Practical Organic

Chemistry
IIT–JEE Syllabus:

Detection of elements (N, S, Halogens); Detection and identification of the

following functional groups: hydroxyl (alcoholic and phenolic), carbonyl (aldehyde
and ketone), carboxyl, amino and nitro; Chemical methods of separation of
monofunctional organic compounds from binary mixtures.

INTRODUCTION
The identification of organic compounds differs from that of the inorganic salts in the
respect that inorganic salt analysis is very systematic while there is no such systematic
scheme for the analysis of organic compounds. However, the following operations are
generally useful for the identification of unknown organic compounds:
(i) Preliminary tests
(a) Physical state
(b) Colour
(c) Odour
(d) Ignition test
(e) Saturation test
(f) Solubility
(ii) Detection of elements
(iii) Detection of functional groups
(iv)Determination of melting or boiling point and
(v) Preparation of derivatives (if any)

DETECTION OF ELEMENTS
Organic compounds consist mainly of carbon, hydrogen and oxygen. Hence, detection of
these elements are not necessary. In addition to the above elements, organic compounds
often contain nitrogen, halogens, and sulphur. Hence identification of organic compounds
means detection of nitrogen, halogens and sulphur only.

(a) Lassaigne’s test (for nitrogen, sulphur and halogens)

Nitrogen, sulphur and halogens are generally detected by this test. Cut a small piece of
sodium metal with a knife, press it between the folds of a filter paper to wipe out the
kerosene oil and transfer to a fusion tube. Add a little of the organic compound. Heat the
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 2

fusion tube first gently and then strongly to dullred. Continue heating for some time and
then immerse the hot tube into 1520 ml distilled water. The tube must be broken into
pieces. Grind the whole mass thoroughly and then filter. Use this filterate for testing the
presence of nitrogen, sulphur and halogens in the organic compound.
The following reactions occur when sodium is fused with an organic compound.
Carbon and nitrogen from the organic compound react with sodium to form sodium
cyanide.
Na + C + N  NaCN
Halogen and sulphur present in the organic compound react with sodium to form sodium
halide and sodium sulphide respectively.
Na + X  NaX (X = Cl, Br, I)
2Na + S  Na2S
When nitrogen and sulphur both are present, sodium thiocyanate is formed.
Na + C + N + S  NaCNS
These substances being soluble are extracted with water and identified.
(i) For Nitrogen: The following reactions take place when the filtrate is treated first with
ferrous sulphate solution, then with ferric chloride and finally with excess of dilute
sulphuric acid.
2Na + 2H2O  2NaOH + H2
FeSO4 + 2NaOH  Fe(OH)2 + Na2SO4
Fe(OH)2 + 2NaCN  Fe(CN)2 + 2NaOH
Fe(CN)2 + 4NaCN  Na4[Fe(CN)6]
Sodium ferrocyanide
3Na4[Fe(CN)6] + 4FeCl3  Fe4[Fe(CN)6]3 + 12NaCl
ferricferrocyanide
(prussian blue)
An intense blue colouration is produced due to the formation of Prussian blue.
Hydrazine (NH2NH2), Benzene diazonium salts do not give Lassiagne’s test of
nitrogen.

(ii) For sulphur

(a) Na2S + Na2[Fe(CN)5NO]  Na4[Fe(CN)5NOS]
sodium sulpho nitroprusside
(violet colour)
(b) Na2S + (CH3COO)2Pb  PbS + 2CH3COONa
lead sulphide
(black)

(iii) For halogens:

(a) NaCN + HNO3  NaNO3 + HCN
NaCl + AgNO3  AgCl + NaNO3
Curdy white
NaBr + AgNO3  AgBr + NaNO3
pale yellow
NaI + AgNO3  AgI + NaNO3
bright yellow
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 3

Before adding AgNO3 solution, the filtrate is boiled with conc. HNO3 to
decompose NaCN, if present. Otherwise, a white precipitate will be formed even in
absence of halogen.
(b) In this test acidify a little sodium extract with dil. HNO3 or dil. H2SO4 and add
CHCl3 or CCl4 and excess of chlorine water. If organic layer becomes yellow or
brown, bromine is present and if violet, iodine is present. Chlorine is not detected
by this test.
2NaBr + Cl2  2NaCl + Br2
CHCl3 + Br2  Yellow or brown layer
2NaI + Cl2  2NaCl + I2
CHCl3 + I2  Violet layer
(iv)For nitrogen and sulphur: (when both are present)
(a) C + N + S  Na
NaCNS
3NaCNS + FeCl3  Fe(CNS)3 + 3NaCl
ferric thiocyanate
(red colour)
(b) NaCNS + HCl  HCNS + NaCl
thiocyanic acid
4HCNS + Co(NO3)2  H2[Co(SCN)4] + 2HNO3
cobaltithiocyanic
acid (blue)

Bielstein’s test

Many organic compounds containing halogens impart a green colour to the Bunsen flame
when heated on a copper wire. The green colour is developed due to the formation of
volatile halides of copper. However, urea (H2NCONH2) and thiourea (H2NCSNH2) do not
contain halogens even then they given Bielstein’s test. Fluorine is unable to respond this
test as it is volatile.

Formula used in the determination of empirical, molecular and structural

formulae
12 weight of CO 2 formed
Percentage of carbon =   100
44 weight of organic compound
2 weight of CO 2 formed
Percentage of hydrogen =   100
18 weight of organic compound
Percentage of nitrogen
28 volume of Nitrogen at NTP evolved
= 22400  weight of organic compound
 100 (Duma's method)
1.4  volume of acid  Normality of acid
= weight of organic compound
(Kjeldal's method)
35.5 weight of AgCl formed
Percentage of chlorine= 143.5  weight of organic compound  100
80 weight of AgBr formed
Percentage of bromine = 188  weight of organic compound  100
127 weight of AgI formed
Percentage of iodine = 235  weight of organic compound  100
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 4

32 weight of BaSO
4 formed
Percentage of Sulphur = 233  weight of organic compound  100
Percentage of oxygen = 100  Sum of percentage of all other elements percent in the
compound.
Molecular formula = n  Empirical formula
Molecular weight
 n= Empirical formula weight
Molecular weight of acid = Equivalent weight  Basicity
 weight of silver salt 
Molecular weight of acid = Basicity    107 
 weight of silver
 
1  weight of platinum salt  195 
Molecular weight of base=  acidity  
 weight of platinium
 410 
2  
Molecular weight = 2  Vapour density
2  weight of compound  22400
Molecular weight = volume of vapour given by subs tan ce at NTP
100  K f  weight of subs tan ce
Molecular weight =
Tf  weight of solvent
where Kf = Molal freezing point depression constant
Tf = Depression in freezing point
100  K b  weight of compound
Molecular weight =
Tb  weight of solvent
where Kb = Molal boiling point elevation constant
Tb = Elevation of boiling point

DETECTION OF FUNCTIONAL GROUPS

Detection of functional groups is an important step in the analysis of organic compounds.
It largely depends on the correct determination of the constituent elements.

(a) Tests for carboxylic group

(i) Litmus test: Place a small quantity of the organic compound or its aqueous solution
on a piece of moist blue litmus paper. If the paper turns red, carboxylic group may be
present.
(ii) Sodium bicarbonate test: Add a small quantity of the organic compound to about
5 ml sodium bicarbonate solution taken in a testcube. Compound dissolves with brisk
effervescences.
RCOOH + NaHCO3  RCOONa + H2O + CO2

(iii) Take a small quantity of the organic compound and add 45 ml of alcohol in a
testtube. Add a few drops of conc. sulphuric acid and warm on a water bath. A fruity
smell indicates the presence of an ester.
RCOOH + R OH H2SO4  RCOOR + H2O
Ester
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 5

(b) Tests for aldehyde group

(i) Schiff test: Take 5 ml of Schiff’s reagent in a testtube and shake with organic
compound (do not heat). A pink colour is formed within two minutes.
Cl NH2

H2N C
H
2SO
3

orSO2 gas
2H2O
NH2

pRosaniline hydrochloride

Cl N H S O 2H

H 2N C
 R CHO
 
H O 3S
N H S O 2H

S c h i f f’ s r e a g e n t ( c o l o u r l e s s )

Cl NHSO2H

H2N C
+ RCHO.H2SO3

NHSO2H

(Pink colour)
(ii) Fehling’s test: Mix equal volumes of Fehling’s (A) and Fehling’s (B) solution in a
testtube. Add a small amount of the organic compound and boil for some time. A red
precipitate of Cu2O is obtained.
RCHO + 2CuO  RCOOH + Cu2O
Red
(iii) Tollen’s test: Take about 5 ml of Tollen’s reagent in a testtube. Add a small
quantity of the organic compound and heat on a water bath. A shining silver mirror is
formed on inner walls of the testtube.
RCHO + 2[Ag(NH3)2]OH + H2O  RCOONH4 + NH3 + 2NH4OH + 2Ag
Tollen’s reagent Silver mirror

(iv)Benedict’s test: Take 45 ml of Benedict’s reagent in a testtube. Add a few ml of the
organic compound (or a solution prepared in alcohol or water). Heat the mixture to
boiling. Formation of red precipitate indicates the presence of aldehydes.
RCHO + 2Cu(OH)2 + NaOH  Cu2O + RCOONa+ + 3H2O
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 6

(c) Tests for ketonic group

(i) Ketones, unlike aldehydes, do not restore the pink colour of Schiff’s reagent nor do
they reduce Fehling’s solution or ammoniacal silver nitrate solution. However, they
form crystalline precipitate with 2,4dinitro phenylhydrazine and also with sodium
bisulphite reagent.
N O 2 NO2
R R
C=O+H 2NH N N O 2 
  C = NHN NO2
R ’ R’
R R OH
C=O+NaHSO3    C
R’ R’ SO3Na
(Bisulphiteaddition
compound)
(ii) Sodium nitroprusside test: Treat 1 ml of the organic compound with 1 ml of freshly
prepared solution of sodium nitroprusside followed by excess of NaOH solution. A
winered colour is obtained.

(d) Tests for phenolic group

(i) Litmus test: Place a trace of the organic compound on the moist blue litmus paper. It
turns red.

(ii) Neutral FeCl3 test: When phenols are treated with neutral ferric chloride solution,
they form coloured complexes. The colour of the complex may be violet, red, blue or
green. This is a characteristic reaction of compounds having enolic group. (=COH).
All enols respond to this test.
With relatively milder oxidizing agents such as ferric chloride (Fe 3+) a resonance
stabilized phenoxyl radical is formed. This radical soon undergoes dimerization which
may take place by orthoortho, orthopara, parapara coupling reaction.
OH O O O O
H H
+Fe3+ 
 
 
 


H Fe2+ +H+
O O O
H H H
O O O
+ H +
H H

The phenoxyl radicals are highly coloured and therefore, products are also coloured.
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 7

(iii) Anilne Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in
icecold water and add aqueous solution of sodium nitrite dropwise. To this cold
solution, add organic compound already dissolved in sodium hydroxide solution. A red
or orange precipitate is obtained.
NaNO2 + HCl  HNO2 + NaCl
Cl
+ HNO + HCl  + 2H2O
NH2 2 0C
  NN

Cl

NN + OH NaOH
 N=N OH
 NaCl
Benzenediazonium Phenol  H 2O phydroxy azobenzene (dye)
chloride

(iv)Phthalein test (Fluorescein test): Heat gently some organic compound and phthalic
anhydride with a few ml of conc. sulphuric acid in a testtube. Pour the heated mixture
to about 50 ml of water taken in a beaker and then add sodium hydroxide solution till it
became alkaline. A beautiful pink or purple colour appears.

OH OH
C=O C + H 2O
+ H2SO4 

O=C—O OH O=C—O OH

O N a+
2N aO H
C
O
O =C  O  N a +
(pink or purple)
(v) Bromine water test: Take aqueous or alcoholic solution of the organic compound in a
testtube. Add excess of bromine water. A yellowish white precipitate is obtained.
OH OH
Br Br
+ 3Br2 


Phenol
Br
(2,4,6tribromophenol)

(vi)Ceric ammonium nitrate test: Treat a few drops of the ceric ammonium nitrate with
34 ml hot aqueous solution of the organic compound. A green or brown precipitate is
obtained.
(NH4)2[Ce(NO3)6] + 2C6H5OH  [Ce(NO3)4(C6H5OH)2] + 2NH4NO3
phenol green or brown ppt.
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 8

(vii) Liebermann’s test: Take a little amount of the compound and fuse with a few
crystals of NaNO2 in a testtube. Cool the testtube and add 1 ml conc. H 2SO4. A deep
green colour is obtained which changes to pruple, to blue and finally, when poured into
large excess of water, to red. When a little NaOH solution is added to the aqueous
solution, the same green, purple or blue colour reappears.
T
auto
me
riz
e
H
O N=O O 
NOH
HO  2 
NaNO H 2SO 4

(g
ree
nco
lou
r)

 O
Phenol N OH O N ONa+
H 2SO 4 NaOH

Indophenol (red) Indophenol (blue)

(e) Tests for alcoholic group

Alcohols may be considered as neutral compounds. They are soluble in water or dioxane.
(i) Sodium test: Take 34 ml of the organic compound in a testtube. Add a thin slice of
sodium metal. A brisk effervescence due to the evolution of hydrogen takes place.
(Organic compound should be free from water).
2ROH + 2Na  2RONa + H2
(ii) Ester test: Warm the given liquid with acetic acid in presence of sulphuric acid. A
fragrant smell indicates the formation of ester.
ROH + CH3COOH H2SO4  RCOOCH3 + H2O
Alcohols give crystalline esters with 3,5dinitrobenzoyl chloride. These esters have
sharp melting points and can be used for testing a given alcohol.
N O2 NO 2

RO
H lC
+C 
ROC +H
Cl
O O
N O 2 NO 2

(iii) Oxidation test: Take some organic compound, 5 ml of K2Cr2O7 solution and 23
ml of conc. H2SO4 in a testtube. Heat the testtube after fitting a delivery tube. The
distillate is passed into another testtube containing water. Test the aqueous solution of
the distilalte for aldehyde group. A positive test indicates the presence of primary
alcoholic group in the given compound.
[O]
RCH2OH  RCHO + H2O

(iv)Ceric ammonium nitrate test: Shake a few drops of ceric ammonium nitrate with
1 ml of the organic compound. A red colour is produced (Phenols give a green or
brown colour).
2ROH + (NH4)2[Ce(NO3)6]  [Ce(NO3)4(ROH)2] + 2NH4NO3

Distinction between primary, secondary and tertiary alcohols

Lucas test: Add 34 drops of alcohol to 2 ml of Lucas reagent (anhydrous ZnCl 2 + conc.
HCl) in a testtube. Shake the mixture and allow to stand at room temperature. If a cloudy
precipitate is obtained immediately then it is a tertiary alcohol, if obtained after 23
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 9

minutes then it is a secondary alcohol, while no cloudy precipitate even after long standing
means it is a primary alcohol.
…
…

+ 
 Cl  

ROH
+Zn
Cl
2 
RO Zn
C2
l 
R R
Cl
+ 
H [
Zn(
O H
)Cl
2]

(f) Tests for primary amines(NH2)

(i) Carbylamine test: Heat the organic compound with alcoholic KOH and chloroform in
a testtube. A highly offensive smell is evolved due to formation of isocyanides.

RNH2 + CHCl3 + 3KOH  R  N  C + 3KCl + 3H2O
This test is applicable to aliphatic and aromatic primary amines.

(ii) Dye test: This test is applicable only for aromatic primary amines. Dissolve a small
amount of the organic compound in dil. HCl. Cool it in icecold water. Add cold
solution of sodium nitrite with constant shaking and then add naphthol prepared in
NaOH solution. An orangered dye is obtained.
NaNO2 + HCl  HNO2 + NaCl
Cl

NH2 + HNO2 + HCl  N  N + 2H2O

OH OH
Cl

NN + N=N
+ HCl

naphthol (Orangered dye)

(g) Tests for secondary amines (NH)

Liebermann’s nitroso test: Dissolve some organic compound in 3 ml of conc. HCl

and then add 23 ml of water. Cool the solution in icecold water and then add 34 ml
of cold dilute NaNO2 solution. A white or yellow emulsion is produced. Take 45
drops of the above emulsion in a test tube. Add 45 drops of phenol and conc. H2SO4.
A blue colour develops. Addition of water changes blue colour to red which again
changes to blue on adding NaOH solution.

(h) Tests for nitro group

(i) Reduction test: Take a small amount of the organic compound in a testtube. Add a
few ml of conc. hydrochloric acid and one or two pieces of granulated zinc or tin. Heat
the mixture gently for few minutes. Decant the clear liquid into a testtube. Cool it in
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 10

icecold water and then add cold dilute solution of sodium nitrite. Pour this cold
solution into an alkaline solution of naphthol. An orangered dye is obtained. This
test is applicable only to aromatic nitro compounds.
Zn + 2HCl  ZnCl2 + 2[H]
C6H5NO2 + 6[H]  C6H5NH2 + 2H2O
NaNO2 + HCl  HNO2 + NaCl
C6H5NH2 + HNO2 + HCl  C6 H 5 N 2 Cl  + 2H2O
OH OH
Cl

NN + N=N
+ HCl

naphthol (Phenyl azo naphthol dye)

(ii) Mulliken’s test: Take a small amount of the organic compound in a testtube. Add a
few ml of water or alcohol, 1 ml of calcium chloride or ammonium chloride solution
and then a pinch of zinc dust. Boil the mixture for few minutes. Cool and then filter.
Treat this filtrate with ammoniacal silver nitrate solution. A grey or black precipitate is
obtained.
Zn + 2H2O  Zn(OH)2 + 2[H]
C6H5NO2 + 4[H]  C6H5NHOH + H2O
C6H5NHOH + Ag2O  C6H5NO + H2O + 2Ag
Grey
This test is also applicable for aromatic nitro compounds.

QUANTITATIVE ELEMENTAL ANALYSIS

After determining the constituent elements of an organic compound, the next step is to
determine their amounts by quantitative methods. The methods usually involve
combustion, oxidation etc. of an organic compound so that they may change into such
inorganic compounds as can be estimated either by volumetric or gravimetric method.

ESTIMATION OF CARBON AND HYDROGEN

Liebig’s Combustion Method: A weighed amount of the compound is heated in a current
of dry air free from carbon dioxide or pure oxygen till the carbon of the compound
changes to CO2 and hydrogen into water. Carbon dioxide and water thus formed are
trapped in a suitable apparatus and weighed.
C + 2CuO  CO2 + 2Cu
2H + CuO  H2O + Cu
The percentage composition is then calculated.
Calculation
Let the weight of the sample = W g
Let the weight of water formed = x g
(Increase in weight of CaCl2 tube)
and let the weight of CO2 formed = y g
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 11

(Increase in weight of potash bulb)

Since 44 g of CO2 are formed from 12 g of carbon,
12
 y g of CO2 are formed from  y g of carbon
44
Since 18 g of water are formed from 2 g of hydrogen,
2 1
 x g of water are formed from  x g of hydrogen = x g of hydrogen
18 9
12
Now, W g of the substance contains  y g of carbon
44
12  100 y
 100 g of the substance contains g carbon
44  W
x
Again W g of the substance contain g of hydrogen
9
100x
 100 g of the substance contain g of hydrogen
9W
12  100y
 Percentage of carbon =
44  W
100 x
and percentage of hydrogen =
9W

ESTIMATION OF NITROGEN
(i) Duma’s Method: In this method the organic compound is heated with copper oxide
strongly. Carbon, hydrogen and sulphur are oxidized to CO 2, H2O and SO2 respectively,
while nitrogen is set free. These gases are passed through a nitrometer containing 30%
KOH solution. Carbon dioxide and sulphur dioxide are absorbed, steam condenses and
nitrogen collects by the displacement of KOH solution. From the volume of the collected
nitrogen, the percentage of nitrogen is calculated.
y z
CxHyNz + CuO  xCO2 + H2O + N2 + Cu
2 2
Calculation
Let the weight of the sample = W g
Volume of moist N2 = V cc
Room temperature = t°C
Barometric pressure = P mm
Aqueous tension at t°C = f mm
P1V1 P V
We know,  2 2
T1 T2
(P  f )  V 760  V2
or  (V2 = Volume of N2 at NTP)
(273  t ) 273
( P  f )  273  V
V2 = cc
760  ( 273  t )
( P  f )  273  V
Volume of N2 at NTP in cc =
760  ( 273  t )
Now, 22400 cc of N2 at NTP weigh 28 g.
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 12

( P  f )  273  V  28(P  f )  273  V 

 at NTP weigh   g
760  ( 273  t )  760  22400(273  t ) 
28( P  f )  273  V
W g of the substance contain g N2
760  22400( 273  t )
28(P  f )  273  V  100
 100 g of the substance contains
760  22400W (273  t )
28 Volume of N 2 at NTP
Percentage of Nitrogen =   100
22400 Weight of substance

(ii) Kjeldahl’s Method: The principle of this method is that when an organic compound
containing nitrogen is heated with concentrated sulphuric acid, the nitrogen is converted
into ammonium sulphate. The resulting solution on treatment with excess of sodium
hydroxide solution gives off ammonia. Ammonia is then absorbed in excess of standard
sulphuric acid. The amount of ammonia and hence the amount of nitrogen is determined
by finding the amount of acid neutralized by back titration of the residual acid with a
standard alkali solution. From this the percentage of nitrogen is calculated.

Calculation:
Let the weight of the substance = W g and let V cc of N acid is required to neutralize the
ammonia evolved.
 V cc of N acid = V cc of N NH3
1000 cc of N NH3 = 17 g of NH3 = 14 g of nitrogen
14
V cc of N NH3 =  V  N = 0.014 NV g
1000
100
 Percentage of nitrogen = Weight of nitrogen  Weight of subs tan ce
0.014  N  V  100
=
W
Kjeldahl’s method fails to detect nitrogen from azo compounds (–N = N–),
O
Azoxy , nitroso (–NO) compounds and nitrogen present in pyridine ring.
(–N = N–)

ESTIMATION OF HALOGEN
(i) Carius Method: The compound containing halogen is heated with fuming nitric acid
in a sealed tube (Carius tube) in presence of silver nitrate. Carbon and hydrogen present
are oxidized to carbon dioxide and water. The halogens react with silver nitrate to give the
precipitate of silver halide. The precipitate is collected, washed, dried and weighed.
Calculation
Let the weight of the substance be W g.
Weight of the silver halide be y g.
Atomic weight of ha log en
Weight of halogen = Molecular weight of silver halide  y g
Atomic weight of halogen 100
 Percentage of halogen = Molecular weight of silver halide  y  W
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 13

ESTIMATION OF SULPHUR
The compound is heated with fuming nitric acid. Sulphur present is oxidized to sulphuric
acid. Barium chloride solution is added. The precipitate of barium sulphate is obtained. It
is collected, washed, dried and weighed.
Weight of BaSO 4 Atomic weight of Sulphur
% of Sulphur =   100
Molecular weight of BaSO 4 Weight of Organic compound
Silver salt method for determining molecular weight of organic acids
This method is based on the fact that organic acids form insoluble silver salts which on
ignition leave a residue to metallic silver.
A small quantity of organic acid is treated with water or a suitable solvent and then a slight
excess of ammonia solution added. The solution is boiled to expel excess of ammonia.
Excess of silver nitrate solution is added to this solution when a white precipitate of
insoluble silver salt is obtained. The precipitate is filtered and washed successively with
water, alcohol and ether and then dried in an air oven.
A known weight of the silver salt is taken in a weighed crucible and ignited till
decomposition is complete. The crucible is cooled and then weighed. Heating, cooling and
weighing is continued till the final weight is constant.
Calculation
Weight of crucible + lid = W g
Weight of crucible + lid + silver salt = W1 g
Weight of crucible + lid + residual silver = W2 g
Weight of silver salt = (W1  W) g
And weight of silver = (W2  W) g
(W2  W) g of silver is obtained from (W1  W) g of silver salt.
( W1  W )  108
108 g of silver is obtained from g of silver salt.
( W2  W )
( W1  W )  108
Equivalent weight of silver salt =
( W2  W )
But equivalent weight of acid = Equivalent weight of Ag salt  108 + 1
= Equivalent weight of Ag salt  107
 ( W1  W )  108 
 Molecular weight of the acid =   107  n
 ( W2  W ) 
(where n = basicity of the acid)
FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 14

Pla tinichloride method for determining molecular weight of organic bases

Organic bases (e.g. amines) form insoluble salts known as platinichlorides when treated
with hydrochloroplatinic acid [H2PtCl6]. These salts are represented by the general formula
B2H2PtCl6, where B is one equivalent of the base. These salts on ignition leave a residue of
metallic platinum.
The base is dissolved in HCl and a solution of platinic chloride PtCl 4 is added. The yellow
crystalline salt that separates out is filtered, washed and dried. A known weight of the
dried salt is ignited is a crucible.
Calculation
Let X1 g of the platinichloride leave on ignition X2 g of platinum.
X2 g of Pt is left by X1 g of the salt on ignition.
 X  195 
195 g (At. weight of Pt) is left by  1  g of the salt on ignition.
 X2 
X1
Molecular weight of the salt =  195
X2
Molecular weight of H2PtCl6 = 410
 X1 
  195   410
Equivalent weight of base B = B2 H 2 PtCl 6  H 2 PtCl 6  X 2 

2 2
If the acidity of the base is n, then
 X   n
Molecular weight of base =  1  195   410 
 X 2   2
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 15

SOLVED SUBJECTIVE EXAMPLES

EXAMPLE 1
0.25 g of an organic compound on combustion gave 0.495 g of CO 2 and 0.2025 g of
H2O. Calculate the percentage of carbon and hydrogen in the compound.
SOLUTION
Given weight of the substance = 0.25 g
Weight of CO2 formed = 0.495 g
Weight of H2O formed = 0.2025 g
44 g of CO2 are formed from 12 g of carbon.
12
 0.495 g are formed from  0.495 of carbon
44
12  0.495
Now 0.25 g of the substance contains g carbon.
44
12  0.495  100
 100 g of the substance contains = 54.55 g
44  0.25
Since 18 g of H2O are formed from 2 g of hydrogen.
2
 0.2025 g H2O are formed from  0.2025 g hydrogen
18
2  0.2025
Now, 0.25 g of the substance contains g hydrogen
18
2  0.2025  100
 100 g of the substance contains = 9.09 g hydrogen
0.25  18
% of carbon = 54.55
% of hydrogen = 9.09

EXAMPLE 2
0.159 g of an organic compound gave 14.01 cc of nitrogen at 19°C and 719.5 mm
pressure by Duma’s method. Calculate % of nitrogen in the organic compound.
Given: Aqueous tension of water = 11.5 mm of Hg at 19°C.
SOLUTION
Aqueous tension at 19°C = 11.5 mm
We know,
P1 V1 P V
 2 2
T1 T2
(719.5  11 .5)  14.01 760  VN at NTP
or 
( 273  19) 273
708  14.01  273
VN 2 at NTP = cc
760  292
Now, 22400 cc of N2 at NTP weigh 28 g
28
 1 cc of N2 at NTP weigh g
22400
708  14.01  273 28  708  14.01  273
 cc = g
760  292 22400  760  292
28  708  14.01  273
0.159 g of the compound contains g N2
22400  760  292
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 16

28  708  14.01  273  100

 100 g of the compound contains = 9.60 g of nitrogen
22400  760  292  0.159
Percentage of nitrogen = 9.6%

EXAMPLE 3
0.69 g of an organic compound after heating with concentrated sulphuric acid was
distilled with excess of NaOH. Ammonia liberated was passed into 100 cc of N HCl
solution. The excess of the acid neutralized 80 cc of N NaOH. Calculate the percentage
of nitrogen in the compound.
SOLUTION
80 cc of N NaOH = 80 cc of N HCl = Volume of residual acid
Volume of acid neutralized = (10080) cc N = 20 cc of N HCl = 20 cc of N NH3
Now, 1000 cc N NH3 = 14 g of nitrogen
14  20
20 cc N NH3 = g of nitrogen
1000
14  20
0.69 g of the substance contains g of nitrogen.
1000
14  20  100
 100 g of the substance contains = 40
0.69  1000
 Percentage of nitrogen = 40%

EXAMPLE 4
0.26 g of an organic compound on heating with fuming nitric acid and silver nitrate
give 0.31 g of silver bromide. Calculate the percentage of bromine in the compound.
SOLUTION
Now, AgBr  Br
or (108+80) g = 80 g
 188 g of AgBr give 80 g of bromine.
80
 0.31 g of AgBr give  0.31 = 0.1319 g bromine
188
Now, 0.26 g of the substance give 0.1319 g bromine.
0.1319  100
 100 g of the substance gave = 50.7
0.26
 Percentage of bromine = 50.7

EXAMPLE 5
40 g of an organic compound gave 0.60 g of barium sulphate after Carius method. Find
out the percentage of sulphur in the compound.

SOLUTION
Since, BaSO4  S
233 g 32 g

233 g of BaSO4 gives 32 g of sulphur.

32
0.60 g of BaSO4 gives  0.60 g of sulphur = 0.082 g sulphur
233
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 17

0.082
 Percentage of sulphur =  100 = 0.205%
40

EXAMPLE 6
0.167 g of the silver salt of a monobasic organic acid left on ignition 0.108 g of silver.
Calculate the molecular weight of the acid.
SOLUTION
Weight of Ag salt = 0.167 g and weight of Ag left = 0.108 g.
0.167
The weight of Ag salt that would leave 108 g of silver = 108 = 167 g
0.108
Equivalent weight of acid = 167  108 + 1 = 167  107 = 60
Molecular weight of the acid = 60  1 (basicity) = 60

EXAMPLE 7
Calculate the molecular weight of a monobasic base, 0.298 g of whose platinichloride
left 0.0975 g of platinum on ignition.
SOLUTION
Weight of the platinichloride = 0.298 g (X1) and weight of platinum = 0.0975 g (X2).
0.298
 195  410 596  410 186
Equivalent weight of the base = 0.0975 =  = 93
2 2
2
Molecular weight of the base = 93  1 (acidity) = 93

EXAMPLE 8
A mono acid organic base on analysis gave the following results: 0.10 g of the base gave
0.28 g of CO2 and 0.075 g of water and 0.20 g of the base gave 31.32 ml N 2 measured at
15°C and 760 mm, 0.30 g of the platonic chloride left on ignition 0.093 g of platinum.
What is the molecular formula of the base?
SOLUTION
The molecular formula is derived as follows
(a) Calculation of % of elements
12 0.28
% of carbon =   100 = 76.36%
44 0.10
2 0.075
% of hydrogen =   100 = 8.33%
18 0.10
28 Volume of N 2 at NTP  100
% of nitrogen = 
22400 Weight of organic compound
28  31.32  100
% of nitrogen = = 13.05%
22400  0.3
(b) Calculation of relative number of each atom:
76.36 8.33 13.05
C= = 6.36; H = =8.33 and N = =0.90
12 1 14
(c) Calculation of simplest ratio:
6.35 8.33 0.90
C= 7;H= = 9 and N = 1
0.90 0.90 0.90
(d) Determination of empirical formula:
It comes to be C7H9N, its empirical formula weight = 84 + 9 + 14 = 107
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 18

(e) Determination of molecular weight:

The molecular weight of the base is given by,
1 Weight % hexachloroplatinate salt 
B = 2 195  Weight % pt
 410
 
1 195  0.3  1
B=   410  [629  410]  109.5
2  0.093  2
B = 109.5
Molecular weight 109.5
n = Empirical weight  107  1
Hence, molecular formula = empirical formula = C7H9N

EXAMPLE 9
A sample of a gaseous hydrocarbon occupying 1.12 litre at NTP was completely burnt in
air and gave 2.2 g of CO 2 and 1.8 g of H2O. Calculate the weight of compound taken
and volume of O2 at NTP required for its burning. Also calculate the molecular formula
of the hydrocarbon.
SOLUTION
Volume evolved at NTP
Molecular of compound = 22400 ml or 22.4 litres is occupied
by each subs tan ce
1.12
= = 0.05 mol
22.4
2.2
Moles of CO2 produced = = 0.05 mol
44
1.8
Moles of H2O produced = = 0.10 mol
18
Suppose the hydrocarbon is CxHy
Then
 y
CxHy +  x   O2  xCO2 + y/2 H2O
 4
 1 mole of CxHy gives = 0.05 a mol of CO2
 0.05 x = 0.05
0.05
 x= 1
0.05
y
Now, 1 mole of CxHy gives = mol of H2O
2
y
 0.05 mol of CxHy will give = 0.05 mol of H2O
2
y
 0.05
2
= 0.10
 y=4
Hence, the hydrocarbon is CH4
16  1.12
Weight of 1.12 litre CH4 at STP = = 0.8 g
22.4
Also, CH4 + 2O2  CO2 + 2H2O
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 19

 1 mol of CH4 requires 2  32 g oxygen

 0.05 mol of CH4 requires 2  32  0.05 = 3.2 g CO2
CH4 requires O2 = 3.2 g

EXAMPLE 10
An organic compound, A containing C, H, N and O, on analysis gives 40.32% carbon,
9.59% hydrogen and 19.18% nitrogen. A on boiling with NaOH gives off NH3 and a salt
which on acidification gives a monobasic nitrogen free acid B. The silver salt of B
contains 59.67% silver. Deduce the structures of A and B.
SOLUTION
Percentage of oxygen = 100  (49.2 + 9.59 + 19.18) = 21.91

Percentage Relative No. of

Elements Atomic weight Simplest ratio
composition atoms
49.12 4.11
C 49.32 12 = 4.11 =3
12 1.37
9.59 9.59
H 9.59 1 = 9.59 =7
1 1.37
19.18 1.37
N 19.18 14 = 1.37 =1
14 1.37
21.91 1.37
O 21.91 16 = 1.37 =1
1.37 1.37
Hence empirical formula of A = C3H7NO
Because A, gives NH3 on boiling with NaOH, it can be an amide.
Now, silver salt of B, has 59.67% silver.
 100  108 
Hence equivalent weight of acid =    107 = 74
 59.67 

Molecular weight of monobasic acid = 74  1 = 74

Molecular formula of acid = C3H6O2
 Structural formula of acid B is C2H5COOH.
Molecular formula of amide = C3H7NO.
Hence structural formula of amide (A) is C2H5CONH2.
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 20

 STRAIGHT OBJECTIVE TYPE

 O - Level
1. Nitrogen in an organic compound can be estimated by
(a) Kjeldahl’s method (b) Duma’s method
(c) both (a) and (b) (d) None of the above

2. Which of the following compounds is of violet colour

(a) Na4[Fe(CN)5NSO3]3 (b) Na3[Fe(CN)6NSO]2
(c) Na2[Fe(CN)5NSO]3 (d) Na4[Fe(CN)5NOS]

3. A compound containing 80% carbon and 20% hydrogen is likely to be

(a) C6H6 (b) C2H5OH
(c) C2H6 (d) CHI3

4. Aniline, chloroform and alc. KOH on heating gives

(a) Phenyl isocyanide (b) Phenyl cyanide
(c) Chlorobenzene (d) Phenol

5. Methyl ketones are usually characterized through

(a) Tollen’s test (b) Iodoform test
(c) Schiff test (d) Benedict’s test

6. Which of the following is used for separating aniline from nitrobenzene?

(a) Na2CO3 (b) HCl
(c) NaHCO3 (d) NaCl

7. The compound that does not give a blue colour in Lassaigne’s test is
(a) Aniline (b) Glycine
(c) Hydrazine (d) Urea

8. 0.2 g of an organic compound on complete combustion produces 0.18 g of water, then the
percentage of hydrogen in the compound is
(a) 5 (b) 10
(c) 15 (d) 20

9. In which of the following compounds, nitrogen cannot be tested by Lassaigne’s test?

(a) C6H5NH2 (b) NH2.NH2.H2O
(c) CH3CONH2 (d) C6H5NO2

10. When a nitrogen containing organic compound is strongly heated with conc. H2SO4, the
product is
(a) HNO3 (b) (NH4)2SO4
(c) NH3 (d) N2
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 21

11. To determine the weight of a halogen in organic compound, the compound is heated with
fuming HNO3 in presence of
(a) Ag (b) AgNO3
(c) Ag2CO3 (d) Ag2SO4

12. A mixture of onitrophenol and pnitrophenol can be separated by

(a) Sublimation (b) Steam distillation
(c) Fractional crystallization (d) Distillation

13. In Lassaigne’s test for nitrogen the blue colour is due to the formation of
(a) FerricFerro cyanide (b) K4[Fe(CN)6]
(c) Na4[Fe(CN)6] (d) NaCN

14. Nitrogen is estimated by

(a) Liebig method (b) Carius method
(c) Duma’s method (d) None of these

15. An organic compound is found to contain C = 39.9%, H = 6.7%, O = 53.4%. Its empirical
formula is
(a) CHO (b) CHO2
(c) CH2O2 (d) CH2O
16. Which of the following compounds will give blood red colour in the Lassaigne’s test for
nitrogen?
(a) (NH2)2C = O (b) H2N(C6H4)SO3H
(c) C6H5SO3H (d) CHCl3

17. In Kjeldahl’s method, nitrogen element is estimated as

(a) N2 (b) NO
(c) NH3 (d) NO2

18. 0.10 g of an organic compound containing phosphorus gave 0.222 g of Mg 2P2O7. Then the
percentage of phosphorus in it is
(a) 62 (b) 6.2
(c) 31 (d) 13

19. A gaseous hydrocarbon has 85% carbon and vapour density of 28. The possible formula of
the hydrocarbon will be
(a) C3H6 (b) C2H4
(c) C2H2 (d) C4H8

20. If empirical formula of an organic compound is CH2O and its 6.02  1023 molecules
weight 60 g, then it can be
(a) CH3OH (b) C2H5OH
(c) HCOOH (d) HCOOCH3
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 22

 I - Level
1. In the estimation by Duma’s method 0.59 g of an organic compound gave 112 ml nitrogen
at NTP. The percentage of nitrogen in the compound is about
(a) 23.7 (b) 11.8
(c) 20 (d) 47.5
2. If 0.2 g of an organic compound containing C, H and O on combustion yields 0.147 g CO 2
and 0.12 g water, the percentage of oxygen in it is
(a) 73.29% (b) 78.45%
(c) 83.23% (d) 89.50%
3. A dibasic acid containing C, H and O was found to contain C = 26.7% and H = 2.2%. The
vapour density of diethyl ester of the acid was found to be 73. What is molecular formula
of the acid
(a) CH2O2 (b) C2H2O4
(c) C3H3O4 (d) C4H4O4
4. The percentage of sulphur in the organic compound, when 0.2595 g of a sulphur
containing organic compound in a quantitative analysis by Carius method yielded 0.35 g
of barium sulphate is
(a) 14.52% (b) 16.52%
(c) 18.52% (d) 19.52%
5. If 0.228 g of silver salt of dibasic acid gave a residue of 0.162 g of silver on ignition, then
molecular weight of the acid is
(a) 70 (b) 80
(c) 90 (d) 100
6. ClCH2COOH is heated with fuming nitric acid in the presence of AgNO 3 in a Carius tube.
After filtration and washing a white precipitate is obtained. The precipitate is
(a) AgNO3 (b) Ag2O
(c) AgCl (d) ClCH2COOAg
7. The Lassaigne’s extract is boiled with dil. HNO3 before testing for halogens because
(a) Silver halides are soluble in HNO3.
(b) Na2S and NaCN are decomposed by HNO3.
(c) Ag2S is soluble in HNO3.
(d) AgCN is soluble in HNO3.
8. The silver salt of a monobasic acid on ignition gave 60% of Ag. The molecular weight of
the acid is
(a) 37 (b) 33
(c) 73 (d) 77
9. 0.1914 g of an organic acid is dissolved in about 20 ml of water. 25 ml of 0.12 N NaOH is
required for the complete neutralization of the acid solution. The equivalent weight of the
acid is
(a) 65 (b) 64
(c) 63.8 (d) 62.5
10. If the percentage of nitrogen in an organic compound is 12.5% then how much of the
organic compound should be taken so as to produce 50 ml of N 2 at 300 K and 715 mm
pressure (Aqueous tension = 15 mm)?
(a) 0.419 g (b) 0.149 g
(c) 0.914 g (d) 0.941 g
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 23

 E - Level

1. Which of the following is a technique most suitable for purification of cyclohexanone

from a mixture containing benzoic acid, isoamyl alcohol, cyclohexane and
cyclohexanone?
(a) crystallization (b) I.R. spectroscopy
(c) sublimation (d) gas chromatography

2. Absolute alcohol is prepared by

(a) Fractional distillation (b) Kolbe’s method
(c) Vaccum distillation (d) Azeotropic distillation

3. 0.24 g of a volatile liquid on vaporization gives 45 ml of vapours at STP. What will be the
vapour density of the substance? (Density of H2=0.089 g L-1)
(a) 99.39 (b) 39.95
(c) 95.53 (d) 59.93

4. If a compound on analysis was found to contain C = 18.5%, H = 1.55%, Cl = 55.04% and

O = 24.81% then its empirical formula is
(a) CHClO (b) CH2ClO
(c) C2H5OCl (d) ClC2H5O

5. A liquid decomposes at its normal pressure. It can be purified by

(a) sublimation (b) fractional distillation
(c) vacuum distillation (d) steam distillation

6. The best solvent to remove butter stain from cloth is

(a) CHCl3 (b) C2H5OH
(c) C2H5OC2H5 (d) H2O

7. In peroxidase anhydrase enzyme the percentage of selenium (Se) by mass is 0.5%. If

atomic mass of Se is 78.4U, then minimum molecular mass of peroxidase anhydrase
enzyme is
(a) 1.568 ×103 U (b) 1.568 × 104 U
(c) 1.568 U (d) 2.136 × 104 U

8. In a hydrocarbon, mass ratio of hydrogen and carbon is 1 : 3, the empirical formula of

hydrocarbon is
(a) CH2 (b) CH4
(c) CH3 (d) CH

9. If we want to study the relative arrangement of atoms in a molecule, we study

(a) empirical formula (b) molecular formula
(c) structural formula (d) none of these
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 24

10. Which of the following statements is wrong?

(a) In the estimation of carbon, an organic compound is heated with CaO in a combustion
tube.
(b) Using Lassaigne’s test nitrogen and sulphur present in an organic compound can be
tested.
(c) Using Beilstein’s test the presence of halogen in a compound can be tested.
(d) Lassagine’s test fails to identify nitrogen in diazo compound.

11. 0.833 mole of a carbohydrate with empirical formula CH2O has 10 g of hydrogen. What is
its molecular formula?
(a) C5H10O5 (b) C6H12O6
(c) C3H4O3 (d) C3H5O3

12. A chemical compound is heated and dried. To get accurate weight of this compound
(a) weigh in warm condition (b) weigh after cooling
(c) cool in desiccator (d) blow air through it

13. The ammonia evolved from the treatment of 0.03 g of an organic compound for the
estimation of nitrogen was passed in 100 mL of 0.1M sulphuric acid. The excess of the
acid required 20 mL of 0.5M sodium hydroxide solution for complete neutralization. The
organic compound is
(a) acetamide (b) benzamide
(c) urea (d) thiourea

14. 116 mg of a compound on vapourization in a Victor Mayer’s apparatus displaces 44.8 mL

of air measured at STP. The molecular mass of the compound is
(a) 58 (b) 116
(c) 232 (d) 44.8

15. An organic compound having molecular mass 60 is found to contain C = 20%, H = 6.67%
and N = 46.67% while rest is oxygen. On heating it gives NH 3 along with a solid residue.
The solid residue gives violet colour with alkaline copper sulphate solution. The
compound is
(a) CH3NCO (b) CH3CONH2
(c) (NH2)2CO (d) CH3CH2CONH2
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 25

 LINKED COMPREHENSION TYPE

Paragraph– 1
Given are the isomers of C8H8O2.
O O

COEt CHO CO2H OH C – CH3 CO2CHO

OCH3 CH3 OCH = CH2 OH OH

(a) (b) (c) (d) (e) (f)
Questions:
1. Which isomer gives positive iodoform test?
(a) a (b) b
(c) d (d) e

2. Which isomer gives positive Tollen’s test, also reacts with FeCl3?
(a) b (b) f
(c) c (d) d

3. Which isomer reacts with NaHCO3?

(a) c (b) d
(c) e (d) f
4. Which isomer on hydrolysis gives 1, 4-dihydroxybenzene?
(a) a (b) d
(c) e (d) f

Paragraph2
An organic acid (A) is widely used as a food additive. Its elemental composition is 41.4%
carbon, 3.5 % hydrogen and rest being oxygen. A solution made by dissolving 0.150 g of
(A) in water and diluting to a volume of 100 ml gave rise to an osmotic pressure of
240.3 mm of Hg at 298 K. For complete titration of 0.573 g sample of (A), 94.1 ml of
0.105 M NaOH was required to reach end point. Each mole of (A) reacts with 1 mole of
HCl to give an addition product and with 1 mole of H2 to give a reduction product
Questions:
1. The molecular weight of the food additive is
(a) 58 (b) 116
(c) 174 (d) 232

2. The basicity of organic acid (A) is

(a) 1 (b) 2
(c) 3 (d) 4
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 26

3. The molecular formula of the acid (A) would be

(a) C5H8O3 (b) C2H2O2
(c) C7H12O2 (d) C4H4O4
4. Which can’t be possible structures of the acid (A)?
HOOC COOH HOOC H
(a) C = C (b) C = C
H H H COOH

O
(c) H2C = C  C  O  H (d) CH2 — CH2
C=O COOH COOH
OH

5. If the compound (A) does not show geometrical isomerism, its structure would be
HOOC COOH HOOC H
(a) C = C (b) C = C
H H H COOH

O
(c) H2C = C  C  O  H (d) CH2 — CH2
C=O COOH COOH
OH

Paragraph– 3
To arrive at the molecular formula and at the structural formula the different steps
involved are
(1) Qualitative analysis (2) Quantitative analysis
In the quantitative analysis the different steps involved are
(a) Extra element detection (b) Functional group analysis
In the quantitative analysis the percentage of every element is determined and then the
empirical and molecular formulae are determined. Both these are followed by structural
elucidation.
Questions:
1. Which of the following reagent is used to distinguish products of hydrolysis of
CH3COOCH=CH2
(a) NaHCO3 (aq) (b) Luca’s reagent
(c) Baeyer’s reagent (d) Cerric ammonium nitrate (aq)
2. Which of the following reagents can be used to identify benzene in one go?
(a) Bromine water test (b) CHCl3 + AlCl3 (anhydrous) test
(c) I2 + NaOH (d) No test is available
3. The number of hydroxyl groups in a compound not containing any other functional group
can be determined by
(a) CH3COCl (b) CH3MgBr
(c) CH3OCH3 (d) Both (a) and (b)
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 27

Paragraph4
Figure I illustrates a solubility based characterization procedure, often used by organic
chemists, for the qualitative analysis of monofunctional organic compounds. Table 1 lists
the organic compounds comprising the various solubility classes of Fig. I.

Figure I
Group Compounds
I Salts of organic acids, amino acids, amine chlorides
Sugars (carbohydrates) and other polyfunctional compounds with hydrophilic
groups
II Arenesulfonic acids
Monofunctional carboxylic acids, alcohols, ketones, aldehydes, esters, amides and
nitriles with 5 or less carbon atoms
Monofunctional amines with 6 or less carbon atoms
III Phenols with ortho-and/or para-électron withdrawing groups, β-diketones
Carboxylic acids with 6 or more carbon atoms
IV Sulfonamides, nitro-compounds, with α-hydrogens
Phenols, oximes, enols imides and thiophenols with 6 or more carbon atoms
V Some oxy-ethers, anilines, aliphatic amines, with 8 or more carbon atoms
VI Neutral compounds containing sulfur or nitrogen with 6 or more carbon atoms
VII Ethers with 7 or less carbon atoms
Monofunctional esters, aldehydes, ketones, cyclic ketones, methyl ketones with
between 6 and 8 carbon atoms; epoxides
VIII Ethers, most other ketones
Unsaturated hydrocarbons, aromatic compounds, particularly those which possess
activating groups
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 28

Questions:
1. A certain water insoluble compound is insoluble in 5% sodium hydroxide, insoluble in 5%
HCI, and insoluble in concentrated H2SO4 and soluble in 5% sodium bicarbonate. In which
class should this compound be classified?
(a) III (b) IV
(c) VIII (d) IX
2. Benzoic acid should be soluble in which of the following solvent pairs?
(a) Water and 5% HCI (b) 5% NaOH and 5% NaHCO3
(c) 5% HCI and 5% NaOH (d) 85% H3PO4 and 5% NaOH
3. Low molecular weight amino acids fall into group I in Table 1. This is most likely due to
the fact that low molecular weight amino acids are:
(a) hydrophilic and basic (b) hydrophobic and amphoteric
(c) hydrophobic and lipophilic (d) hydrophilic and amphoteric
4. A critical step in acid catalyzed ester hydrolysis is the attack of water molecules on the
protonated ester. If the water molecules are replaced with an alcohol, then the reaction will
involve:
(a) transesterification of one ester to another
(b) reduction to the corresponding aldehyde
(c) base protonated ester hydrolysis to the corresponding acid
(d) decarboxylation to the corresponding C-H unit
5. A water soluble unknown is unreactive in the presence of sodium bicarbonate, gives a
positive 2,4-DNP test and negative Fehling's and Iodoform tests. In which of the following
classes should this compound be classified?
(a) Aldehyde (b) Ketone
(c) Carboxylic acid (d) Alcohol
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 29

 MATRIX MATCH TYPE

1.
ColumnI ColumnII
(A) Cerric ammonium nitrate solution (p) Carboxylic acid
(B) Neutral FeCl3 (q) 1o, 2o, 3o Nitro compounds
(C) NaHCO3 (aq) (r) Phenols
(D) Victor Meyer’s test (s) Alcohols

2.
ColumnI ColumnII
(A) Ammonical AgNO3 (p) The position of double bonds
(B) I2/NaOH (q) Presence of strongly acidic group
(C) NaHCO3 (r) Presence of acetylinic group
(D) Ozonolysis (s) Methyl Ketones
3.
Column– I Column –II
(A) 1-Butyne, 2-Butyne (p) neutral FeCl3
(B) Benzoic acid, Phenyl formate (q) I2/OH–
(C) 1-Butanol, 2-Butanol (r) NaHCO3
Pent-1-ene-2-ol, Pent-tene-3-ol (s) Tollen’s

4.
ColumnI (Mixture) ColumnII (Method for separation)
(A) o– and p–nitrophenols (p) Steam distillation
(B) Naphthalene and urea (q) Simple distillation
(C) Heptane and octane (r) Sublimation
(D) Benzene and nitrobenzene (s) Gas chromatography
5.
ColumnI ColumnII
(A) O (p) Different colouration with Neutral
FeCl3
CH3C OH
(B) NO2 (q) Decolourization of Br2 water

O2N OH

NO2
(C) (r) Brisk effervescence with NaHCO3
SO3H
OH
(D) CH2=CHCH2CCH3 (s) Yellow ppt with I2/NaOH

O
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 30

6.
Column-I Column-II
(A) (p) I2/NaOH
NHCH3, H3C NH2
(B) CH3COCH2CHO, CH3COCH2COOH (r) Anhydrous ZnCl2/HCl
(C) HCOOH, HCHO (r) C6H5SO2Cl
(D) (s) NaHCO3
CH2OH, COCH3
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 31

 SUBJECTIVE TYPE
1. A sample, containing 0.45 g of an organic compound, gave on combustion 0.792 g of CO 2
and 0.324 g of H2O. Another 0.24 g of this substance was Kjeldahlized and the ammonia
evolved was observed in 50 ml of N/4 H 2SO4. The excess acid required 77 ml of 0.10 N
NaOH for complete neutralization. Calculate the empirical formula of the compound.

2. 0.1325 g of an organic substance gave 0.225 g of barium sulphate in Carius method of

estimation of sulphur. Calculate the percentage of sulphur.

3. 0.369 g of an organic compound having carbon, hydrogen and oxygen was subjected to
combustion by Liebig’s method. It gave 0.369 g of CO 2 and 0.189 g of H2O. Calculate the
% of elements in the compound.

4. 0.423 g of an organic compound gave on combustion of 43.2 ml of nitrogen measured at

19.5°C and 733.5 mm of pressure. Find the % of N in the compound aqueous tension at
19.5°C is 17.8 mm.

5. A Duma’s nitrogen analysis of a 5.72 mg sample of pphenylene diamine gave 1.31 ml of

nitrogen at 20° and 746 mm. The gas was collected over saturated aqueous KOH solution
(the vapour pressure of water is 6 mm). Calculate the percentage of nitrogen in the
compound.

6. A dibasic organic acid containing 26.66% of carbon and 2.22% of hydrogen, gave a silver
salt containing 71.05% of silver. What is the molecular formula of the acid? Give its
structural formula also.

7. A dibasic organic acid gave the following results on analysis, 0.2496 g of acid gave 0.3168
g of CO2 and 0.0864 g of H 2O. 0.1092 g of acid is exactly neutralized by 21 ml N/10–
NaOH. Calculate the molecular formula of the acid.

8. 0.177 g of a dibasic acid gave on combustion 0.2642 g CO 2 and 0.081 g H2O. 0.2988 g of
its silver salt left 0.1944 g of silver on ignition. Write structural formula of its possible
isomers. What experiment would you perform to assign it a definite formula?

9. An organic compound contains 69.4% C, 5.8% H. A sample of 0.303 g of this compound

was analyzed for nitrogen by Kjeldahl method. The ammonia evolved was absorbed in
50 ml of 0.05 M H2SO4. The excess acid required 25 ml of 0.1 M NaOH for neutralization.
Determine molecular formula of the compound, if its molecular mass is 121. Draw
possible structures of this compound.

10. 0.0663 g of an organic compound gave 0.0621 g of carbon dioxide and 0.0381 g of water.
0.0980 g of the same compound gave 0.4860 g of barium sulphate. In a vapour density
determination, 0.205 g of the substance displaced 52.6 ml of air over water at 293 K and
773 mm of Hg pressure. The vapour pressure of water is 17 mm of Hg at 293 K. What is
the molecular formula of the compound?
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 32

11. A sample of 0.22 g of a volatile compound containing carbon, hydrogen and chlorine
yielded 0.195 g CO2 and 0.0804 g water on combustion in oxygen. 0.120 g of the
compound occupied a volume of 37.24 ml at 105°C and 768 mm of Hg pressure. Calculate
the molecular formula of the compound.

12. 10.57 mg of an organic compound gave on combustion 1.08 ml of nitrogen, measured at

19.5°C and 733.5 mm of pressure. Find the percentage of the nitrogen in the compound.
Given: Vapour pressure of water at 19.5°C is 17.8 mm.

13. 6 mg of an organic compound containing phosphorus gave 11 mg of Mg 2P2O7 by the usual

analysis. Calculate the percentage of phosphorus in the compound.

14. The quantative analysis of a well known broad spectrum antibiotic says that it contains
C = 57.49%, H = 5.39%, N = 8.39%, S = 9.58%. If each molecule of the antibiotic
contains one atom of sulphur, deduce the molecular formula of the antibiotic.

15. A monoacid base contains 53.3% carbon, 15.5% hydrogen and 31.2% nitrogen. 1.0 g of
the chloroplatinate of the base gave 0.39 g of platinum. What is the molecular formula of
the base?
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 33

ANSWERS
 STRAIGHT OBJECTIVE TYPE
 O - Level
1. c 2. d 3. c 4. a 5. b
6. b 7. c 8. b 9. b 10. b
11. b 12. b 13. a 14. c 15. d
16. b 17. c 18. a 19. d 20. d

 I - Level
1. a 2. a 3. b 4. c 5. c
6. c 7. b 8. c 9. c 10. a

 E - Level
1. d 2. d 3. d 4. a 5. c
6. a 7. b 8. b 9. c 10. a
11. b 12. c 13. c 14. a 15. c

 LINKED COMPREHENSION TYPE

Paragraph-1
1. d 2. b 3. a 4. b
Paragraph-2
1. b 2. b 3. d 4. d 5. c
Paragraph-3
1. c 2. b 3. d
Paragraph-4
1. d 2. b 3. d 4. a 5. b

 MATRIX MATCH TYPE

1. A-s, B-r, C-p, D-q
2. A-r, B-s, C-q, D-p
3. A-s, B-r, C-q, D-p
4. A-p, B-r, C-s, D-q
5. A-p, s, B-p, r, C-q, p, r, D-q, s
6. A-r, B-p, s, C-s, D-p, q
 SUBJECTIVE TYPE
 FUNDAMENTALSPRACTICAL ORGANIC CHEMISTRY CH 34

1. C4H8N2O

2. 23.32%

3. C = 27.27%, H = 5.69% and O = 67.04%

4. N = 11.22%

5. N = 26%

H–O–C–C–O–H
6. C2H2O4, 7. C3H4O4
O O

8. Molecular formula: C4H6O4

Possible structures:
COOH
CH2 – COOH
CH3 – CH
CH2 – COOH COOH
Succinic acid Methyl malonic acid
Can be distinguished by decarboxylation.

9. Molecular formula = nC7H7NO = C7H7NO

Structure
O
CHO C – NH2
NH2

10. C2H6S2 11. C2H4Cl2

12. 11.22 % 13. 51.20

14. C16H18N2SO4 15. C2H7N