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GROUP OF AN ORGANIC COMPOUND
S. No. Experiment Observation Inference
1 Physical Characteristics:
a) State Solid/liquid
b) Colour Colourless/ _ _ _ _ _ colour
Pleasant/ phenolic/ aniline like/
c) Odour oil of bitter almond/
characteristic
2 Solubility:
a) Cold Water Soluble
(Test the aqueous solution with Blue Litmus turned to Red Acidic
Blue and Red Litmus Papers) Red Litmus turned to Blue 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
Hydrocarbons, nitrohydro
e) Ether carbons, alkyl or aryl halides,
(Note: Insoluble in water, Soluble esters and ethers. Higher
acid and alkali) molecular weight alcohols,
aldehydes and ketones
Insoluble in Ether but soluble May be Carbohydrates or
in water Urea
3. Flame Test:
a) Burns with a sooty flame Aromatic
Glass rod is dipped in the
compound and subjected to b) Burns with nonsooty flame Aliphatic
flame
c) Charring Carbohydrates, etc
4. Test for Unsaturation:
a) Baeyer’s Test: Compound is a) Decolourisation of KMnO4
added to aq. KMnO4 solution with brown ppt.
b) Compound is added to b) Decolourisation of Br2
Bromine in CCl4 (2%) without evolution of HBr
The compound decolourises
Unsaturated
both the reagents
The compound does not
Saturated
decolourise the two reagents
(OR)
The colour of one reagent is
Saturated
discharged and the colour of the
other is not
Dr. S. Paul Douglas, Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 1
Br Br
C C + Br 2 C C (Vicinal Dibromide)
(Brown)
(Clear)
OHOH
C C + KMnO 4 C C + MnO 2 (Glycol)
(Purple) (Brown)
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 two 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
added and boiled. To this (Prussian Blue)
solution dil H2SO4 is added to
get clear solution
Na+C+N®NaCN
6NaCN + FeSO 4®Na 4 [Fe(CN) 6 ] + Na 2 SO 4
Na 4 [Fe(CN) 6 ]+ 2Fe 2 (SO4) 3 ® Fe 4 [Fe(CN) 6 ] 3 + 6Na 2 SO 4
(Prussian Blue Clour)
a)White Precipitate soluble in
b) Test for Halogens: The Chlorine Present
NH4OH
Sodium Fusion Extract is
b) Cream coloured Precipitate ,
acidified with dil HNO3, boiled, Bromine Present
sparing soluble in NH4OH
cooled and AgNO3 solution is
c) Yellow Precipitate insoluble
added Iodine Present
in NH4OH
Na+Cl/Br/I ®NaCl/NaBr/NaI
NaX + AgNO 3 ® AgX (ppt) + NaNO 3
c) Test for Sulphur: The
Black precipitate of PbS is
extract is acidified with acetic Sulphur is Present
obtained
acid and Pb(CH3COO)2 solution
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
1 Carboxylic acid group present
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
(due to the formation of esters Carboxylic acid group is present
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 test with FeCl3)
Phenols:
2 (Acidic, Insoluble in NaHCO3
but soluble in NaOH)
a) Test with FeCl3 A prominent Colour change
The compound is dissolved in other than the yellow colour of
1ml of alcohol or suspended in FeCl3 obtained Phenolic hydroxyl group present
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
allowed to cool and twice the Phenolic hydroxyl group present
volume of Conc. H2SO4 added
and rotate the test tube slowly to (Note: Only some Phenols give
mix this test as mentioned above)
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
KOH, heat, cool and then add Yellow precipitate formed Alcoholic group present
1.0ml of ether followed by 23
drops of CS2
Non insoluble layer separates at 1 0 Alcohol
c) Distinction between 1 0 , 2 0
once
and 3 0 alcohols: To 2 ml of the
Cloudiness appears after 45 2 0 Alcohol
compound 8ml of Lucas reagent
minutes
added and shake
Solution remains clear 3 0 Alcohol
Dr. S. Paul Douglas, Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 3
S. No. Experiment Observation Inference
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 Carbohydrate present
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
Carbohydrate present
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
Reducing sugar
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 2,4dinitrophenyl May be aldehyde or ketone
Precipitate is formed
hydrazine reagent are added
(gently heat and cool if
necessary)
R
R
O + H 2 NHN NO 2 NHN NO 2
H or R'
H or R'
O 2 N O 2 N
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 Aldehyde group present
the compound added the
mixture is gently warmed on a
water bath with vigorous
shaking from time to time
Dr. S. Paul Douglas, Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 4
S. No. Experiment Observation Inference
c) Fehling’s Test:
Aldehyde group present
To 1 ml of the compound 1 ml
The solution usually turns green
of 10% Na2CO3 solution and a (Aliphatic aldehydes reduce
and on standing a fine yellow or
few drops of Fehling;s solution Fehling’s solution rapidly,
red precipitate of cuprous oxide
are added and mixture is boiled Benzaldehyde slowly and
slowly separates out
gently for 1 minute Salicylaldehyde does not reduce
it)
d) Schiff’s Test
The compound is added to the
decolourised Schiff’s Reagent.
The Schiff reagent is the A characteristic magenta or Aldehyde group present
reaction product of Fuchsine purple colour develops
(pararosanilin) and sodium
bisulfite
Dr. S. Paul Douglas, Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 5
S. No. Experiment Observation Inference
7 Primary Amines: (Soluble in HCl, Basic, Nitrogenous)
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
Primary amine Present
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 Primary amine is confirmed
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
Secondary Amine Confirmed
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. Tertiary amine Present
Then NaOH solution is added A green colour is obtained.
b) Potassium Ferrocyanide
Test:
The compound is dissolved in
Bulky white precipitate is
dil HCl and aq. Solution of Tertiary Amine Confirmed
obtained
K4Fe(CN)6 is added to it
Dr. S. Paul Douglas, Dept. of Engineering Chemistry, A. U. College of Engg. Andhra University 6
S. No. Experiment Observation Inference
8 Nitro Compounds: (Neutral, Nitrogenous)
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 nitro 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% alcohol and 0.5 g
of Zn dust and 0.5 g of NH4Cl/ CaCl2. The mixture is boiled for 5 minutes and filtered.
i) The filtrate is added Tollen’s Black Precipitate or Silver
Nitro group present
reagent (A+B) mirror is formed
RNO2 + 4H ® RNHOH + H 2 O
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
9 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
10 Hydrocarbons (Neutral)
Note: This test should be done only after proving the absence of other functional groups
The compound is shaken with
conc. H2SO4 till a clear solution
is obtained. The contents are a) Compound did not regenerate Hydrocarbon Present
warmed if necessary while
dissolving. b) Compound regenerated Ether Present
The clear solution is poured
over ice
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:
1. Carboxylic acid / Substituted Aromatic
A) Carboxylic Acids Acidic Substances without Nitrogen
2. Phenols / Substituted Phenols
3. Alcohols
4. Carbonyl Compounds – Aldehydes and Ketones
5. Esters / Phenolic Esters
B) Neutral Compounds without Nitrogen
6. Carbohydrates
7. Hydrocarbons / Halogenated Hydrocarbons
8. Ethers
9. Amines 1 0 or Primary / 2 0 or Secondary /
C) Basic Nitrogen Containing Compounds
3 0 or Tertiary
10. Nitro Compounds
D) 11. Amides Neutral Nitrogen Containing Compounds
12. Anilides
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 characterisation 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 DERIVATIVES
1. ALCOHOLS 3,5dinitrobenzoate
2. PHENOLS benzoate, acetate, bromoderivative
3. ALDEHYDES AND semicarbazone, 2,4dinitrophenyl
KETONES hydrazone, oxime
4. ACIDS anilide, amide, ptoluidide.
benzoyl, acetyl and sulphonamide
5. AMINES
derivatives
METHODS FOR THE PREPARATION OF DERIVATIVES
1. ALCOHOLS:
(i) 3,5Dinitrobenzoates
3,5Dinitrobenzoyl chloride is usually partially hydrolysed and should be prepared in the pure
state by heating gently a mixture of 3,5dinitrobenzoic 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 watch 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 3,5dinitrobenzoyl chloride is mixed with the alcohol (0.5 1 mL) in a loosely corked dry
test tube and heated on a steam bath for about 10 min. Secondary and tertiary alcohols 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 time, 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. Collect 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 hydroxide 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 precipitates 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) 2,4Dinitrophenylhydrazones
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 hydroxide (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 induced by scratching the
sides of the test tube with a glass rod. The oximes may be crystallised from alcohol.
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 acetic anhydride
(3 mL) for 15 min. Cool the reaction mixture and pour into 20 mL cold water. Boil to decompose the
excess acetic anhydride. Cool and filter by suction the insoluble derivative. Recrystallise from ethanol.
(ii) Benzoyl derivatives (benzamides)
Suspend 1 g of the amine in 20 mL of 5% aqueous sodium hydroxide in a wellcorked flask,
and add 2 mL benzoyl chloride (fume hood!), about 0.5 mL at a time, with constant shaking. 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 obtain 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.