GROUP IV TESTS

EXPERIMENT OBSERVATION INFERENCE PRINCIPLE AND REACTIONS

TESTS FOR AMINES

ACETYLATION TEST Primary and secondary amines react with acetyl chloride to form amides, which
precipitate from the solution.
Sample in a dry test tube+ 0.5ml Acetyl Evolution of heat and HCl gas Amine
chloride added dropwise.

Pour the above mixture to a beaker A solid derivative is obtained

containing 10ml water

BENZOYLATION TEST
Sample in a dry test tube + 2ml Evolution of heat and HCl gas & Amine Primary and secondary amines react with Benzoyl chloride to give solid
dil.NaOH + 0.5ml Benzoyl chloride A solid derivative is obtained derivatives.
added dropwise

Carbylamine Test (Isocyanide

reaction) Aliphatic and aromatic primary amines give carbylamine test. The
Foul smell of carbylamines Aliphatic or Aromatic Carbylamine (Isocyanide) produced in the reaction has a foul odor.
Sample + 3 drops chloroform Primary amine
+2ml ethanolic KOH. Mix well
and warm gently
AZO DYE TEST
Take three test tubes .
Test tube 1. Sample + 2ml conc.HCl
Test tube 2. 2ml Sodium Nitrite solution
Test tube 3. 0.2g beta-Naphthol + 1ml
dil.NaoH
Cool the test tubes in an ice bath. Add
solution No.2 to 1 dropwise. Add the
above mixture to test tube no.3
HINSBERG TEST
Sample + 5ml dil.NaOH + 0.5ml
Benzenesulfonyl chloride. Shake
virorously cool and separate the residue
if present in the solution
Orange Red Dye
No residue is obtained and
thesolution on adding dil.HCl gives
a precipitate
Residue is obtained which on
adding dil.HCldoes not dissolve.
Residue is obtained on adding
dil.Hcldissolves.
This test is given by aromatic primary amines. Aromatic primary
Primary Aromatic Amine amines undergo diazotisation reaction with nitrous acid to form
diazonium salts. These diazonium salts undergo coupling reaction
with β-naphthol to form orange colouredazo dye.
Primary aliphatic amines react with nitrous acid to give unstable
salts which decompose spontaneously liberating nitrogen
gas.Secondary and tertiary amines react with nitrous acid to give
yellow nitroso compounds.
Hinsberg reagent is called benzenesulfonyl chloride.Primary
amines react with benzenesulfonyl chloride &NaOH gives N-
Primary amine
alkylsulphonamide which contains an acidic hydrogen and hence
dissolves in NaOH solution to form the soluble sodium salt. The
solution thus obtained on acidification gives a precipitate of free
sulfonamide which is insoluble in HCl.
Secondary amine A secondary amine will form an insoluble sulfonamide directly
and acidification does not cause any change.
Tertiary aminesdo not react. On acidification unreacted tertiary
Tertiary amine amine reacts with acid to give soluble salts
 GROUP V TESTS
EXPERIMENT OBSERVATION INFERENCE PRINCIPLE AND REACTIONS

2,4-DNP TEST Aldehydes and ketones react with 2,4-dinitrophenylhydrazine to

3 drops liquid sample or 1ml solid Orange red precipitate Aldehyde or Ketone form 2,4-dinitrophenylhydrazones which are insoluble solids
sample dissolved in methanol + 2ml 2,4-
Dinitrophenyl reagent

Sodium Bisulphite test Saturated solution of sodium bisulphite in water, when mixed with
aldehydes gives a white crystalline bisulphite addition compounds
Sample + 2ml saturated solution White crystalline precipitate Aldehyde or Ketone
of Sodium bisulphite

SCHIFF’S TEST Schiff’s reagent is a red solution of rosaniline hydrochloride

2 drops liquid sample or 1ml solution of Pink colour Aldehyde dissolved in water which is decolourised by passing
solid in alcohol + 1ml Schiff’s reagent
sulphurdioxide.Dilute solutions of aldehydes when added to
No Pink colour Ketone Schiff’s reagent restores its pink colour slowly.
 EXPERIMENT
FEHLING’S TEST
Mix 1ml of Fehling’s A and 1ml of
Fehling’s B solutions in a test tube + 3
drops liquid sample or 1ml solid sample
solution in alcohol. .Heat on a boiling
water bath for five minutes
BENEDICT’S TEST
2ml Benedict’s Reagent+ 3 drops liquid
sample or 1ml solid sample solution in
alcohol. .Heat on a boiling water bath for
five minutes
. In Benedict test also, Cu2+ions are reduced to Cu+ions in thesame manner as in
OBSERVATION INFERENCE PRINCIPLE AND REACTIONS
Fehling’s solution (alkaline cupric tartrate complex)
Reddish Brown precipitate Aliphatic Aldehyde Fehling’s reagent is freshly prepared bymixing equal amounts of Fehling’s
solution A and Fehling’ssolution B. Fehling’s reagent deteriorates on
keeping,whileFehling’ssolutions A and B are quite stable.
Fehling’s solution A is anaqueous copper sulphate solution
Fehling’s solution B isan alkaline solution of sodium potassium tartarate
(Rochelle’s salt).The reagent contains Cu2+ion complexed with tartarate ions.
Thestructure of the complex is given below. Complex formation decreases the
cupric ion concentrationbelow that necessary for precipitation of cupric
hydroxide.
Aldehydes reduce Fehling’s solution to produce a red precipitate of copper(I)
oxide (cuprous oxide). Aldehydes undergo oxidation to give acids
Benedict modified the original Fehling’s test by using a singlesolution which is
Reddish Brown precipitate Aliphatic aldehyde more convenient for the test. Benedict’s solutionis more stable than Fehling’s
reagent and can be stored for a longtime. It is an alkaline solution containing a
mixture of coppersulphate and sodium citrate (2Na3C6H5O7.11H2O).
the case of Fehling’s reagent.
 EXPERIMENT OBSERVATION INFERENCE PRINCIPLE AND REACTIONS

TOLLENS TEST Tollen’s reagent is an alkaline solution of silver cationcomplexedwith ammonia,

0.1g sample + 2ml Freshly prepared Silver mirror on walls of the test Aldehyde Aldehydes reduce tollens reagent to metallic silver
Tollens Reagent. Warm the test tube in a tube or a grey black precipitate
warm water bath for five minutes.

TESTS FOR KETONES

IODOFORM TEST This test is given by acetaldehyde, all methyl ketones and all
Dissolve sample in 1ml water(If alcohols containing CH3-CH CH-OH group. The reaction gives a
Yellow precipitate of Iodoform Methyl Ketone
insoluble dissolve in 1ml yellow precipitate of iodoform.
dioxane) +2ml dil.NaOH + add
Iodine solution dropwise till dark
color of iodine persists. Warm on
a waterbath at 600C

NITROPRUSSIDE TEST
Sample + Freshly prepared
Red color Methyl Ketone
solution of sodium nitroprusside
+ dil.NaOh
 EXPERIMENT OBSERVATION INFERENCE PRINCIPLE AND REACTIONS

TESTS FOR ALCOHOLS Brisk efferevescence is observed Sodium metal undergoes reaction with hydroxyl groups of many alcohols to liberate
and sodium gradually dissolves Alcohol hydrogen gas and form the salt of the alcohol
Sample in a dry test tube + a piece of
freshly cut sodium metal

ACETYLATION TEST
Sample in a dry test tube + add Alcohols and phenols react with acetyl chloride to form esters, which is
Vigorous reaction with evolution of Alcohol indicated by the formation of a topoily layer in the beaker.
0.5ml Acetyl chloride dropwise. HCl

Allow to stand for 2min. and pour Separation of an oily layer and a
into a beaker containing water pleasant ester like smell

ESTERIFICATION TEST Carboxylic acid reacts with alcohol in presence of conc. sulphuric
Sample + 1ml ethanol or methanol + 3 Sweet fruity smell of ester Alcohol
acid to form ester that is identified by the presence of a fruity
drops conc.H2SO4. Heat gently for 2 smell.
minutes. Cool pour reaction mixture into
a beaker containing sodium carbonate
solution and smell immediately

Ceric Ammonium Nitrate Test Alcohols react with ceric ammonium nitrate to give a red colored complex.
1ml Sample solution in water (If
Red Colour Alcohol
insoluble then use dioxane) + 3
drops Ceric ammonium nitrate
solution.
 EXPERIMENT
LUCAS TEST
Sample + 6ml Lucas reagent.
Close the test tube and shake and
observe for 5 min.
TESTS FOR ESTERS
PHENOLPHTHALEIN TEST
2ml sample + 1 drop Phenolphthalein +
2 drops dil.NaOH. warm the solution
HYDROXAMIC ACID TEST
Sample + 1ml Hydroxylamine
hydrochloride solution in ethanol
+ 1ml dil.NaOH. Boil, Cool and
acidify with 2ml dil.HCl. Then
add 2 drops neutral ferric chloride
solution
OBSERVATION
Solution remain clear
Solution becomes cloudy
Solution separates into two layers
immediately
Pink Color disappears
Magenta color
INFERENCE PRINCIPLE AND REACTIONS
Lucas reagent contains zinc chloride and concentratedhydrochloric acid.
Primary Alcohol This reagent reacts with primary, secondaryand
secondary tertiary alcohols at different
rates.
Tertiary alcohols reactalmost instantaneously, secondary alcohols react in
about 1-5minutes
5minutes and primary alcohols react very slowly. The reaction
Secondary Alcohol maytake 10 minutes to several days.
Tertiary Alcohol
Alcohols are soluble in Lucas reagent but the formed alkylhalides are not
soluble. Therefore, formation of two layers in thereaction medium indicate
the occurrence of the reaction.
Primary alcohols – Layers do not separate
Secondary alcohols – Layers separate within 1-5
1 minutes
Tertiary alcohols – Layers separate immediately
Esters are hydrolysed by sodium hydroxide to give alcohol and sodium salt of
Ester the acids.
Esters combine with hydroxylamine to yield an alcohol and hydroxamicacid
.The solution is then treated with ferric chloride to produce the ferric
hydroxamate complex, which has a characteristic burgundy or magenta color.
Ester