Part I

GENERAL PROCEDURE FOR THE SYSTEMATIC QUALITATIVE

ANALYSIS OF ORGANIC COMPOUNDS
i. Preliminary investigations.
a. Physical State.
b. Color
c. Odour.
d. Ignition on china porcelain.
e. Action of 30% sodium hydroide solution.
f. Action of hot concentrated sulphuric acid.
g. !eaction "ith ferric chloride.etc.
ii. #etection of elements$ %ive details for the detection of nitrogen& sulphur and
halogens
iii. #etection of functional groups$ %ive the procedure for the detection of functional
groups especially for the group's( that is found to be present.
iv. #etermination of melting 'boiling( point$ )he Compound is found to melt 'boil(
at....C.
v. Probable Compound$ On the basis of the standard data of the melting 'boiling(
points of substances having particular functional groups's(& the given compound is
most probably.........
vi. Special tests of the compound$ %ive the special test's(& if any& for the particular
compound.
vii. #erivatives$ %ive the methods of the preparation of at least t"o important
derivatives and also mention their melting points observed by you.
*
Result:
+ence the given organic compound is$
*. Aromatic,Aliphatic
-. Saturated,.nsaturated
3. Special element present,/ot present
0. 1unctional group present
2. 3elting point
4. Probable compound based on melting point and derivatives prepared5
PRELIMINARY INVESTIGATIONS
1. Phys!"l st"te "#$ !%l%u&
In organic compounds the colour is generally associated "ith the presence of
certain functional groups i.e. particular group in the compound is responsible for a
particular shade. +o"ever& it should also be noted that several organic compounds are
colourless in the pure state but oidi6ed to coloured compound by atmospheric air&
e.g. amines. )he different important groups along "ith their most usual colours are
summari6ed belo" in the solid and li7uid states.
A. S%l$s
Colour Possible compounds
8ello" Iodoform& ben6oin& 9en6yl anthracene&
7uionones and nitro compounds.
Orange Ortho:nitro aniline.
Pin; /aphthols.
9ro"n
#iamines& aromatic higher amines and
aminophcnols.
-
'. L(u$s
Colourless to red bro"n Amines.
8ello" to Orange /itro compounds.
). O$%u&.
3ost of the organic compounds possess characteristic odo"gt;e: odour of
some compounds is so characteristic that it can be used even to distinguish the
particular class of compounds or sometimes even a single compounded from that of
others.
O$%u& P%ss*le !%+,%u#$s
Carbolic or Phenolic Phenols
/aphthalene li;e /aphthalene& p:dichloro or p:dibromo ben6ene.
3ice li;e Acetamide.
9itter almond li;e 9en6aldehyde. nitroben6ene
Pleasant Alcohols& ethers& esters
<ery pungent =o"er aliphatic acids and their halogen derivatives.
-. Test .%& Al,h"t! %& "&%+"t! #"tu&e:
/ I0#t%#
)he nature of organic compound '"hether aliphatic or aromatic( can be
established by the ignition test.
)he compound is placed on a nic;el spatula. )he latter is then heated first
slo"ly and then strongly in a burner flame. If the compound burns "ith an non:smo;y
flame& it is an aliphatic compound 'ecept chloroform& chloral hydrate and ethyl
acetate "hich burn "ith a smo;y flame(5 "hile if it burns "ith a sooty or smo;y flame
the compound is aromatic in nature. )he aliphatic and aromatic nature of compound
may further be ascertained by the follo"ing tests.
3
i. Nt&"t%# test. )a;e * gm. 'or lml.( of the compound in a test:tube. Add
-ml. Of conc. +/O3 and -ml. of conc +
-
SO
0
. +eat the contents for about
2 minutes&cool and pour the contents in cold "ater: formation of a yello"&
oily li7uid or solid indicates the presence of an aromatic compound 5
other"ise it is an aliphatic compound.
ii. Le R%se# test. )a;e 0.- gm. 'or 3:0 drops( of the organic compound&3:0
drops of formaldehyde solution and 2ml& Of con +-SO0.Sha;e the
contents "ell and then "arm:formation of red& orange& violet or green
colour or precipitate indicates the presence of an aromatic compound5
other"ise it is an aliphatic compound.
iii. I0#t%# %# !h#" ,%&!el"#: Place a small amount of the compound on a
porcelain dish and then heat it first gently and then strongly. /ote the
change in appearance& the odour produced and the residue left.
1ollo"ing are the notable observations and inferences of various important
compounds.
Observation Inference
9urns "ith luminous flame Aroma>tic or unsaturated
Smo;y flame... Aliphatic compounds
Smell of ammonia Amides
<iolet vapours Iodoform
Chars but does not melt .ric acid& sulphonic acid& starch
#ar;ens& s"ells& chars "ith
9urnt Suger Odour
Carbohydrates& lartaratcs& lactates ? 0 glucose
and some citrates.
0
1. S%lu*lty
2/ A!t%# %. )34 s%$u+ hy$&%5$e s%lut%#:
)reat a small amount of the compound "ith nearly 2ml of the al;ali solution
and note do"n the change in the cold state.
Observation Inference
#issolves in /aO+& reprecipates on adding Aromatic acids& Phenol
Con. +C=
3iture sets to a "hite solid @sters of diabasic acids
+ighly coloured solution /itrophenols& nitoracids& salicylaldehyde
Colour becomes deep on standing polyhydricphenols& some aminophenols
8ello" to bro"n resin Aliphatic aldehydes
/o" heat the solution and note the change
Compound dissolves some esters or acid anhydrides
Ammonia is evolved Amides& imides& urea& thio:urea&
8ello" or bro"n solution sulphonamide sugars 'ecept sucrose(& polynitro
compounds& halogennophenols& halogenonitro
hydrocarbons.
Chloroform li;e odour Chloral.
/ A!t%# %. h%t !%#!e#t&"te$ sul,hu&! "!$:
)reat a small amount of the given compound "ith concentrated sulphuric acid&
note the change and then "arm it.
Observation Inference
@volution of CO
-
"ithout charring urea.
@volution of CO
-
and CO.
And miture becomes yello"
"ithout charring.
Aliphatic hydroy acids
@volution of CO and ,or CO
-
And SO
-
"ith immediate blac;ening
Carbohydrates& aliphatic hydroy
acids.
9lac;ening but no effervescences. Polyhydric phenols.
Pungent vapours "ithout charring Carboylic acids 'simple(
/ A!t%# %. N"HCO
-
:
2
0.l g of the substance treated "ith -ml of saturated /a+CO3 soln.
#issolves "ith bris; effervescence of CO
-
Acid or acidchloride.
6/ A!t%# %. Dl. HCl:
0.2g of the substance treated "ith -ml of dil. +CI and sha;e "ell.
#issolves in +C* and reappears on adding 9asic substance 'Amines(
*0% /aO+ solution.
7. Re"!t%# 8th Neut&"l .e&&! !hl%&$e:
)his regent is fre7uently used for identifying the presence of phenols and
aliphatic a:hydroy acids.& )a;e nearly t"o ml. of the compound solution either in
"ater or in alcohol and add to it one or t"o drops of neutral ferric chloride solution
and note the changes as belo".
Observation Inference
!ed colour but disappears =o"er fatty acids& maleic acid
by adding dil.+C=. or amino acid.
Intense transitory bluish:green o:phenylene diamine
Colour.
Intense red:bro"n colour ortho or meta:phenylene diamine.
Or ppt.
Purple colour salicylaldehyde& salicylic acids& salicylamide
acetylsalicylic acid& phenyl salicylate.
9lue or red colour Phenols& resorcinols& cresols& arninophenols.
%reenish colour or ppt. Catechol. Auinolnes of naphthol.
#eep yello" colour aliphatic a:hydroy acids
Pale bro"n ppt. dissolves in
div +C=
#icarboyiic acids soluble in "ater.
1erric chloride may also be used for identifying certain amines. In practice& the
compound is dissolved in dilute hydrochloric acid and t"o drops of ferric chloride
solution are added to the solution.
Observation Inference
%reen or blue green colour diphenylarnine& aniline
4
/:methylaniline
<iolet colour P:anisidine.
!ed colour P:phenetidine.
!ed ppt. O:phanylenediamine.
9lue ppt. O:naphthylamine& o:toluidine.
9. Re"!t%# 8th T%lle#:s &e"0e#t:
0.* g of the substance dissolved in suitable solvent and add -ml of )ollenBs
reagent. Carm on "ater bath.
9lac; ppt or bright silver mirror Presence of Aldehydes& carbohydrates&
polyhydric Phenols or other reducing agents
;. Test .%& s"tu&"t%# %& U#s"tu&"t%#
*. Action of potassium permanganate$ Potassium permanganate is a very
important oidi6ing agent in neutral& acid as "ell as in al;aline medium.
. I# #eut&"l +e$u+:
#issolve the substance in "ater and then add to it 0:2 #rops of neutral
potassium permanganate solution "ith constant sha;ing :violet colour discharged in
case of olefinic compounds.
. I# "!$! +e$u+:
Perform above test using potassium permanganate solution acidified "ith
dilute sulphuric acid and then "arm the contents:violet colour discharged in case of
olefinic compounds& or easily oidisable compounds 'aldehydes& ;etones& oalates
and formates.(
. I# "l<"l#e +e$u+:
Perform the test as in 'i( but using solution made al;aline "ith a fe" drops of
dilute sodium carbonate solution :violet colour discharged in case of aldehydes&
Phenolic acids& formates and cinnamates.
In case colour is discharged on "arming ?a hydroy acids& vi6& citric& lactic&
tartaric& etc. may be present.
D
-. 0.0 g of the substance E* ml of "ater 3:0 drops of 9romine "ater. Sha;e "ell.
8ello" colour decolori6ed. .nsaturated compound
8ello" color persist Saturated compound
8ello" color decolori6ed F ppt
is 1ormed Saturated compound : amines& phenol.
=. TESTS FOR SPECIAL ELEMENTS
1. L"ss"0#e:s test .%& #t&%0e#> sul,hu& "#$ h"l%0e#s:
Preparation of Lassaigne's extract of sodium fusion extract: Place a fe"
crystals or drops of an un;no"n compound in a fusion tube. 3old the test tube in an
inclined position and place a freshly cut out piece 'the si6e of a "heat grain( of
sodium metal slightly above the substance. 3old the test tube hori6ontally using tongs
or "ooden clamp. 1irst heat sodium until it melts. /o" set the test tube in the vertical
position so that the hot drops fall onto the test:substance. 3eat the miture to redness.
Plunge the red hot tube once in a china dish having nearly *0:*2 ml. of distilled "ater
"hen the fusion tube "ill be torn out& if not& do so yourself "ith the help of tongs.
9oil the resulting product. 1ilter the hot solution and "ash the residue "ith small
amount of distilled "ater. )he filtrate so obtained is ;no"n as =assaigeBs filtrate or
etract and used for testing nitrogen& sulphur and halogens. =assaigneBs etract should
be colourless. 8ello" or bro"n colour indicates incomplete decomposition of the
original substance. If so& repeat the eperiment using a ne" portion of the same
substance.
/a E CE/ /aC/
- /a E S /a
-
S
/a E C E SE/ /aSC/
/a E G /aG
H
i. Test .%& #t&%0e#: )a;e a small 7uantity of the etract in a test tube and ma;e
it al;aline 'if it is not so( by adding a fe" drops of sodium hydroide. Add 0.*
to 0.- gms& of solid ferrous sulphate 'a blac; precipitate "ill appear if sulphuc
is present(& boil the resulting solution and then acidity it "ith cone. +
-
SO0 or:
+C=. )he formation of Prussian blue precipitate or green colour indicates the
presence of nitrogen.
4/aC/ E 1eSO
0
/a
0
1e 'C/(
4
E/a
-
SO
0
Sodium ferrocyanide
o-
1eSO
0
1e
-
'SO
0
(
3
3/a
0
1e 'C/(
4
E 31e
-
'SO
0
(
3
1e
0
'1e'C/(
4
(
3
E 4/a
-
SO
0
ferric ferrocyanide
P&e!"ut%#s: 'i( Since the yello" colour of ferric chloride fades the Prussian blue
colour& it is better to avoid the addition of ferric chloride during the above test.
Similarly& on the same ground acidification "ith conc. +
-
SO
0
is preferred to
concentrated +C=.
'iii( Some compounds li;e urea and its derivatives although possess nitrogen& they do
not respond the above test5 the reason being the deficiency of carbon in these
compounds and hence in the above test "henever there is some doubt& the "hole of
the process must be repeated using miture of the compound "ith some amount of
cane sugar to provide sufficient amount of carbon.
1unction of conc. +
-
SO
0
or +C= )he function of the acid is to dissolve the
precipitate of ferrous or ferric hydroide 'formed by reaction "ith 1eSO
0
and /aO+(
as the ferrous or ferric sulphate or chloride.
1eSO
0
E -/aO+ /a
-
SO
0
E 1e'O+(
-

1e
-
'SO
0
(
3
E 4/aO+ 3/a
-
SO
0
E -1e'O+(
3

I
1e'O+(
-
1eSO
0
or 1eCI
-
E-+
-
O
-1e'O+(3 1e-'SO0(3or1eCl3E4+-0
)est for sulphur$ 1ollo"ing tests may be adopted for sulphur.
i. Acidify the =assaigneBs etract "ith dilute acetic acid and then add a fe"
drops of lead acetate& a blac; precipitate "ill be formed.
'C+
3
COO(
-
Pb E /a
-
S -C+
3
COO/a E PbS
9lac;
ii. Add fe" drops of freshly prepared dilute solution of sodium nitroprusside
'since in a7ueous solution& it is unstable( to the etract& the appearance of a
purple colour confirms the presence of sulpur.
/a
-
J1e'C/(
2
/OK E /a
-
S /a
0
J1e'C/(
2
/O
2
K
Sod.nitroprusside Sod. Sodiom Sulphorino pruside
'<iolet(
. Test .%& #t&%0e# "#$ sul,hu& 8he# ,&ese#t t%0ethe&:
#uring performing the test for nitrogen if a blood red colour is developed after
adding ferrous sulphate crystals& nitrogen and sulphur seem:to be present together.
4 /aSC/ E 1e 'SO
0
(
3
-1e 'SC/(
3
E 3/a
-
SO
0
ferric sulphocyanide 'red colour(
*0
Conc.+-SO0
Or Conc. +Cl
Conc. +
-
SO
0
Or Conc +Cl
?. DETECTION OF FUNCTIONAL GROUPS
)he tests of various important functional group are summari6ed belo".
1. CAR'O@YLIC ACIDS
3ost aliphatic carboylic acids are soluble in cold "ater& "hile aromatic acids
are sparingly soluble in cold "ater but readily soluble in hot or boiling "ater. )he
presence of carboylic group can easily be the follo"ing tests.
2/ Lt+us tests:
=i;e phenols& the carboylic acids turn blue litmus solution to red. 1or this
test& one drop of blue litmus solution is added to the a7ueous solution of the acid& the
appearance of red colour indicates the presence of a phenol or an acids.
P&e!"ut%#: As sometimes 'vi6. in case of very "ea; acids( it becomes
difficult to note the change in colour thus the test must be performed on a "hite tile.
2/ S%$u+ *!"&*%#"te:
Add some drops of concentrated sodium bicarbonate solution to the acid in
test tube or better on a "atch glass or a "hite tile. @volution of effervescences of
carbon dioide indicates the presence of a carboylic group.
!COO+ E /a+CO
3
!COO/a E +
-
O E CO
-
Precaution$ Some phenols li;e -&0&4 :trinitrophenol and -&0&4:tribromophenol
also behave li;e acids and hence evolve carbon dioide on treatment "ith sodium
bicarbonate.
2/ l%$"teA%$$e test:
%rind e7ual amounts of the carboylic acid& potassium iodide and potassium
iodatc& the appearance of bro"n colour o"ing to the formation of free iodine indicates
the presence of a carboylic group.
4!COO+E2LIELIO
3
4!COOLE3+
-
OE3I
-
In case the compound is li7uid ta;e a little amount of it& 2:4 drops of -%
potassium iodide solution and 2:4 drops of 0% potassium iodate solution. Cor; the
**
test:tube and place in boiling "ater for *:- minutes. Cool and add about 2:*0 drops of
starch solution. 9lue colour indicates COO+ group.
26/ Este& test:
Carm nearly * ml. of the acid& -ml. of methyl or ethyl alcohol and a small
amount of concentrated sulphuric acid for *:- minutes on the "ater bath& in a test
tube. Cool and pour the solution to a china dish:having some sodium carbonate
solution& fruity smell of ester indicates the presence of acid
!COO+ E C-+2O+ !.C:OC-+2E+-O
26/ Fe&&! !hl%&$e test:
/eutrali6e 0.2 gm of the acid "ith ecess of ammonia in a boiling test tube.
9oil the solution to remove ecess of ammonia& cool and a fe" drops of neutral ferric
chloride solution. /ote the colour of the resulting solution and ta;e out inference
according to the follo"ing facts.
A reddish bro"n colour or ppt. is obtained in case of aliphatic mono:
carboylic acids.
A buff or bro"nish coloured precipitate is obtained in case of aromatic
acids and some aliphatic acids li;e succinic and adipic acids.
An intense yello" colour is obtained in case of alpha hydroy acids this
test may also be applied as follo"s. 1irst add a fe" drops of ferric chloride
to a dilute a7ueous solution of phenol and then add this resulting violet
coloured solution to a solution of a alpha hydroy acid in "ater the violet
colour is discharged and a deep yello" tinge appears.
A violet or bluish colour is obtained in case of o:substituted aromatic
hydroy acids.
6. Dete!t%# %. u#s"tu&"t%# # "!$:
i. #issolve a small amount of the acid in chloroform or carbon tetrachloride and add
to -:3 drops of bromine solution in the same solvent 'i.e. either C+C=3 or CC=0(.
*-
O
#isappearance of bromine colour "ithout evolution by hydrobormic acid suggests
the presence of unsaturation in the compound. On the other hand& if the bromine
colour is discharged "ith the evolution of hydrobromic acid& a phenol& aromatic
amino or enol is indicated. )he evolution of hydrobromic acid may be easily
detected by eposing the vapours to a solution of silver nitrate in nitric acid held
on the end of a glass rod.
!.C+ M C+.! E 9r !.C+9r.C+9r.!
2/ '"eye&:s test:
Add one or t"o drops of *:- % L3nO
0
solution to small amount of the acid
dissolved in "ater or acetone disappearance of purple colour indicates the presence of
unsaturation.
Precaution: Some easily oidisable compounds li;e aldehydes& alcohols&
formic acid some aliphatic hydroy acids phenolic acids also respond this test.
26/ Test .%& D!"&*%5yl! "!$s: 3i 0.* g of the substance "ith 0.2g of resorcinol
and 0drops of con. +-SO
0
in a hard glass test tube. +eat for 3:2 minutes pour it into
dil. /aO+. An intense greenish yello" fluorescence indicates a #icarboylic acid.
*3
O+ O+
9r
9r
E +9r
LmnO
0
!.C+:C+.!
!.C+ M C+.! O+ O+
'O( E +
-
O
LmnO
0
!.C+O

!COO+
'O(
L3nO0
). ACID ANHYDRIDES
i. #issolve the compound in ben6ene or chloroform and add some aniline to
the resulting solution. Carm the solution for nearly *:- minutes& and cool.
A "hite precipitate of anilide is formed.
iii Anhydrides produce fruity smelling esters "hen "armed "ith n:butyl
alcohol.
-. PHENOLS
i. Lt+us test: =i;e acids. phenols also turn blue litmus solution colour to
red
ii. S%$u+ *!"&*%#"te: @cept highly negatively substituted phenols
'eg.picric acid(& Phenols in general do not decompose sodium bicarbonate
solution 'difference from acids(
iii. Fe&&! !hl%&$e test: Add one or t"o drops of neutral ferric chloride to a
dilute a7ueous or alcoholic solution of the compound in a test tube& the
appearance of a characteristic colour 'violet& blue or green( indicates the
presence of phenolic group.
4C
4
+
2
O+ E1eCl
3
J'C
4
+
2
0(
4
1eK
:3
E3+C= E3+
E
iv. )a;e a small amount of the phenol in a test:tube& add to it al;ali and a
small 7uantity of a cold solution of dia6otised
*
p:nitroantiine solution 'p:
nitro aniline "ith dil +Cl follo"ed by cold:/a/O
-
solution( red color.
v. Phthalein test.
)a;e a little 'nearly 0.-gm.( of the phenol and an e7ual amount of phthalic
acnhydride in a dry test tube. Add nearly -:3 drops of concentrated sulphuric acid and
*0
Ac
-
OEC
4
+
2
/+
-
Ac/+C
4
+
2
CO/+C
4
+
2
COO+
Anilic acid
EC
4
+
2
/+
-
COO+
COO+
fuse the miture gently for about *2 minutes. Cool and pour the contents to dilute
sodium hydroide solution. Characteristic colours of dyes are obtained as belo".
C%+,%u#$ C%l%u& %. the $ye .%&+e$ C%+,%u#$ C%l%u& %. the $ye F%&+e$
Phenol !ed !esorcinol %reen
o:Croseol !ed +ydro7uinone #eep violet
m:Cresol 9luish:purple N:/aphthol %reen
Catechol 9lue O:/apthol <ery faint green
vi. Nt&%us "!$ test: )a;e a little of the compound in a test iube& add nearly
*ml of Conc. +
-
SO
0
and then add a little sodium nitrite. Sha;e the contents
and "arm gently& appearence of green,purple or blue colour indicates the
presence of phenolic O+ group. )ransfer the contents in little "ater "hen
the blue colour changes to red or blue:red. )he colour "ill again change to
blue or green on addition of a little -0% Sodium hydroide.
*2
vii. AB% $ye test: #issolve -:3 drops of aniline in one ml. of concentrated
hydrochloric acid and cool it in ice. )o this solution add a fe" drops of
cold sodium nitrite solution and then add this solution to a cold solution of
phenol in an ecess of /aO+ solution. Coloured solution or precipitate
indicates the presence of a phenolic group.
Tests .%& ,%lyhy$&! Phe#%ls: 'i( )a;e about - ml. of dilute ammonium hydroide or
/aO+ solution and add to it a crystal as large as rice :grain of the original compound.
Sha;e the content of the test tube :formation of yello" colour changing to red:bro"n
indicates polyhydric phenols.
'ii( )a;e about 3:0 ml. of )ollenBs reagent in a test :tube and add to it *ml of the
a7ueous solution of the original compound :a grey or bro"n precipitate is formed
immediately in case of catechol& 7uinol& pyrogallol& gallic acid and tannic acid5 "ithin
30 seconds in case of orcinal and phloroglucinol5 and "ithin - minutes in resorcinol.
1. ALCOHOLS
Alcoholic group can be detected by the follo"ing tests.
i. A!t%# %. s%$u+: )a;e nearly *ml. of the alcohol 'in case of solid& dissolve it in
the dry ben6ene or ether( in a test:tube and add to it a small piece of freshly cut
sodium:evolution of bric; effervescences of hydrogen suggests the presence of
alcoholic group.
-!O+E-/a -!O/aE+-
2/ Re"!t%# 8th "!etyl !hl%&$e.
)a;e about * ml. of acetyl chloride in a dry test tube and add to it about 0.2
ml. of the original compound :vigorous reaction occurs 'i.e bubbles are freely
evolved( "ith in - minutes "ith the evolution of +C= fumes. 9ring a glass rod dipped
in /+
0
O+ :"hite fumes of ammonium chloride are produced. Chen the reaction
'bubbles( stops& add one ml. of "ater to dissolve the remaining +C= gas5 separation
of an oily layer along "ith the ester li;e odour Confirms the presence of alcohol.
*4
!O+ E C+
3
COCl !OCOC+
3
E +CI
+CI E /+
0
O+ /+
0
C E+
-
O
Dst#!t%# *et8ee# ,&+"&y> se!%#$"&y "#$ te&t"&y "l!%h%ls:
i. )a;e *ml of pure acetone& one drop or *0 mg. of the alcohol and then one drop of
the chromic acid regent. stir the miture immediately:greenish blue coloured ppt.
is formed "ithin t"o seconds in case of primary and secondary alcohols. If no
precipitate or colour change occurs at once tertiary alcohol is indicated.
ii. )a;e * ml. of the compound in a test tube and add 2 ml. of lucas reagent "ith
sha;ing. /ote the follo"ing observations formation of insoluble chloride layer at
once tertiary alcohol. Appearance of cloudiness "ithin 2 minutes secondary
alcohol. Solution remains clear "ith some dar;ening primary alcohol.
iii. #issolve 0.- gm. of the compound in about *0 ml. of 0.0*% solution of bromine
in carbon tetrachloride. Add about 0.- gm. of /:bromosuccinimide and place the
test tube in a "ater bath at H0PC./ote the colour obtained.
Permanent orange colour Primary alcohol.
)ransient orange colour Secondary alcohol.
/o colour )ertiary alcohol.
7. CAR'ONYL COMPOUNDS 2Al$ehy$es "#$ <et%#es/
i. Aldehydes and ;etones& in general& are detected by reaction "ith -& 0:
dinitrophenylhyra6ine it form crystalline -.0:dinitro:phenylhyra6ine.
Add - drops or *.* gm. of the substance in dilute +C= to 3ml. of the -&0:
dinitrophenylhyra6ine solution 'reagent( in dilute +C= and sha;e the miture:yello"&
orange or red coloured crystalline precipitate may be formed at once& or on allo"ing
the miture to stand for *2 minutes& or on gentle "arming on a "ater:bath.
*D
ii. S%$u+ *sul,hte test: 3ost of the aldehydes and ;etones react "ith a
concentrated a7ueous solution of sodium bisulphite to form a crystalline solid.
CMO E /a+SO
3
iii. Solutions of many aldehydes and ;etones develop red colour "hen treated "ith
sodium nitroprusside and al;ali. )o a solution& of the substance add *ml of 3%
sodium nitroprusside solution and 2 drops of *0% /aO+ '!ed or pin; color(.
iv. It is important to note that the above tests are not positive in all aldehydes and
;etones. In case of ;etones only those ;etones "hich have at least one methyl or
ethyl group attached to the carbonyl group respond these tests.
v. Add /essierBs solution to etremely dilute a7ueous solution of aldehydes or
;etones voluminous precipitates. )his test is given only by simpler aldehydes and
;etones.
vi. Fehl#0:s test: 3i -ml. of fehling solution A 'copper sulphate solution( and
1ehimg solution 9 'al;aline tartarate solution(. )o the mied solution add 3 drops
'or 0.*2gm.( of the suspected compound and "arm the resulting solution. )he
appearance of a red precipitate of cuprous oide indicates the presence of an
aldehydic group.
!:C+O E -Cu'O+(
-
!:COO+ECu
-
O E-+
-
O
Note that some ketones like benzoin also reduce Fehitng solution
*H
O+
C
SO
3
/a
vii. S!h..:s test: Add t"o drops of the compound under test to -ml. of the reagent
'pararosaniline hydrochloride solution& the colour of "hich is >ust decolourised by
passing SO
-
(. Sha;e the contents& appearance of a violet or red colour "ithin t"o
minutes indicates the presence of an aldehyde.
*I
/+
SO
-
+
SO
-
/+
/+
-
E
-ArC+O
Sha;e
C
SO
3
+
+
-
/
/+
C
Ar
+SO
3
+
C / C
Ar
SO
3
+
+
viii. T%lle#:s Test: )a;e nearly 3:0 ml. of the freshly prepared )ollenBs reagent in a
clean and dry test : tube and add to this -:3 drops 'or 0.* gm. in case of solid( of
the substance. Sha;e the solution and if no reaction occurs in the cold& "arm 'not
9oil( the tube gently in a bea;er of "ater at 20$ )he formation of a blac;
precipitate of metallic silver or silver mirror indicates the presence of a reducing
substance li;e aldehydes.
P&e!"ut%#s: 'i( )he reagent must freshly prepared but it must be "ashed
a"ay after use. As it forms eplosive substance if stored.
C+O E Ag
-
O COO+ E -Ag
!iii" #ome ketones like p$ruvic acid reduce the %ollen's reagent
i. 'e#e$!t:s test: Add 2ml of 9enedictBs solution to 0.0ml. of -% solution of the
compound. 9oil the solution for t"o minutes and then cool rapidly. 1ormation of
a red precipitate suggests the presence of a reducing sugar or an aliphatic
aldehyde.
!C+O E -Cu
EE
'as citrate comple( E 0O+
:

9. CAR'OHYDRATES
)he carbohydrates may be detected by the follo"ing tests.
i. M%ls!h:s test: #issolve nearly 0.002gm. of the carbohydrate in one ml. of
"ater& add t"o drops of the molischQs reagent '*0% N:napthol in alcohol(
and sha;e. /o" add carefully -ml. of concentrated sulphuric acid along
the side of the test:tube and allo" it to stand for - minutes. )he formation
of a reddish violet colour at the >unction of t"o li7uids indicates the
presence of carbohydrate. ,BSha;eB the contents of the test:tube in a stream
of cold "ater& a deep purple solution is obtained& "hich on dilution "ith
cold "ater yields a violet precipitate.
-0
)ollenBs Silver
!eagent mirror
!COO+ E Cu
-
O E -+
-
O
'red(
Polysaccharides 3onosaccharides Sulphuric Ehydroyfurfural
)riarylmethane compounds '<iolet(
'iv(. '"&.%e$:s test: )he test is used in differentiating the monosaccharides from
disaccharides. )a;e one ml. of the freshly prepared 9arfoedBs reagent '0.33 gm. of
neutral copper acetate dissolved in 2 ml. of cold *% acetic acid( and add one ml. of
the carbohydrate solution to it. +eat the solution in a boiling "ater:bath& formation of
a red precipitate in the blue solution& or on the sides of the tube >ust above the li7uid&
"ithin t"o minutes indicates the presence of a monosaccharide 'glucose& fructose or
galactose(.
;. ESTERS
i. @sters are usually identified by their hydrolysis reaction. )a;e -:3ml of ester
solution in a test tube& add some sodium hydroide solution and a drop of
phenolphthalein& the pin; colour "ill be developed. +eat the reaction miture
for some time& the disappearance of pin; colour indicates the presence of an
ester group.
!COA!B Eal;ali E Phenolphthalein !COO+ E !BO+
=. ALIPHATIC PRIMARY AMINES
Aliphatic primary amines in general can be detected by the follo"ing tests.
i. Carbylamine reaction$ Carm a small amount '0.02 : 0.* gm. or - drops( of
the amine "ith - drops of chloroform and one ml. of alcoholic potash in a
test tube& a nauseating 'foul( odour of isocyanide 'carbylamine( indicates
the presence of a primary aliphatic or aromatic amine.
!/+
-
EC+Cl
3
E 3LO+ !/CE3LClE 3+
-
O
/ote$ It is al"ays advisable to decompose the isocyanide formed by adding
concentrated hydrochloric acid before thro"ing it in the sin;.
-*
heat
Pin; color Pin; color discharged
ii. Re"!t%# 8th #t&%us "!$: #issolve nearly 0.- gm. of the amine in 2ml.
of cone hydrochloric acid& cool it in ice and then add nearly -ml. of ice:
cold sodium nitrite solution& bris; effervescences of nitrogen "ill be
evolved in case the compound is primary amine. Sometimes& "arming on
the "ater:bath is re7uired in order to evolve the nitrogen.
!/+
-
E +O/O !O+E/
-
E +
-
O
iii. R+#:s test: )a;e fiearly 3:drops of the amino solution in 2ml.of "ater&
add to it *ml. of acetone and a drop of sodium nitropursside solution&
appearance of a violet colour "ithin t"o minutes indicates the presence of
primary aliphatic amino group.
?. AROMATIC PRIMARY AMINES
i. C"&*yl"+#! &e"!t%#: Same as in aliphatic primary amines.
ii. Re"!t%# 8th #t&%us "!$: #issolve nearly 0.* gm. of the given amine in
3ml. of concentrated hydrochloric acid in a small bea;er or a large hard
glass test tube. Cool it in ice to nearly 0PC and to this add 2ml. of ice cold
sodium nitrite a7ueous solution "ith constant sha;ing till a slight ecess of
nitrous acid predominates in the solution. Chen the reaction ceases& add
ice cold solution of O:naphthol in al;ali5 the formation of a bright red&
orange red or reddish blue precipitate or colour indicates the presence of
primary aromatic amino group. )he solubility of the dye in /aO+
indicates the presence of a hydroyl group in the amine.
13. ALIPHATIC AND AROMATIC SECONDARY AMINES
i. Re"!t%# 8th #t&%us "!$: #issolve nearly * gm. Of the compound in 3:
2 ml. of dilute hydrochloric acid and cool it is ice cold "ater. )o the above
solution add 0:2ml. *0% sodium nitrite solution drop "ise and "ith
constant sha;ing. Allo" the solution to stand or 2 minutes "hen a yello"
or "hite oil precipitate is produced.
ii. S+%#:s test: )a;e a fe" drops of the compound and add to it dilute
solution of sodium nitroprusside follo"ed by a fe" drops of dilute
acetaldehyde solution:deep blue or violet colours "ill be produced "ithin
--
five minutes.
11. AMINOAACIDS
Al,h"t!: )he presence of one of these acids may detected by the follo"ings
tests&
i. Add fe" drops of 0.-% solution of ninhydrin reagent to the a7ueous solution of
the substance a blue colour is produced.
ii. Add a fe" drops of ferric chloride solution to a7ueous or alcoholic solution of
amino acids 'red colour is developed(&
iii. S%&e#se# test: )a;e near about 0.2gm. of the compound in a test tube and
dissolve it in "ater or alcohol. Add t"o drops of phenolphthalein and then very
dilute sodium hydroide solution till a pin; colour is obtained& In other test tube
ta;e the similar things in the similar order only "ith the difference that here the
amino acid is replaced by 00% formalin solution. Add the solution from the
second test tube to the first5 the disappearance of the pin; colour is indication of
the amino acid.
-3
O
C
C
O
C
O+
O+
+
-
/.C+!.COO+
O
C
C
O
C M /
O
C
C
O
CO
-
E !C+O E +
-
O
Amino acid
9lue Color
A&%+"t!:
a. Aromatic amino acids are more acidic than the aliphatic amino acids cause
a vigorous evolution of carbon dioide from sodium bicarbonate.
b. )hey usually give reddish colour "ith ferric chloride solution.
c. =i;e aromatic primary amines& these undergo dia6otisation "ith nitrous
acid "hich couple "ith al;aline -:naphthol solution to give coloured a6o
dyes.
*-. A=IP+A )IC /I)!O CO3PO./#S
i. #issolve a small amount of the compound in concentrated sodium hydroide
solution and then add an ecess of sodium nitrite solution. /o" add some amount
of "ater follo"ed by drop"ise addition of dilute sulphuric acid. )he appearance
of a red colour "hich disappears on adding ecess of acid and reappears on adding
al;ali indicates the presence of a primary aliphatic nitro group. Secondary nitro
group on similar treatment produces a permanent dar; blue or blue green colour
soluble in chloroform. )ertiary nitro compounds do not respond this test.
ii. !eduction in neutral medium$ #issolve nearly 0.2gm. of the substance in an
e7uirnolar miture of alcohol and "ater by "arming. Add to it some amount of
6inc dust and solid /+
0
C*. 3eat the miture to boil and allo" the reaction to
comlete. 1ilter the solution and add )ollenBs reagent to the filtrate& a blac;
precipitate or mirror "ill be developed.
-0
Rn:/+
0
Cl
!/O
-
!/+O+ E +
-
O
!/+O+ E Ag
-
O !/O E -Ag E +
-
O
1-. AROMATIC NITRO COMPOUNDS
'i( Aromatic nitro compounds give the
'ii( test above
11. AMIDES AND EVIIDES
i. !eaction "ith nitrous acid$ =i;e primary amines& amides and imides evolve
nitrogen on treatment "ith nitrous acid.
!CO/+- E +O/O !COO+ E /
-
E +
-
O
ii. Re"!t%# 8th "l<"l: #issolve 0.- gm of the amide in ecess of concentrated
sodium hydroide solution. +eat the solution to boil& smell of ammonia gas
indicates the presence of amide group.
!CO/+
-
E/aO+ !COO/a E /+
3
)he evolution of ammonia gas can also be detected by the follo"ing tests.
a. 9ring a red litmus paper over the mouth of the test tube& it changes to blue.
b. 9ring a glass red dipped "ith concentrated hydrochloric acid to the mouth
of the test tube:dense "hite fumes of ammonium chloride.
iii. O#ly .%& "&%+"t! "+$es: )o a little of the compound& add some hydroylamine
hydrochloride solution in ethyl alcohol. 9oil the contents for about five minutes&
cool and then add about 0:2 drops of dilute '2%( ferric chloride solution:bluish
red colour
C
4
+
2
CO/+
-
E /+
-
O++C* C
4
+
2
CO/+O+ E /+
0
CI
iv. O#ly .%& "&%+"t! "+$es: )o the a7ueous solution of the aromatic amide add
about D:H drops of 4% hydrogen peroide and heat the contents to boiling. Cool&
add *:- drops of dilute '2%( ferric chloride solution bluish red colour in cold
-2
"ithin a short time or a bro"n colour on "arming.
C
4
+
2
CO/+
-
E+
-
O
-
C
4
+
4
CO/+O+ E +
-
O
Tests .%& U&e": .rea& being the typical member of simple amides& gives certain
characteristic special tests.
i. 'u&et test: 1use a small amount of the urea in a test tube until it >ust melts and
ammonia is evolved. After some time "hen it resolidifies dissolve it in * ml. of
dilute sodium hydroide solution and then add one to t"o drops of very dilute
copper sulphate solution& a pin; colour "ill be developed changing to violet and
lastly deep blue. )his test is also given by o amide and malonamide.
-/A
-
:C:/+
-
/+
-
CO/+CO/+
-
E /+
3
ii. @"#thy$&%l test: #issolve a small amount of the compound in 20% acetic acid
and add to it * ml. of 2% anthydrol solution in methanol& a precipitate "ill
immediately be formed. )he test is given by urea as "ell as its derivatives.
iii. )a;e small amount of urea in a7ueous solution and add to it sodium hypobromite
solution& bris; effervescences of nitrogen and carbon dioide "ill be evolved.
iv. U&e" #t&"te test: 0.*g of the substance E*ml of "ater E*ml of con. +/O
3
. Sha;e
"ell. Chite ppt formed sho"s a diamide li;e urea. .rea oalate test$ 0.*g of the
substance sha;en "ith 3ml of saturated solution of oalic acid. Chite ppt
-4
9en6amide +ydroamic acid
O
O
!/+CO/+
-
E +O.C+
!/+CO/+ .C+
O E +
-
O
indicates the presence of urea.
17. SULPHONIC ACIDS
A&%+"t! sul,h%#! "!$s:
i. )hese may be detected by fusion "ith al;ali as follo"s. 3i about 0.2gm.of the
substance& 3gm. of potassium hydroide and 2 drops of "ater in a nic;el crucible.
+eat the crucible carefully& "ith occasional stirring& so that the miture melts and
remains in the molten state for about *0 minutes. Cool the melt& add about 2 ml. of
"ater and stir the contents to dissolve the mass '"arm& if necessary(. Acidify the
solution : SO
-
gas is evolved "hich may be detected by means of a filter paper
strip impregnated "ith acidified potassium dichromate solution.
ii. )reat the compound "ith phosphorus pentachloride and then "ith phenol in
al;aline medium. A crystalline derivative is obtained.
Ar:SO3+ ArSO-Cl ArSO-:O:C4+2
)he above formed sulphonyl chloride also reacts "ith ammonia to form
crystalline sulphonamide.
ArSo
-
Cl E /+
-
ArSO
-
/+
-
E+CI
19. THIOUREAS
i. 3eat a small amount of the substance "ith - ml. of a7. /aO+ to boiling for about
30 seconds. Cool and add one drop of CO
-
=ead acetate:dar; bro"n or blac;
colour.
!/+.CS./!.! E 0LO+ -!/+
-
E L
-
CO
3
E L
-
S E +
-
O
L
-
S E 'C+
3
COO(- pb pbs blac; precipitate E -C+
-
COOL
ii. )a;e a small amount of the compound in a test tube& add to it an alcoholic solution
of yello" mercuric oide& and "arm : a blac; precipitate of mercuric sulphide "ill
or formed.
-D
PCl
C
4
+
2
:O+
:+Cl
Sulphonamide
!/+.CS./+ E +gO !/+.CO./+! E +gS
iii. 1use 'melt( a small amount of the compound in a test tube& cool and dissolve the
product in "ater. Add a7. ferric chloride solution : a blood red colour "ill be
developed.
1;. HYDROCAR'ONS
Although hydrocarbons have no general test& they can be detected by the
follo"ing tests.
i. I%$#e test: #issolve 0.- gm. Or -:3 drops of the substance in 2 ml. of ben6ene.
)o this add 2 ml. of very dilute solution of iodine in ben6ene and sha;e5 solution
remains violet.
ii. F&e$el A C&".t !%#$e#s"t%# test: 'Only for aromatic hydrocarbons(. )a;e
0.2gm. of anhydrous AICI
3
in a dry test tube. +eat the test:tube "hen. AICI
3
sublimes to deposit on the upper end of the tube. /o" add -:3 drops of a miture
of e7ual amounts of the substance and chloroform. Allo" this solution to come in
contact "ith aluminum chloride : appearance of red& orange& blue or green colour
due to the formation of triphenylmethane dyes indicates aromatic hydrocarbons.
F%&+"l# Test
Sample E CCl
0
E+C+OE+
-
SO
0
Observation red color "ith blac; ppt.
Este&s:
*. Substance E* drop of phenolpthalein E /aO+ dorp"ise "hile "arming the pin;
color disharges
-. +ydroylamine test
Substaance E methanolic soln of hydroylamine E +Cl
3
#!OPS( E 1@C
#!OPS of 3eth. Soln of LO+& boil& cool& add a drop +Cl
3
F acidity "ith CO/C.
+Cl
Purple , "ine color ester confirmed
-H
-I