TestforAmines
Hinsberg's test: In this test, the amine is first treated with Hinsberg's reagent (benzenesulphonyl
(a) chloride) and then shaken with aqueous KOH solution when the three amines behave in different ways.
)A 1° amine
gives a clear solution which on an insoluble N-alkyl benzene
acidification gives
sulphonamide.
H O H
(O-$-CI + H-G-R -HCI
+KOH
H,0
Potassium salt
Benzene
sulphonyl chloride N-Alkylbenzenesulphonamide
(soluble in KOH)
Gi)A2° amine gives an insoluble N, N-dialkyl benzene sulphonamide which remains unaffected on
addition of acid.
R O R
+ H-N-R -K-RR + HCI
2° Amine
Benzene N, N-Dialkylbenzene
sulphonyl chloride sulphonamide
(insoluble KOH)
(iii) A 3 amine does not react at all.
KOH
CoH_ SO,CI R3N Noreaction
Benzene sulphonyl 3° amine
chloride
(b) Isocyanide test (Carbylamine test): Primary amines (aliphatic as well as aromatic) react with
chloroform inthe presence of alcoholic KOH to form foul smelling carbylamine.
RNH, + CHCI; + 3KOH (alc.) RNC + 3KCl + 3H,0
1° amine Alkyl isocyanide
NC
NH,
+ 3KCl + 3H,0
+ CHCI, + 3KOH (alc.)
Aniline Phenyl isocyanide
Secondary and tertiary amines (aliphatic as well as aromatic) do not give this test.
amine with HNO, (NaNO, + dil. HCI)
(C) Azo dye test: It involves the reaction of any aromatic primary
2-naphthol, where a brilliant yellow,
at 273-278 K followed by treatment with an alkaline solution of
orange or red coloured dye is obtained.
273-278 K
(O-N=NCT + 2H,0
O-NH,
Aniline
+ HONO + HCI
Benzene diazonium
chloride
OH
OH
Dil. NaOH + HCI
(O-G=NCr + pH 9-10
Benzene diazonium
chloride 1-Phenylazo-2-naphthol
2-Naphthol (Orange dye)
brisk evolution of N, gas with the formation
pnatiC primary amines under these conditions give a
primary alcohols, i.e.. the solution remains clear.
RNH, + HONO
273-278K R-OH + N, + H,0
Alcohol
273-278K
C,H,NH, + HONO C,H,OH + N,t + H,0
Ethylamine Ethyl alcohol
Amines 413
(6) (i) Tollens' test: When aldehydes are heated with Tollens' reagent (ammoniacal
of the test tube. Ketones silver
solution), they form silver miror On the inner side
test.
do not
respond tonitrthisate
R-CHO + 2|Ag(NH),| + 30H R CO0 + 2Ag ! + 2H,O + 4NH,
(Silver mirror)
Tollens' rcagcnt
(iü) Fehling's test: Aliphatic aldehydes when warmed with afew drops of Fehling's
Teddish brownprecipitate of cuprous oxide. Ketones do not respond to this test. ,solution give a
R CHO + 2Cu + 50H R CO0 + Cu, 0| +t 3H,0
Fchling solution Red brown ppt.
(m) lodoform test: Acetaldehyde, acetone or any ketone having at least one -CH, grOun w
heated with alkaline solution of iodine form yellow coloured precipitate of iodoform.
2NaOH + I; ’ NaOI + Nal + H,0
+
+3NaOI NaOH
’R COCI, ’ RCOO Na + CHI!
R COCH; -NaOH Iodoform
(Yellow ppt.)
(c) Tests for Carboxylic Acids
also give thi.
) Litmus test: Aqueous solutions of carboxylic acids turn blue litmus red. Phenols
test. Alcohols do not respond to this test.
(ü) Sodium bicarbonate test: When carboxylic acid is added to an aqueous solution of sodium
bicarbonate,brisk effervescence of CO, is evolved.
RCOOH + NaHCO, RCOONa + H,0 + CO,t
Carboxylic acid Sodium
carboxylate
Phenols and alcohols do not give this test.
(iiü) Ester formation test: On warming carboxylic acids with an alcohol (e.g., ethanol) in presence of
a small amount of sulphuric acid, a fruity smell of ester is obtained.
RCOOH + R'OH H,SO4 RCOOR' + H,0
Carboxylic acid Alcohol Ester
(Fruity smell)
(iv) Distinction between formicacid and acetic acid.
Tollens' reagent test: Formic acid reduces Tollens' reagent to metallic silver but acetic acid u
not. Ans.
HCOOH + 2[Ag(NH;),]* + 20H 2Ag ! + CO, + 2H,0 + 4NH,
Formic acid (Silver
mirror)
doesnot
HgCl, test: Formic acid reduces HgCI, to give white ppt. of Hg,Cl, while acetic acid
give this test.
HCOOH + 2HgCl, Hg,Cl, ! + 2HCl + CO, t
Formic acid Mercuric Mercurous
chloride chloride
(white ppt.)
