHOH + 2[Ag(NH3)2]OH ® RNH + 2Ag+ 4NH3 + 2H2O


ii) The filtrate is added Red Precipitate of Cu2O is
Fehling’s solution (A+B) and Nitro group present formed heated on a water bath
Amides and Anilides: (Neutral, Nitrogenous) Compound is Strongly heated
a) Smell of ammonia gas turning Amide group present with conc. NaOH
moist red litmus paper blue RCONH2 + NaOH ® RCOONa + NH 3 b) Smell of aniline
(Confirm the formation of Anilide Present aniline by doing carbylamine test)
RCONHPh + NaOH ® RCOONa + PhNH2 Biuret Test for Urea: A little
of the substance is gently heated in a dry test tube until it melts
and then solidifies. The residue A violet colour is produced
Presence of a diamide like Urea is dissolved in a little water, and
a dil. Solution of CuSO4 followed NaOH drop by drop are added
Hydrocarbons (Neutral)
Note: This test should be done only after proving the absence of other functional g
roups The compound is shaken with conc. H2SO4 till a clear solution
a) Compound did not regenerate Hydrocarbon Present
is obtained. The contents are warmed if necessary while Ether Present
dissolving. b) Compound regenerated The clear solution is poured over ice

10

REPORT: The given Compound is: Neutral/ Acidic/ Basic Aromatic/ Aliphatic
Saturated/ Unsaturated Extra Element/s Present: Functional group/s Present:
M.P/ B.P

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 7
The Functional Groups to be identified are:
A) 1. Carboxylic acid / Substituted Aromatic Carboxylic Acids 2. Phenols /
Substituted Phenols 3. Alcohols 4. Carbonyl Compounds – Aldehydes and Ketones
5. Esters / Phenolic Esters 6. Carbohydrates 7.
Hydrocarbons / Halogenated Hydrocarbons 8. Ethers 0 0 9. Amines 1
or Primary / 2 or Secondary / 0 3 or Tertiary 10. Nitro Compounds 11.
Amides 12. Anilides Acidic Substances without Nitrogen

B)

Neutral Compounds without Nitrogen

C) D)

Basic Nitrogen Containing Compounds Neutral Nitrogen Containing Compounds

Dr. S. Paul Douglas,


Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 8
THE PREPARATION OF DERIVATIVES OF ORGANIC COMPOUNDS The preliminary examination
and group classification tests indicate the particular class
(functional group) to which an unknown organic compound may belong. Further charact
erisation and identification depends on the selection and preparation of
a suitable solid derivative and accurate
determination of its melting point (best, between 90 150 ).
The following table lists some of the classes of organic compounds and a selection
of derivatives that may be prepared to characterise them. Check with the
tables of melting points in Vogel which
derivatives are most suitable for the characterisation of your particular compound.
CLASS OF COMPOUND 1. ALCOHOLS 2. PHENOLS 3. ALDEHYDES AND KETONES 4. ACIDS
5. AMINES DERIVATIVES 3,5dinitrobenzoate benzoate, acetate, bromoderivative
semicarbazone, 2,4dinitrophenyl hydrazone, oxime anilide, amide, ptoluidide.
benzoyl, acetyl and sulphonamide derivatives

METHODS FOR THE PREPARATION OF DERIVATIVES 1. ALCOHOLS: (i) 3,5Dinitrobenzoates


3,5Dinitrobenzoyl chloride is usually partially hydrolysed and should be prepared i
n the pure state by heating gently a mixture of 3,5-
dinitrobenzoic acid (1 g) and phosphorus pentachloride (1.5 g)
in a dry test tube, until it liquifies (5 min).* The liquid is poured on a dry watc
h glass and allowed to
solidify. The phosphoryl chlorides are removed by pressing the solid with a spatula
on a wad of filter
paper. The residual acid chloride is suitable for immediate use in the preparation
of the derivatives. The 3,5-
dinitrobenzoyl chloride is mixed with the alcohol (0.5 1 mL) in a loosely corked d
ry
test tube and heated on a steam bath for about 10 min. Secondary and tertiary alcoh
ols require up to 30
min. On cooling add 10 mL sodium hydrogen carbonate solution, stir until the ester
crystallises out,
and filter at the pump. Wash with a little carbonate solution, water and suck dry.
Recrystallise from the
minimum hot ethanol or light petroleum. Cool slowly to avoid the formation of oily
droplets of your ester.
(*Work under fume hood. Fumes are irritating to the eyes and nose.) 2. PHENOLS
(i) Benzoates (SchöttenBaumann method).
To the phenol (0.5 g) is added 5% sodium hydroxide (10 mL) in a wellcorked boiling
tube or
a small conical flask. Benzoyl chloride (2 mL) is added in small quantities at a ti
me, and the mixture shaken vigorously with occasional cooling under the
tap or in icewater. After 15 min the solid
benzoate separates out: the solution should be alkaline at the end of the reaction;
if not alkaline, or if
the product is oily, add a solid pellet of sodium hydroxide and shake again. Collec
t the benzoate, wash
thoroughly with cold water, and recrystallise from alcohol or light petroleum.
(ii) Acetates Acetates of many simple phenols are liquids; however, this
is a suitable derivative for
polyhydric and substituted phenols. The phenol (0.5 g) is dissolved in 10% sodium h
ydroxide solution and an equal quantity of crushed ice is added,
followed by acetic anhydride (2 mL). The mixture is vigorously shaken in a
stoppered test tube until the acetate separates. The product is filtered
and recrystallised from alcohol. Dr. S. Paul Douglas,
Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 9
(iii) Bromo derivatives The phenol (0.3 g) is suspended in dilute
hydrochloric (10 mL) and bromine water added
dropwise until no more decolourisation occurs. The bromo derivative which precipita
tes out is filtered off and recrystallised from alcohol.
3. ALDEHYDES AND KETONES (i) Semicarbazones
Dissolve semicarbazide hydrochloride (1 g) and sodium acetate (1.5 g) in water (8
10 mL),
add the aldehyde or ketone (0.3 mL) and shake. Shake the mixture for a few minutes
and then cool in icewater. Filter off the crystals, wash with a little
cold water and recrystallise from methanol or ethanol. (ii) 2,4-
Dinitrophenylhydrazones Suspend 0.25 g of 2,4dinitrophenylhydrazine in 5
mL of methanol and add 0.5 mL of concentrated sulphuric acid
cautiously. Filter the warm solution and add a solution of 0.2 g of
the
carbonyl compound in 1 mL of methanol. Recrystallise the derivative from methanol,
ethanol or ethyl acetate. (iii) Oximes
Hydroxylamine hydrochloride (0.5 g) is dissolved in water (2 mL). 10% sodium hydrox
ide (2 mL) and the carbonyl compound (0.2 0.3 g) dissolved in alcohol (1 -
2 mL) are added, the mixture
warmed on a steam bath for 10 min and then cooled in ice. Crystallisation is induce
d by scratching the
sides of the test tube with a glass rod. The oximes may be crystallised from alcoho
l. 4. ACIDS (i) Amides, anilides and ptoluidides
The acid (0.5 g) is refluxed with thionyl chloride (2 3 mL) in a fume cupboard for
about 30 mins.* It is advisable to place a plug of cotton wool in the
top of the reflux condenser to exclude
moisture. The condenser is removed and the excess of thionyl chloride is distilled
off (b.p. 78 ). The
acid chloride thus produced is treated with concentrated ammonia solution (5 mL) or
aniline (0.5 1 mL) or ptoluidine (0.5
1 g), when the solid derivative separates out. It is collected and recrystallised
from alcohol adding decolourising charcoal if found necessary.
*Alternately use PCl5 to form the acid chloride. 5. AMINES
(i) Acetyl derivatives (acetamides)
Reflux gently in a small dry flask under a dry condenser the amine (1 g) with aceti
c anhydride
(3 mL) for 15 min. Cool the reaction mixture and pour into 20 mL cold water. Boil t
o decompose the
excess acetic anhydride. Cool and filter by suction the insoluble derivative. Recry
stallise from ethanol. (ii) Benzoyl derivatives (benzamides)
Suspend 1 g of the amine in 20 mL of 5% aqueous sodium hydroxide in a wellcorked fl
ask,
and add 2 mL benzoyl chloride (fume hood!), about 0.5 mL at a time, with constant s
haking. Shake vigorously for 5 10 min until the odour of the benzoyl
chloride has disappeared. Ensure that the
mixture remains alkaline. Filter off the solid derivative, wash with a little cold
water and recrystallise from ethanol. (iii) Benzenesulphonamides
To 1 g of the amine in 20 mL of 5% sodium hydroxide solution in a wellcorked flask
add 1 mL benzenesulphonyl chloride (fume hood!). Shake the mixture until
the odour of the sulphonyl
chloride disappears. Check that the solution is alkaline. Acidify if necessary to o
btain the precipitated derivative. Concentrated hydrochloric acid added
dropwise should be used. Filter the product, wash
with a little cold water and suck dry. Recrystallise from ethanol.
Dr. S. Paul Douglas,
Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 10