Ammoniacal silver nitrate solution (AgNO
3+ NH
4OH)
R—C—H
O
T. R.
R—C—R
O
T. R.
Tollen’stest can be used to
distinguish between aldehydes
and ketones
1. Tollen’sReagent
Silver mirror
[Ag(NH
3)
2OH] or[Ag(NH
3)
2] + OH
O
R—C—O + 2Ag + 2H
2O + 4NH
3R—C—H + 2[Ag(NH
3)
2] + 3OH
O
Compounds which react with Tollen’sreagent are :
All aldehydes (aliphatic and aromatic)
Ketones -All a-hydroxy ketones react with Tollen’sreagent
R
C R
OH
O
O
OH
(Benzoin)
Formic acid
H—C—OH
O
Hemi-acetals
C
H
H
OR’
OH
O
OH
C
R
HOH
2C
OR’
OH
Hemi-acetal
Hemi-acetal
a-Hydroxy hemi ketal
–R’–OH
C=O
R
HOH
2C
a-Hydroxy ketone
Fehling’s Solution comprises of two solutions.
Fehling A Fehling B
Aq. CuSO
4 Alkaline sodium potassium tartarate
(Rochellesalt)
HO—CH—COONa
HO—CH—COOK
Fehling A + Fehling B ---Deep blue colour
OnheatingaldehydeswithFehling’sreagent,aldehydesareoxidizedto
carboxylateionandreddishbrownppt.ofCu
2Oisobtained.
Fehling’s Solution
Aromatic aldehydes (ex: benzaldehyde) do not react with fehlingsolution.
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R—C—H
O
F.R.
R—C—R
O
F.R.
R—C—H + 2Cu
2+
+ 5OH
O
R—C—O + Cu
2O + 3H
2O
O
When methyl ketones react with halogen in the presence of base oxidation
of methyl ketones take place.
R—C—CH
3+3X
2+ 4NaOH
O
Salt of carboxylic acid
R—C—ONa+ CHX
3
O
(Haloform)
CHCl
3–Chloroform (liquid)
CHBr
3–Bromoform(liquid)
CHI
3–Iodoform(yellow solid)
10. Oxidation of methyl ketone (haloform reaction)
Ketones Methyl ketones undergo haloform reaction
R—C—CH
3
O
Aldehydes Only acetaldehyde can undergo haloform reaction
H
3C—C—H
O
Alcohols Alcohols of the following type also undergo haloform
reaction
—CH—CH
3
OH
a
NaOH + X
2is also a mild oxidizing agent
H
3C—CH—CH
3
OH
H
3C—CH
2—OH
NaOX
NaOX
H
3C—C—CH
3
O
H
3C—CHO {Give iodoform test}
Haloform Reaction
Chemical
Test
O
||
H–C–H
O
||
CH
3–C–H
O
||
CH
3–CH
2–C–CH
O
||
CH
3–C–CH
3
2, 4-DNP Test
O.C. +2,4-DNP
Red/
orange ppt
formed
Iodoform
Test
O.C. +
(NaOH + I
2)
Yellow ppt
of iodoform is
formed
Tollen’sTest
O.C. +
Tollen’s
reagent
Silver
mirror is
formed
Fehling’s Test
O.C. +
Fehling (A+B)
Solution
Reddish
brown ppt
is formed
O
||
C
H
O
||
C
CH
3
Test Acetaldehyde CH
3CHO O
||
Acetone H
3C–C–CH
3
(1) Add Fehling’s
reagent
Brown red precipitateNo change
CH
3CHO + 2Cu
+2
+ 5OH
–
CH
3COO + Cu
2O(red brown) + 3H
2O
(2) Add Tollen’stestSilver mirror No change
(i)
Difference between Aldehyde and Ketone
CHEMICAL TEST
Test Ethanal (CH
3CHO) Benzaldehyde (C
6H
6CHO)
(1) Add I
2/NaOH Yellow iodoform (CHI
3)No change
(2) Add Fehling’s
reagent
Red ppt of Cu
2O No change
(ii)
(iii)
Test Pentan-3-one Pentan-3-one
(1) Add I
2/NaOH and heat O
||
CH
3 –C –CH
2CH
2CH
3
Yellow ppt. (CHI
3)
O
||
CH
3CH
2 –C –CH
2CH
3
No change
O
||
4NaOH + 3I
2+ CH
3 –C –CH
2CH
2CH
3CHI
3+ CH
3CH
2CH
2COONa + 3Nal + 3H
2O
(Yellow ppt.)
Chemical Test
Test Acetophenone Benzophenone
(1) Add I
2/NaOH Yellow iodoform (CHI
3)No change
Yellow ppt No change
COCH
3
C
O
COCH
3
4NaOH + 3I
2+ CHI
3+
COONa
+Nal+ 3H
2O
(iv)
Chemical Test
Test Formic acid (HCOOH)Acetic acid (CH
3COOH)
(1) Tollen’sreagentSilver mirror(Ag) No Change
HCOOH+AgNH
32
+
+2ഥO→CO
2+Ag+2H
2O+2NH
3
(i)
Difference between Different-Different Carboxylic Acid
(i)
Test Phenol (White solid)Benzoic acid (White solid)
(1) Add neutral FeCl
3Violet color No Change
(2) Add NaHCO
3(aq)No change Effervescence of CO
2
C
6H
5COOH + NaHCO
3C
6H
5COONa + CO
2+ H
2O
OH COOH
Difference between Phenol and Carboxylic Acid
Test CH
3COCH
3 acetoneAcetic Acid CH
3COOH
(1)Add I
2/NaOH + heat Yellow iodoform
(CHI
3)
No change
4NaOH + 3I
2+ CH
3COCH
3CHI
3+ CH
3COONa + 3Nal + 3H
2O
(2)Add NaHCO
3 No change Effervescence of CO
2
CH
3COOH + NaHCO
3CH
3COONa + H
2O + CO
2
(ii)
Difference between Ketone and Carboxylic Acid
(ii)
Test Acetaldehyde CH
3CHO Acetic acid CH
3COOH
(1)Add Fehling’s
reagent
Red ppt. of Cu
2O No change
(2)Add Tollen’sreagentSilver mirror (Ag) No change
(3)Add NaHCO
3 No change Effervescence of CO
2
Amine
Writethechemicaltesttodistinguishbetween
pre./sec./ter.amine.
ItcanbedistinguishbyHinsbergreagent.Benzenesulphonylchloride
(C
6H
5SO
2CI),whichisalsoknownasHinsberg'sreagent,reactswith
primaryandsecondaryaminestoformsulphonamides.
(i)Thereactionofbenzenesulphonylchloridewithprimaryamineyields
N-ethylbenzenesulphonylamide.Thehydrogenattachedtonitrogenin
sulphonamideisstronglyacidicduetothepresenceofstrongelectron
withdrawingsulphonylgroup.Hence,itissolubleinalkali.
N-Ethylbenzenesulphonamide(soluble in alkali)
S–Cl+H–N–C
2H
5
O
O H O
S–N–C
2H
5+HCl
O
H
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(ii)Inthereactionwithsecondaryamine,N,N-diethyl–
benzenesulphonamideisformed.SinceN,N-diethylbenzene
sulphonamidedoesnotcontainanyhydrogenatomattachedto
nitrogenatom,itisnotacidicandhenceinsolubleinalkali.
N-N-Diethylbenzenesulphonamide
(insoluble in alkali)
S–Cl+H–N–C
2H
5
O
O
C
2H
5
O
S–N–C
2H
5+HCl
O
H
H
3C
(iii)Tertiaryaminesdonotreactwithbenzenesulphonylchloride.
Thistestisusedforthedistinctionofprimary,secondaryand
tertiaryaminesandalsofortheseparationofamixtureof
amines.However,thesedaysbenzenesulphonylchlorideis
replacedbyp-toluenesulphonylchloride.
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Writethechemicaltesttodistinguishbetweenaliphaticand
aromaticamine.
(a)Primaryaliphaticaminesreactswithnitrousacidtoformaliphatic
diazoniumsaltswhichbeingunstable,liberatenitrogengas
quantitativelyandalcohols.Quantitativeevolutionofnitrogenis
usedinestimationofaminoacidsandproteins.
R-NH
2+ HO-N=0 R–OH + N
2+ H
2O
NaNO
2+ HCl HNO
2+ NaCl
R −NH
2 + HNO
2 [R−N
2Cl] ROH + N
2+ HCl
NaNO
2+ HCl
+−
H
2O
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(b)Aromaticaminesreactwithnitrousacidatlowtemperature
(273-278K)toformdiazoniumsalts
BenzenediazoniumChloride
Orange dye if formed
b–nepthol+ NaOH
C
6H
5−NH
2 C
6H
5−N
2Cl +NaCl +2H
2O
NaNO
2+ 2HCl +−
275 −278K
Test
Primary
Amine
Secondary
Amine
Tertiary
Amine
Hinsberg
reagent
C
6H
5SO
2Cl
White ppt
soluble in
NaOH
White ppt
soluble in
NaOH
No
Change
(i)
Difference between Primary, Secondary and Tertiary Amine
Test
Methanamine
(CH
3NH
2)
Dimethyl Amine
(CH
3NHCH
3)
(1)
Add Hinsberg
reagent C
6H
5SO
2Cl
White ppt
(soluble in NaOH)
White ppt insoluble
in NaOH (aq.)
(2)
Add CHCl
3+
KOH(alc.)
Four odourof
isocyanide
No Change
(ii)
CH
3NH
2+ CHCl
3+ KOH CH
3N ≡C + 3KCl + 3H
2O
–+
(iii)
Test Aniline N-methyl-aniline
(1)
Add Hinsberg
reagent
(C
6H
5SO
2Cl)
White ppt solution in
NaOH
White ppt insoluble in NaOH
(2)
Add CHCl
3+
KOH(alc)
Foul odourof
isocyanide
No Change
NH
2
NHCH
3
C
6H
5SO
2Cl + H
2NC
6H
5C
6H
5SO
2–NHC
6H
5C
6H
5SO
2–N –Na
OH
NaOH
y
C
6H
5
NH
2
+ HCCl
3+ 3KOH
N ≡C
+ 3KCl + 3H
2O
(i)
Test Aniline
Methylamine
(CH
3NH
2)
(1) Add Br
2/H
2O
Colourof Br
2(aq.)
decolourised
No change
NH
2
NH
2
+ 3Br
2(aq)
NH
2
Br
Br
Br
+HBr
(Colourless)
Difference between Aliphatic and Aromatic
(ii)
Test
Cyclohexylamine (Aniline)
(1)AddNaNO
2and
HClandthenadd
phenolinpresence
ofabase
N
2gasisliberated
andnocolourationis
observed.
Stablediazoniumsalt
isformedwhichreacts
withphenoltoform
orangedye.
NH
2NH
2