,emistry Chemistry : Organic chemistry

Pre-Medical
for the
ORGANIC CHEMISTRY
l\owi.ng in
DETECTION OF EXTRA ELEMENTS {NITROGEN, SULPHUR AND HALOGEN) IN ORGANIC COMPOUNDS
Nitrogen, sulphur and halogens present in an organic compound are detected by Lassaigne's test.
Organic compounds are fused with dry sodium in fusion tube and fused mass after extraction with water is
boiled and filtered, the filtrate is called sodium fusion extract
Preparation of Lassaigne's Extract
phuric acid
To prepare Lassaigne's extract of the compound take a small, dry piece of sodium in an ignition tube, then
:arch iodine
which of the put a little of given organic compound over sodium. Heat ignition tube first gently to fuse sodium then
strongly, to red-hot. Drop the red-hot tube in about 10-15 ml water containing dish or hard glass boiling
test-tube. Crush the contents in water, boil and filter. The filtrate is Lassaigne's extract.
)0-
is added to a • During preparation of sodium fusion extract covalent compound Is converted into ionic compound .
is obtained of • The following reactions takes place
Na + C + N ~ NaCN
2Na+S ~ Na2S
2Na + Xi ~ 2NaX (X = Cl, Br or I)
Test for Nitrogen
For the detection of nitrogen take 2 ml sodium extract, add a drop of NaOH and 0-5 ml freshly prepared
FeSO 4 solution and boil. Cool and add dil. H 2SO4 and few drops of ferric chloride solution. If a blue colour
(prussian blue) or precipitate is obtained. The presence of nitrogen is confirmed.
(i) Na + C + N ➔ NaCN
(ii) FeSO 4 + 2NaOH ➔ Fe(OH) 2 + Na 2SO4
(iii) Fe(OH) 2 + 2NaCN ➔ Fe(CN) 2 + 2NaOH
(iv) Fe(CN) 2 + 4NaCN ➔ Na4 [Fe(CN)6 ]
sodium ferrocyanide
(v) 3Na4 [Fe(CN) 6] + 4FeC13 ➔ Fe4 [Fe(CN) 6 Ja + 12NaCl
Prussian blue
or
3Na4 [Fe(CN) 6] + 2Fez(SO,J 3 ➔ Fe 4[Fe(CN) 6] 3 + 6Na 2S0 4 .
. This test fails in case of diazo compounds .

(8
. If the amount of nitrogen present is less, then Prussian blue is present in collaidal form and the solution
looks green.
i 1 Test for Sulphur
~3 44 45
3 (a) Sodium fusion extract is acidified with acetic acid and lead acetate is added to it, a black precipitate
3 3
of lead sulphide is formed, which indicates presence of sulphur.
Na 2S + (CH 3COO) 2Pb - PbS + 2CH3COONa
black
(b) Sodium fusion extract is treated with freshly prepared sodium nitroprusside, appearance of violet
colour (purple) indicates presence of sulphur.
Na 2S + Na,[Fe(CN) 5 NO] - Na,[Fe(CN)5 NOSJ
(sodium nitro prusside) (violet)

t-
ALLIM® Chemistry : Organic chemistry
(

Pre-Medical
• · forrned' w hi c h
In. case both rn·t rogen and sulphur are present in an organic compound sodium thiocyanate IS
gives blood r~d colpur with neutral FeCl 3 solution.
Na + -C + N + S ~ NaSCN
3NaS~N + FeCl 3 ~ Fe{SCN) 3 + 3NaCI
N
{blood red)
{or)
2
[Fe{SCN)r
{blood red)
• If sodium fusion is carried out with excess of sodium, the thiocyanate decomposes to yield cyanide and
sulphide, these ions gives their usual tests. Sul

NaSCN + 2Na ~ NaCN + Na 2S

• On treating s?<1ium fusion extract with sodium nitroprusside, appearance of a violet colour further indicates
the presence of sulphur.
S 2- + [Fe(CN) 5N0] 2- ~ [Fe(CN)5NOSt
Violet
Test for presence of N and S both
Take about 2-3 ml of sodium fusion extract and add FeCl3 solution. Appearance of blood-red colour
confirms the presence of nitrogen and sulphur both. Halo:

3NaCNS<oq) + FeCl3 ~ Fe(CNS) 3 + 3NaCl

blood-red colour
Test for Halogens
Sodium fusion extract is acidified with nitric acid and then treated with silver nitrate solution .
•
(i) White precipitate, soluble in ammonium hydroxide indicates presence of chlorine.
NaCl + .AgN0 3 - AgCl + NaN03
(white ppt)
NitrogE
AgCl + 2NH 40H - [Ag(NHJ 2]Cl + 2Hp
and
(soluble complex)
Yellowish precipitate, sparingly soluble in ammonium hydroxide indicates presence of bromine. sulphur
(ii)
NaBr + AgN0 3 - AgBr + NaN0 3 togethe:
(yellowish ppt)

(iii) Yellow precipitate, insoluble in ammonium hydroxide indicates presence of loci'me .

Nal + AgN0 3 - Agl + NaNQ 3
yellow
precipitate
Nitrogen and sulphur are also present in the compound the sod· fus·
. . . . . ' ium ion extract is boiled with
concentrated mtric acid to. decompose sodium cyamde & sodium sul Ph'd f
I e ormed during
. . Lassaigne's test,
otherwise they interfere with silver mtrate test for halogens.
NaCN + HN0 3 - NaN0 3 + HCN
Na 2S + 2HN0 3 - 2NaN0 3 + H2S
. .
If NaCN and Na 2S are not decomposed, then white and black prec1p1tates of A CN · d
respectively with silver nitrate solution. g and Ag2S are forrne

4
C'
mistry Chemistry : Organic chemistry

. which Pre-Medical
ELEMENTA L ANALYSIS CHART
Lassaigne method (Detection of Elements)
Element Sodium Extract (S.E.)
Confirmed Test Reactions
Nitrogen
Na+C+N ~ NaCN S .E.+FeSO 4+NaOH, FeSO 4 +2NaOH➔ Fe(OH) +Na SO
2 2 4
(S.E.) boil and cool,+FeCl 3 + Fe(OH) 2 +6NaCN➔NaiFe(CN)J+2NaOH
cone. HCI Blue or
3Na4 [Fe(CN)J+4FeCl3
green colour
~ Fe4[FeCN]J 3 + 12NaCI
mide and
Prussian blue
Sulphur
2Na+S -4 Na 2S (S.E.) (i) S.E.+ sodium nitro (i) Na 2 S+Na 2 [Fe(CN) NQ] ➔Na (Fe(CN) NQS]
5 4 4
prusside (A) (A) deep violet
r indicates
A deep violet colour, CHaCOOH )
(ii) Na2S+(CH3COO) 2Pb
(ii) S.E.+CH3COOH
PbS.J- + 2CH3COONa
+ (CH 3CQO) 2 Pb
black ppt.
A black ppt.
red colour S.E. + HNO 3 + AgNO 3
Halogen Na+Cl -4 (i) White ppt. soluble in NaX+AgNO HN00
NaCl (S.E.) ➔ AgX.J,
3
aq. NH3 confirms Cl ppt

(ii) Yellow ppt partially

soluble in aq. NH3 AgCl+ 2NH (aq)~[Ag( NH ) )Cl
3 3 2
confirm Br
white ppt soluble
(iii) Yellow ppt insoluble
in aq NH 3 confirms I
Nitrogen Na+C+N+S ~ As in test for nitrogen; NaSCN + FeC1 3 ➔ [Fe(SCN)]C1 2 + NaCl
and NaSCN(S.E.) instead of green or blue blood red colour
Thiocyanato-s-iron
sulphur colour, blood red an) chloride
mine.
together coloration confirms
presence of N and S
both

boiled with
;aigne's test,

; are formed

f::::=::a:z<*':uan:2:2:a::3:mmn
• ¥2%i'ii ~~
5,~r.mM--=
df#zli± - ~ =i=sii i@Cmaaim:::::m:~••••••• • -
·•-•~•gAAim;;i
ALLIM® Chemistry : Organic chemistry
Pre-Medical

Detection of the Functional Groups Present in Organic Compounds

~omplete-identification of an organic compound requires the following tests and in the order as given :
(1) Physical state, colour and odour, (ii) Aliphatic or aromatic, (iii) Test for unsaturation or saturation, (iv)
Detection of elements like nitrogen, sulphur, halogens, etc., (v) Functional group test, (vi) Specific tests, (vii)
Melting and boiling points, (viii) Derivatives.
We know that functional group determines the group or the homologous series of the compound. Some
compounds contain more than one functional groups Here we are concerned with compounds containing
one functional group. It should be remembered that in a few homologous series (viz., alcohol, aldehyde,
carboxylic acid, etc.) the first member in which hydrogen (H) is present in place of alkyl group (R) gives some
tests different to those of other members of the series, but the functional group tests do not differ much. The
following functional groups are to be identified' ·

Table : Functional groups

S.No. Name of the group Formula Group and Example
1. Alcoholic or hydroxy (-ol) R-OH (R = aliphatic) Alcohol, CHpH, C 2H 50H(alkanol)
2. Phenolic (-Phenol) Ar-OH (Ar = aryl) C 6H50H (phenol)
3. Aldehyde (-al) -CHO Aldehyde (Alkana!) HCHO, CH3 CHO,
C 6H 5CHO (benzaldhyde)
4. Carboxylic (-oic) -COOH Carboxylic or alkanoic acid HCOOH,
CH3COOH
5. Ketonic (-one) >C=O Ketone (Alkanone) CH3COCH3 .
6. Amino (-amine) -NH 2 Amine CH3 NH21 C 2 H 5 NH2
Physical Examination of The Compound
For an organic compound the following physical properties are observed :
(i) Physical state, (ii) Colour and (iii) Odour (smell).
Aliphatic or Aromatic Test
The test to find out whether the compound is aliphatic or aromatic is done
by burning. A little of the substance is taken on glass rod or spatula and put in
non-luminous (i.e., oxidizing) flame. The aliphatic compounds bum with non-smoky
flame and aromatic compounds bum with smoky flame . 3.
Smoky flame ➔ Aromatic in nature
Non-smoky flame ➔ Aliphatic in nature
•
l. Test for Carboxylic acids
The first member is formic acid (HCOOH) which is different from other m b f
· ac1'd aIso :
following test are given by formic em ers o this series . But the
(i) Litmus test : The aqueous solution of the given organic compound tu bl .
. b henol • ms ue htmus to red. This test is
also given y P • F
(ii) Sodium bicarbonate test : On adding the given organic compound .
. • T
solution of sodium bicarbonate, a bns. k effervescence is given and CO m. a test-tube contammg
. . aqueous
phenols. 2
gas is evolved. This is not given by
RCOOH + NaHC0 3 ➔ RCOONa + H,0 + CO 2
(Ill) Esterlfication test : A small quantity of the given organi
ethyl alcohol and 0.5 m cone. H2S04 • A sweet fruity smell is obt~ codmdpou nd is heated gently with 1-2 rnl
the presence of - COOH group. ame ue to fo .
rmation of ester. It confirms
RCOOH + C2H.OH H,so, ➔ RCOOC H + H O
2 6 2
c chemistry Chemistry : Organic chemistry

2. Test For Alcohols: Pre-Medical

s
(I) Sodium Metal
given:
aturatlon, (iv) ROH+Na
Alcohol
~ RO-Na• +.!.H
2 2 (g)
:ific tests, (vii) !Sodium aikoxlde)

When Na-metal reacted with alcohol Hi(g) evolve

,pound. Some
(II) Ceric Ammonium Nitrate Oxidation (CAN Test)
nds containing
iho\, aldehyde, OR
. (R) gives some (NHJ2Ce(NOJ6 + ROH -(NHJi6e(NOJ5 + HN0 3- Ce(Im
iHer much. The eerie ammonium nitrate alcohol (red) colour
(yellow) decolourise
• Positive Test: Color changes from yellow to red first then to colorless solution. (1 min. to 12 hrs)
• Note : Phenols gives brown or black colour .
(iii) Lucas Test
l(alkanol) • This test distinguishes 12 , 22 & 3 2 alcohol from each other
• It uses, anhydrous ZnCl2 in cone. HCI (lucas reagent)
, CH3CHO, R-OH (HO+ZnO,) ) R-Cl+H20
• 3° alcohols give white turbidity solution immediately
acid HCOOH, • 2° alcohols give white turbidity solution within 5 to 10 minutes
• 1° alcohols does not give white turbidity at room temperature
)CH 3• Note : Benzyl alcohol also react immediately
12 (iv) Victor-Mayer Test
• This test also distinguishes 1°, 2° & 3° alcohol
Reagent : Red P + 12 , NaN02 , HN0 2 , NaOH
1° Alcohol - Red colour
2° Alcohol - Blue colour
3° Alcohol - Colourless

3. Tests for Phenols

Phenols undergo reaction with yellow eerie ammonium nitrate to produce brown or black products.
OAr
I
(NHJ2Ce(NOJ0 + ArOH - (NHJ2Ce(N0 3)5 + HN0 3
eerie ammonium phenol (brown or black)
this series. But the nitrate (yellow)

s to red. This test is Phenols reduce potassium permanganate solution and undergo oxidation to quinones.
The manganese is reduced from + 7 which gives a purple solution to +4 which is brown.

nY
containing aqueous

6
OH 0
This is not given by

3 + 4 KMnO, - 3 + 4Mn0, + 4KOH + H,O

:I gently with 1-2 rnl Phenol

1 of ester. It confirms qulnone brown
ALLI ®

Pre-Medical Chemistry : Organic chemistry

(i)

-
6
OH

phenol
+3Br,-
BryYBr
y
+3HBr

Br
2 ,4 ,6-tribromophenol
(white)
• Positive Test: decolorization of bromine .
• This is good for water soluble phenols
(ii) Ferric Chloride - Pyridene Reagent

3ArOH +
phenol
30 N
+ FeCl3 Fe(OAr), + 3
(Coloured complex)
r~©]
~
ci-

H
• Positive Test: Production of blue, violet, purple, green, or red-brown colors
• Good for all types of Ar-OH .

• Positive test for _phenols

(
AA
OH O )

• Carboxylic acid with FeC13 gives red colour only when saturating with NH3 •
(iii) Libermann' s nitroso test :
When phenol is reacted with NaN0 2 and concentrated H 2S04 , it provides a deep green or blue
colour which changes to red on dilution with water. It regain green or blue colour, when NaOH
solution is added.

@-oH HONO, oN---@-OH ~ o=C)=NoH 5.

p-Nitrosophenol Quinoxim

__;==\_ ,-------·,:;:
o~NtQt!.!.~
OH ~o H2SO• O==O=N
_
-0
~ O H ~OH > Sod. salt of
20 indophenol (blue)
Indo phenol (Red)
Classification Tests for Aldehydes and Ketone
4.
(i) 2 , 4 -Dinitrophenyl Hydrazine
;=(_N02
+ 0 2N ---\___rNHNH2 pH(4.5-6.0)

aldehyde 2 ,4-dinitrophenylhydrazine
or ketone 2,4-dinitrophenylhydrazone

Positive Test: formation of yellow, orange or red _PPt.

The pre cipitate may be o ily at first and become crystalline on stand·
mg.
 Chemistry : Organic chemistry

(ii) Pre-Medical
Sodium sulphite (NaHSO )
3
0
II I
/C"-. + NaHS0 3 ~ -C-OH
I
SO 3-Na+
Aldehyde Sodium Bisulphite White crystalline adduct
or ketone

• Positive Test: By aldehydes and methyl ketone

• Only some cyclic ketones give positive results (ppt)
• This reaction is greatly inhibited by the steric constraints about the carbonyl group .
(iii) lodofonn Test (For Methyl Ketones)
0
II
/C"'-.. + 312 + 3NaOH - CHls(s) + 3Nal + 3H20
R CH 3 Iodoform
methyl ketone (yellow solid)
Sodium slat of
the carboxylic acid
• Positive Test: Yellow ppt for methyl ketones
• Disadvantages : Some compounds that can be easily oxidized to methyl ketones give also positive
results
• The principal types of compounds that give a positive test:
OH 0
blue I II
/C~ + 12 + 2NaOH - /C'-.. + 2Nal + 2H20
iOH R CH 3 R CH3
2°alcohol methyl ketone ·

5. Tests that give positive results with aldehydes and negative results with Ketones
(i) Tollens Reagents Ag(NH,) 2 0H

0 0
II II
C 2Ag(s) + /c......._
+ 2Ag{NH3)zOH -
of R/ '-..H R o · NH4 +
(blue) T aliens reagent salt of
aldehyde carboxylic acid
Positive Test: Formation of silver mirror (Ag) or colloidal (granular) grey or black Ag precipitate.
(ii) Schiff's Reagent

2 ~
R/'-..H
+H 3:;
l~I
0
-CH1D-NHS02H]
2 T\-J' --+

H0 3S
aldehyde schiffs reage nt

H
,~-o·=to-NH+rH
CI1 + H,SO,

(viole t-purp le solution dye)

ffl'II
 .
ALLI"® . .~ chemistry: Organic chemistry
Pre-Medical
('ii) ~
s
1
Bendicts solution and Fehling's Solution
• Positive Test : yellow or yellowish green ppt.
• All aldehydes give positive result except aromatic aldehydes (negative)
Cu2 O(s)
(red,yellow,or yellowish green)

ArNHNH2 + 2Cu+ 2 - ArH + ArOH + N2(g) + Cu2O(s)

arylhydrazine (blue) phenol (red, yellow, or
yellowish green)

6. Tests for Amines

(i) Nitrous Acid
i
• Reaction of amines with nitrous acid (HONO) classifies the amine not only as 1 °, 2°, or 3°, but also 6
as aliphatic or aromatic. A
• The diazonium salt of the primary aromatic amine reacts with sodium 2-napthol to produce a red- 7
orange azo dye. Ai
(ii) Hinsberg Test 8.
• Based on the ~eaction of the amine with benzenesulphonyl chloride (Hinsberg reagent), it can be
used to seperate 1°, 2°, and 3° amines. All
9.
An
10,

11.
Ans
12.
Ans.

13.
Ans.
14.
Ans. j

15. I'
Ans. F
16. p
bi
Ans. B,
17. W
Ans. Al,

MP 817551¥ , ¥¥11 itE 185 1

?mistry Chemistry : Organic chemistry
MW&t Ki6ri\fii¥ Pre-Medical
IMPORTANT QUESTIONS
1. What is a functional group?
Ans. The group of atoms that lar I d t · ·
ge Y e ermines the properties of an organic compound is called functional group.
2. Why is alcohol dried before carrying out sodium metal test ?
Ans. Because water also reacts w·th · d · ' ·
1
s00IUm an gives hydrogen gas with brisk effervescence.
3. Liebermann's test is used for which class of compounds?
Ans. Phenols.
4. Which is more acidic : alcohol or a phenol?
Ans. A phenol.
5. Which of the two is more acidic: Phenol or carboxylic acid?
Ans. Carboxylic acid.
3°, but also
6. Name a reagent used to detect carbonyl group in a compound?
Ans. (2, 4-clinitrophenyl hydrazine)
face a red-
7. Name two tests which distinguish aldehydes from ketones?
Ans. Tollen's test and Fehling's test.
8. Both phenols and alcohols contain (-OH) group. How can it be ascertained that the given compound is
), it can be
alcohol or phenol?
Ans. Phenols are acidic in nature and turns blue litmus red whereas alcohol cannot
9. What is Tollen's reagent? ·
Ans. Ammonical solution of silver nitrate
10. How is presence of Ketonic group in an organic compound confirmed?
Ans. Ketones give positive test with 2,4-dinitrophenyl hydrazine.
11. Dye test is given by which class of compounds?
Ans. Aromatic amines.
12. How Lassaigne's solution is prepare?
Ans. Take a small piece of dry Na in a ignition tube. Add to it a small amount of given organic compound. First
heat it gently and then strongly till red hot. Now put this red hot ignition tube in a boiling tube containing
distilled water. Heat the contents of boiling tube and filter. The filtrate is Lassaigne's solution.
13. Which class of compounds turns blue litmus red ?
Ans. Carboxylic acids and phenols.
14. How will you know whether the given compound is aliphatic or aromatic?
Ans. Bum the given compound in flame with the help of glass rod or copper wire. Compound bums with sooty
flames aromatic. Aliphatic compound bums with non-sooty blue flame
15. Name the functional group other than carboxylic group which turns blue litmus red?
Ans. Phenolic group
16. Phenols turn blue Litmus paper into red colour. Then why do not give effervescence with sodium
bicarbonate?
Ans. Because phenols are weaker acid than carbonic acid.
17. Why do aldehydes produce a shining silver deposit with Tollen's reagent?
Ans. Aldehydes reduces silver ions to metallic silver
ALLIM® Chemistry : Organic chemistry
Pre-Medical
18. What. ·t
1,/ s ni rating mixture?
Ans. An e~q- · I .
. . wmo ar mixture of cone. HNO and cone H SO
' 19 ' \:: 3 • 2 4
• Wha\ is the use of Schiff' s reagent ?
Ans. It is used to detect aldehyde group.
2
0. Name the three class of compounds which give sodium metal test?
Ans. Alcohol, Phenol, and Carboxylic acid.
21 · 3
Give simple chemical tests to distinguish between propanal and propanone.
.Ans. (i) By Tollen's test Ai

(a) Propanal reduces Tollen's reagent, fehling solution, benedict solution but propanone (ketone)
does not reduces.
(b) lodoform test :

Propanone (CH,-g-CH~ gives iodoform test but propanal (CH3-CH2-CHO) does not.

·22. Giv~ si~ple chemical tests to distinguish between acetophenone and benzophenone.
• \' ' I

Ans._ Acetophenone and Benzophenone can be distinguished using the iodoform test.
Acetophenone gives iodoform test but benzophenone does not.
·23. Give simple chemical tests to distinguish between phenol and benzoic acid.
Ans. · Phenol arid benzoic acid can be distinguished by ferric chloride test and NaHC0 3
test.
(a) Phenol gives voilet colour with FeCl3 •
(b) · Benzoic acid gives CO 2 with NaHC03 while phenol does not.
· 24. · Give si~pl~ chemical tests to distinguish between benzoic acid a'nd ethyl benzoate
.~ _' &nzoic ·acid and Ethyl benzoate can be distinguished by sodium bicarbonate test.
31.
:·· · Sodi~ ·bi~rbonate test :
Ans.
~• ·&nzoic acid react with NaHC0 3 to produce brisk effervescence due to the evolution of CO2 gas but
ethylbemoate does not.
25. Give·simple ·chemical° tests to distinguish between pentan-2-one and pentan-3-one
'· ~ : · ·Pentan-2~~ne' and pentan-3- one can be distinguished by iodoform test. Pentan-2-one gives iodoform test
p
but pentan'-3-one does not.
26. Give simpl~' chemical tests to distinguish between benzaldehyde and acetophenone.

Ans. Benzaldehyde and acetoph~none can be distinguished by the (a) Tollen's test (b) lodoform test. Benzaldehyde
gives Tollen's test where as acetophenone gives iodoform ·test.
27. Give simple chemical tests to distinguish between ethanal and propanal.
32. Gh
Ans • ethanal and propanal can be distinguished by iodoform test. Ethanal gives iod o form test but propanal does
not. Ans. Cai
28 • Give one chemical test to distinguish between methylamine and dimethylamine. solt
beir
Ans. Methylamine gives carbylamirie reaction on heating with CHCl 3 and alcoholic KOH.
Gives foul smelling (Carby! amine)
CH 3 NH2 +°CHCI, + 3KOH ~ CH 3 NC + 3KCI + 3H 0
Carbylamlne 2

where as Dimethylamine does not give this reaction.

 chemistry : Organic chemistry
!mistry
Pre-Medical
29. Give one chemical test to distingu·is h between secondary and tertiary amines.
Ans- Secondary amines given Hinsber 's . .
. . g test. Its gives insoluble substance with Hinsberg's reagent
which 1s not affected by base. ·

R2NH + Benzene
C6HsS02Cl
Sec. amine sulphonyl
⇒ Rl~luble
NSO tiC~6•H• s (N , N-Dialkyl benzene sulphonamide)
chloride lllkall

Where as tertiary amine does not react with Hinsberg's reagent.

30. Give one chemical test to distinguish between ethylamine and aniline.
Ans. Aniline gives azo dye test : Dissolve Aniline in cone. HCI and add ice - cold solution of HN02 (NaN02 + dil
HCl) at 273 Kand then treat it with an alkaline solution of 2-napthol. Appearance of brilliant orange or red
ne (ketone)
dye indicates aromatic amine (ie Aniline).
Wher~ as aliphatic amine (ie ethylamine) does not form dye. It will give brisk effervescence due to the
evolution of N2 but solution remain clear.
t.
@-NH 2 + con. HCl + HN02 273
K @-w = NCr + 2H20
Benzene diazonlum
Chloride

D11. NaOH
PH,.,.
+HCI

2-Naphthol 1-Phenylazo-2-naphthol
(Orange dye)
31. Give one chemical test to distinguish between aniline and benzylamine.
Ans. Nitrous acid test : Benzylamine reacts with nitrous acid (HN02) to form a diazonium salt which being
: CO 2 gas but unstable even at low temperature, decomposes with evolution of N2 gas.

C H CH 2NH 2 ~g• >[ C6 H 5 CH- N= Nc1-J ~ C 6 H5 CH 20H + N2 + HCl

6 5

s iodoforrn test Aniline reacts with HN0 2 to form benzene diazonium chloride which is stable at 273-278 Kand hence does
not decompose to evolve N2 gas.
~
~
NaNO,HCI
• ,H, 273 - 21s l
~o.
~ NaNCr
;t. Benzaldehyde
Benzenediazonium chloride ·
Aniline

32. Give one chemical test to distinguish between aniline and N - methylaniline.
ut propanal does Carbylamine test : Aniline being a primary amine gives carbylamine test, i.e, when heated with an alco~olic
Ans. solution of KOH and CHC1 , It gives an offensive smell of phenyl isocyanide. In contrast, N-methylarulme,
3
being secondary amine does not give this test.
c 6H.6NH2 c . H 5 NC
+CHCl 3 +3KOH-~ Phenyllloc)lankle
(ale.)
Anlllne\l'•mln•) (offm.slwsmell)

-
0<a, /KOHi"'! 1No reaction
C6 H 6 - NH - CHa
N- mathylanlllne (2'•mln•)
ALLI e
Chemistry : Organic chemistry Chem
Pre-Medical
PREPARATION OF ORGANIC COMPOUND
Preparations
p . compounds highlight the importance of some common organic reactions.
organic Of
reparation of com monIY use d compounds hke . ..
aspmn-a pain .
. killer, .
1odoform-a . . fectant h eIps th e
d1s111
students to know the practical problems and the method Involved in the f9rmation of compounds.

EXPERIMENT- I
Object: To prepare acetanilide from aniline.
I
Requirements: 100 ml conical flask, cork, air condensor, Burner, measuring flask, ice, etc.
(i
Chemicals required : Aniline, acetic anhydride, glacial acetic acid.
Theowy: When aniline is treated with acetic anhydride in presence of glacial acetic acid, acetanilide is
formed . (li
0 (ii
II

© ·
NH 2 O
II
O
II
+ H3C-C-O--C-CH3
Acetic anhydride
glacial acetic acid ,
NH-C-CH3

~
l8J
+ CH 3COOH
Acetic acid
R«

Aniline Acetanilide

Procedure: Pr,
(i) Take 10 ml of aniline in conical flask and add acetic anhydride and glacial acetic acid. Shake the (i)
mixture thoroughly. Heat it using air condenser. (ii)
(ii) Pour the hot liquid into a beaker containing 200 ml of ice cold water and stir it. White shining crystals
of acetanilide starts separating. Wash the precipitate with cold water and then dry.
OI
(iii) Recrystallisation : Put crude acetanilide into a mixture of acetic acid and water in the ratio 1:2. Heat
RE
it. Cool the beaker slowly. Crystals formed are dried and weighed.
ice
Result: White shining crystals of acetanilide is formed
Ch
Melting point = 113°C
Th,
Precaution :
(i) Small amount of zinc is added to the reaction mixture . It reduces coloured oxides and checks (30

(ii)
(Iii)
oxidation.
Avoid excess heating.
Ice cold water should be added only when the contents of the flask comes to room temperature.
« Bel

Excess of acetic anhydride should not be used.

(iv) Pr0<

ii3PiH@ii§•f4 (i) i

Object: To prepare p-nitroacetanilide from acetanilide.

(ii) f
Requirements : 100 ml conical flask, 250 ml beaker, 100 ml measuring flask, funnel, glass rod, test
ti
tube, filter paper, ice, etc.
Resul
Chemicals required: Acetanilide, Cone. HN0 3 , Cone. H28S0 4 , and methylated spirit.
Meltin:
Theory : Direct acetylation of aniline is not done because of its easy oxidation of R-NH 2 group. Preca
Therefore, it is first converted into acetanilide for protecting nitro group. Acetanilide is ortho and para
on nitration mixture of ortho and para nltro acetanilide is obtame . acetan illde
• d , o-mtro
directing . Therefore
in methylated spirit leaving behind crystals of p-nitro acetanilide R
Is fairly soluble
ti
· eac on occurs as :
y Chemistry : Organic chemistry

0 Pre-Medical
II

-l~.
.s. 0
H-N-C-CH II
~ <=<:: HNo,
1e
+ con,. H,00, ' .
+ . J '·.:.

N02
p-nitro acetanilide o-nitro acetanillde
Procedure:

~
(i) 1
Tak~ O powdered acetanilide in a 100 ml beaker and add 10 ml of glacial acetic acid. Stir the
is
mixture with glass rod to get a clear solution.
(ii) Remove the beaker fr fr .
om eezmg mixture and leave it to stand at room temperature for half an hour.
(iii) Fllter wash the prod t "th Id .
' uc WI co water and recrystallise from methylated spirit to get pure
nitroacetanilide.
Result:
Colour = Colourless to white
Melting point = 215°C
Precautions:
the (i) Nitric acid should be handled carefully as it has corrosive action.
(ii) Nitric acid should be added dropwise .
.tals
EXPl: HIMENT-:1

leat Object : Preparation of p-amino azobenzene (aniline yellow)

Requirements: 100 ml conical flask, 250 ml beaker, 100 ml measuring cylinder, glass funnel, glass rod,
ice, filter paper, etc.
Chemicals required : Aniline, benzene dlazonium chloride, cone. HCl, etc,
Theory : Benzene diazonium chloride reacts with aniline in acidic medium at slightly high temperature
eeks (30 to 35°C) to form aniline yellow.

©-N-NfCl+HI-@--~ 30 ~:S"C @-N•N-@--NH2+HCI

Benzene diazonlum chloride Anlllne p-amlno azobenzene (aniline yellow)

Procedure:
(i) Mixture of 5ml aniline, 2ml HCl and 5ml benzene dlazonium chloride Is shaken In 100 ml conical
flask.
(ii) After heating for about 20 minutes,. reaction mixture Is allowed to cool first at room temperature and
, test
then In ice cold water. ·
Result: Yellow coloured crystals formed are of aniline yellow.
Melting point .. -6°C
:roUP· Precaudons: 1. Aniline should be pure.
I para 2 _Temperature and pH should be controlled.

-
111ilide
 I ®

Chemistry : Organic chemistry

Cher
Pre-Medical

EXPERIMENT-4
Exercise . Prepar 1.od0 f 1.
• e orm {CHI3) from acetone (CH COCH )
Theory : lodoform is s th . b a 3 . Ans-
. · yn esise Y haloform reaction iodoform is formed when acetone is treated with I2
m presence of NaOH. 2.
12 is produced by treating Kl with NaOCI Ans-

NaOCJ + 2KI + H p ~ 12 + NaCl + 2KOH

3.
Ans.
CH3COCH3 + 312 ~ Cl3COCH3 + 3HI
4.
ClaCOCH3 + NaOH ~ CHI 3 +CH3COONa
Ans.
3HI + 3NaOH ~ 3Nal + 3H2O
5. \
CH3COCH3 + 312 + 4NaOH ~ CHI3 + 3Nal + 3H2O + CH 3COONa
Ans. F
Iodoform
is
(yellow ppt)
6. v\
Apparatus : Conical flask (250 ml), Buchner funnel, test tube, breaker (250 m) etc.
Chemical Required :
1 . Acetone = 10ml
Ans. c,
2. 10% KI = 40 ml
3. 10% NaOH = 15 mL
7. Wr
4 . 7% NaOCl = 40 ml
Ans. Na
Procedure:
For
1. Take 10 ml acetone, 40 ml 10% KI solution and 15 mL 10% NaOH solution in a clean conical flask
of 250 ml capacity.
2. Prepare a fresh 7% NaOCI solution in a separate beaker. Now add 40 mL of this solution to the
conical flask slowly with constant shaking.
3. Keep the above mixture for some time at room temperature, yellow crystals of iodoform separates
out.
_ Filter the crystals with the help of Buchner funnel. Impure sample of iodoform is obtained.
4

Buchner funnel and ruter flask

Purification of impure iodoform by recrystallization

Take the impure idoform in a boiling tube and add to it sufficient alcohol to dissolve it. Heat the boiling tube
by putting it in a hot water bath. Riter the solution in another boiling tube, allow it to cool in cold water.
Crystals of pure iodoform separates.
Decant the mother liquor, separate the crystals, dry them and weigh.
Result : Colour of the Crystals = yellow
Shape of the Crystals =· Hexagonal
 chemistry : Organic chemistry

Pre-Medical
IMPORTANT QUESTIONS
1. What is acetylation?

Ans. The process of removal of -OH, -NH:i, or >NH group by acetyl group is known as acetylation.
2. Name some acetylating agents.
Ans. Acetyl chloride, acetic anhydride .
3. What is oleum ?
Ans. Fuming H 2S04 is called oleum. Its formula is H Sp •
2 1

4. Why direct nitration of anillne is not done?

Ans. Because NH2 group of aniline gets oxidized?
5. What is coupling reaction?
Ans. Reaction in which arene diazonium salts react with phenol, aniline, etc. to form coloured dyes called azo dye
is callled coupling reaction.

6. What is the formula of benzene diazoniurn chloride.

+
N=NCr

Ans. c,ii,-N-N-0 o, ©
7. Write chemical name and formula of aniline yellow.
Ans. Name-p-Aminoazobenzene.

;k Formula : @--N=N-@--NH 2

:es

tube
ater.
ALL •
EXERCISE: MULTIPLE CHOICE QUESTIONS

I
following Column I with C I U CHO
and h oumn
. c oose the correct option from the codes
given below. (2)~

Column-I Cz8s
Column-II
(Distinguish) (By reagent) 0
A. Methanol and diethyl ~ CHO

~ 'CH, ~
1 Lucas
ether reagent (3) (4)
B. Methanol and ethanol 2 Sodium CH3 ~s
metal 5. Hinsberg reagent is .. .I ... which reacts with ...II...
C. Phenol and 3 Iodoform amines to form sulphonamides.
cyclohexanol test Identify I and Il for the given statement and
D. n-propyl alcohol and 4 Ferric choose the correct option.
tert-butylalcohol chloride
(l)J➔ @-s0 2c1 ; Il➔ primary and secondaiy
Codes
A B D
1➔@-s02c1 ;II ➔ secondary and tertiary
C
(1) 2
(2)
4 3 1
(2) 2 3 4 1
(3) 2 (3) I ~ H2CI ;II ➔ primary and secondary
3 1 4
(4) 3 2 1 4
2. Assertion (A) A bright silver mirror Is produced (4) 1➔@-cH2CJ ;II ➔ secondary and tertiary ]
during the warming of an aldehyde with freshly
prepared ammoniaepl silver nitrate solution. 6. Assertion (A) : N-ethylbenzene sulphonamide is
Reason (R) A bright silver mirror Is produced . soluble in alkali medium.
due to the formation of silver metal. Reason (R) : The hydrogen attached to nitrogen 1,
(1) Both (A) and (R) are true and (R) is the in sulphonamide is strongly acidic due to the
correct explanation of (A). presence of strong electron withdrawing
(2) Both (A) and (R) are true and (R) is NOT the sulphonyl group.
correct explanation of (A). (1) Both (A) and (R) are true and (R) is the
17
(3) (A) is true but (R) is false: correct explanation of (A).
(4) (A) is false but (R) is true. (Z) Both (A) and (R) are true and (R) is NOT the
Tollen's_test occur in correct explanation of (A). 18
3.
(1) Acidic medium (3 ) (A) is true but (R) is false.
(2) Alkaline medium (4) (A) is false but (R) is true.
(3) Neutral medium 7.
HCHO and HCOOH are distinguished by
(4) Both acidic and alkaline medium treating with
4. An aromatic compound 'X' with molecular (1) Tollens reagent
(2) NaHC03
formula C9H,P gives the following chemical
(3) Fehling's solution (4) Benedict solution

-
tests 8. Formaldehyde can not
I. Forms 2, 4-DNP derivative, be distinguished frorn
acetaldehyde by
II. Reduces Tollen's reagent,
m. Undergoes Cannizzaro reaction and (1) Fehling's solution
IV. On vigorous oxidation 1,2-benzene
dicarboxylic acid is obatined.
(2) Schiffs reagent
(3)Ammonla ~
Xis :- (4) Ammonical AgNO
s ~
 g/ ;_.-,. Acetone reacts with 1odine 02) to· from iodol ' · · · 0• -
._ . Pre-Medical
in the presence of - . onn Which compound bum sooty fi~ t
(1) CaC03 (2) NaOH (1) R-OH (2) R-CHb . .. -
(3) CaO (4) MgCO OH I
,r,, ·,
'

10. What is the IUPAC name of acetanilide

(1) N-phenylethanamid e
(2) Pent-2-ene
(4)@ '•'•.'
·(3) Pent-1-ene-4-yne 20. Which compound bum non sooty flame ?
(4) Hexa-1, 3-dien-5-yne NH2
11. What is the function of zinc dust in synthesising (1) R-OH (2)@
acetanilide?
(1) Prevent the reduction
OH
(2) Prevent the hydrolysis
(3) Prevent the oxidation
(4) Prevent the dissolution
(3)@ (4)@
12. Which of the following is a basic dyes
. (2) Aniline yellow 21. Which functional group is present in aspirin.
(1) Cango red ·
(3) Alizarin · (4) Indigo
13. Which of the following compounds will gives
(1)-CHO (2) )c = o
Lassaigne's test for nitrogen.
(1) N8zNH2 (2) NH4Cl (3) NaCN (4) NaN03
(4)-COOH
14. An organic compound containing N, Sand Oas
extra elements is fused with sodium metal and
then extracted with water. The· species which is 22. Liebermann's nitro test is used for which class of
not present in the sodium extract is compounds
, (1) CN (2) CNS (3) N0 3 (4) s2- (1) Phenol (2) Ketone
15. The red colour product in the Lassaigne's extract (3) Ether · (4) Carboxlic acid
is due to formation of 23·. What is tollen's reagent?
(1) [Fe(SCN) 2 r1 (2) [F~(CNS))2+ (1) NH4 (2)AgN03
(3) Fe(CN)3 · (4) Fe(CNS)3 '. I (3) AgN03+ NHPH (4) CuS04
16. Which of ·the following has violet colour? 24. Dye test is given by which class of compounds
(1) Na 2 {Fe(CN)s NO] (2) Aliphatic Amine
(1) Carboxlic
(2) Na 4 [Fe(CN)s(NO)S] (3) Aromatic amine (4) OH
(3) NaCNS 25. Which compound turns blue litmus to red?
(4) None of these · .
(1) R-OH (2) R-CHO
17. Which of the following cannot be tested m an
organic compound by using Lassaigne's method. R'-.
(1) N · (2) F (3) ~ (4) P . (3) / C = 0 (4) Phenol
R
18. Which of the following reactions take place m
l.assaigne's test for the detection of N present in
an organic compound .
(1) Na + C + N ➔ NaCN
>Y
(2) FeS04 + NaCN ➔ Na4[Fe(CN)6]
(3) 2Na4 [Fe(CN)6] + Fe2(S04)3 .
➔ 2NaFem[Feu(CN)6 ) + 3N~S04
(4) All of thease

,rn
ANSWER KEY