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 group
(iv) Qualitative elemental analysis

5.1 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.

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
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  Na 4 [Fe(CN)6 ]
Sodium ferrocyanide

3Na4[Fe(CN)6] + 4FeCl3  Fe 4 [Fe(CN)6 ]3  12NaCl

ferricferrocyanide
(prussian blue)

An intense blue colouration is produced due to the formation of Prussian blue.

Diazo compounds (– N = N –) do not give test of nitrogen.
(ii) For Sulphur
(a) Na2S + Na2[Fe(CN)5NO]  Na 4 [Fe(CN)5 NOS]
sodium sulpho nitroprusside
(violet colour)

(b) Na2S + (CH3COO)2Pb  PbS  2CH 3 COONa

lead sulphide
(black)

(iii) For halogens

(a) NaCN + HNO3  NaNO3 + HCN
NaCl + AgNO3  AgCl   NaNO 3
Curdy white

NaBr + AgNO3  AgBr   NaNO 3

pale yellow

NaI + AgNO3  AgI   NaNO 3

bright yellow

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  Yelow or brown layer
2NaI + Cl2  2NaCl + I2
CHCl3 + I2  Violet layer
(iv) For nitrogen and sulphur: (when both are present)
Na
(a) C + N + S 
 NaCNS
 3NaCNS + FeCl3  Fe(CNS)3  3NaCl
ferric thiocyanate
(red colour)

(b) NaCNS + HCl  HCNS  NaCl

thiocyanic acid

4HCNS + Co(NO3)2  H 2 [Co(SCN)4 ]  2HNO 3

cobalti  thiocyanic acid
(blue)

Beilstein’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, nitrogen compound urea also imparts green colour to
the flame.
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
28 volume of Nitrogen at NTP evolved
Percentage of nitrogen =   100 (Duma’s
22400 weight of organic compound
method)
1.4  volume of acid  Normality of acid
= (Kjeldal’s method)
weight of organic compound
35.5 weight of AgCl formed
Percentage of chlorine =   100
143.5 weight of organic compound
80 weight of AgBr formed
Percentage of bromine =   100
188 weight of organic compound
127 weight of AgI formed
Percentage of iodine =   100
235 weight of organic compound
32 weight of BaSO 4 formed
Percentage of sulphur =   100
233 weight of organic compound
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  195 
Molecular weight of acid = Basicity ×   107 
 weight of silver 
 1  weight of platinum salt  195 
Molecular weight of base =  acidity    410 
2  weight of platinium 
Molecular weight = 2 × Vapour density
2  weight of compound  22400
Molecular weight =
volume of vapour given by substance at NTP
100  K f  weight of substance
Molecular weight =
Tf  weight of solvent
Where Kf = Molal freezing point
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

5.2 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.
H SO
4  RCOOR  H O
RCOOH + ROH 
2
2
Ester

(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.
 NH2 NHSO2H
Cl– Cl–
H2N+ C H2SO3 H2N+ C R–CHO
or SO2 gas HO3S
– 2H2O
NH2 NHSO2H

p-Rosaniline hydrochloride Schiff’s reagent (colourless)

NHSO2H
Cl–
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 + Cu 2 O 
Re d
(iii) Tollen’s test: Take about 5 ml of Toolen’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(NH 3 )2 ]OH  H 2 O  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
(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
bisulphate reagent.
NO2 NO2

R R
C = O + H2NHN NO2 C = NHN NO2
R R
R R OH
C = O + NaHSO3 C
R R SO3Na
(Bisulphite addition 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 (Fe3 +) 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.
(iii) Aniline Dye test: Dissolve a little aniline in dilute hydrochloric acid, cool in ice-cool 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–

0°C N  N + 2H2O
NH2 + HNO2 + HCl

Cl–

NaOH
NN+ OH N=N OH
–NaCl
–H2O
Benzenediazonium Phenol 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 H2SO4 C + H 2O
+

O = C –– O OH O = C –– O OH

O–Na+
2NaOH
C

O = C – O–Na+ O
(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] + 2C6 H 5 OH  [Ce(NO 3 )4 (C6 H 5 OH)2 ]  2NH 4 NO 3
phenol green or brown ppt.

(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 purple, 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.
Tauto-
NaNO2 + H2SO4 merize
HO HO N=O O N – OH
(green colour)

Phenol NaOH
O N OH O N O–Na+
H2SO4
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.
H SO
ROH + CH3COOH 
2 4  RCOOCH + H O
3 2

Alcohols give crystalline esters with 3, 5-dinitrobenzoyl chloride. These esters have
sharp melting points and can be used for testing a given alcohol.
NO2 NO2

R – OH + Cl – C R–O–C + HCl

O O
NO2 NO2

(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 distillate 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 ZnCl2 + 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 minute
then it is a secondary alcohol, while no cloudy precipitate even after long standing means it
is a primary alcohol.
   Cl
R – OH + ZnCl2 R  O  ZnCl 2 
 R 
 RCl
| 
H [Zn(OH)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.
RNH 2 + CHCl 3  3KOH  R  N  C  3KCl  3H 2 O
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 –)

(i) 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. H 2SO4. 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 ice-cold water and
then add cold dilute solution of sodium nitrite. Pour this cold solution into an alkaline 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  C6H5N2+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.

5.3 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 = Wg
Let the weight of water formed = xg (increase in weight of CaCl2 tube)
and let the weight of CO2 formed = yg (increase in weight of potach bulb)
Since 44 g of CO2 are formed from 12 g of carbon,
12
 yg of CO2 are formed from × yg of carbon
44
Since 18 g of water are formed from 2g of hydrogen
2 1
 xg of water are formed from × xg of hydrogen = xg of hydrogen
18 9
12
Now, Wg of the substance contains × yg of carbon
44
12  100y
 100 g of the substance contains g carbon
44  W
x
Again Wg 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
100x
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 = Wg
Volume of moist N2 = V cc
Room temperature = t°C
Barometric pressure = P mm
Aqueous tension at t°C = f mm
PV PV
We know, 1 1  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 = cc
760  (273  t)
Now, 22400 cc of N2 at NTP weigh 28 g
(P  f)  273  V  28(P  f)  273  V 
 at NTP weigh  760  22400(273  t)  g
760  (273  t)  
28(P  f)  273  V
Wg 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 = Wg 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 substance
0.014  N  V  100
=
W

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 Wg
Weight of the silver halide be yg
Atomic weight of halogen
Weight of halogen =  yg
Molecular weight of silver halide
Atomic weight of halogen 100
 Percentage of halogen = y
Molecular weight of silver halide W
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 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 = Wg
Weight of crucible + lid + silver salt = W1g
Weight of crucible + lid + residual silver = W2g
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
 (W  W)  108 
 Molecular weight of the acid =  1  107   n (where n = basicity of
 (W2  W) 
the acid)
Platinichloride 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 platonic chloride PtCl4 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.
X2g of Pt is left by X1g 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
B H PtCl 6  H 2 PtCl 6  X 2 
Equivalent weight of base B = 2 2 
2 2
If the acidity of the base is n, then
 X   n
Molecular weight of base =  1  195   410  
 X 2   2

Illustrations

Illustration 1
0.70 g of an organic compound was Kjeldahlised and the liberated ammonia was absorbed in 100
mL of N/10 H2SO4. After absorption the left over acid required 10 mL of N/5 NaOH for complete
neutralization. Calculate the percentage of nitrogen in the given compound.
Solution
10 mL N/5 NaOH  20 mL N/10 NaOH  20 mL N/10 H2SO4
Acid consumed = (100 – 20) mL of N/10 H 2SO4
Ans. N = 16%
Illustration 2
0.4 g of an organic compound was Kjeldahlised and ammonia evolved was absorbed into 50 mL
of seminormal solution of sulphuric acid. The residual acid solution was diluted with distilled
water and the volume was made to 150 mL. 20 mL of this diluted solution required 31 mL of 0.05
N NaOH for complete neutralization. Calculate the percentage of nitrogen in the compound.
Solution
20 mL diluted acid solution  31 mL of 0.05 N NaOH
31
150 mL diluted acid solution   150 mL 0.05 N NaOH
20
 232.5 mL 0.05 N H2SO4
 23.25 mL 0.5 N H2SO4
Ans. N = 46.81%
Illustration 3
In Kjeldahl method the gas evolved from 1.325 g sample of a fertilizer is passed into 50 mL of
0.2030 N H2SO4. 25.32 mL of 0.1980 N NaOH are required for the titration of the unused acid.
Calculate the percentage of nitrogen in the fertilizer.
Solution
25.32 mL 0.1980 N NaOH
 25.32 mL 0.1980 N H2SO4
 24.696 mL 0.2030 N H2SO4
 24.7 mL 0.2030 N H2SO4 Ans. N = 5.43%
Illustration 4
1.5 g of an organic compound in a quantitative determination of phosphorus gave 2.5090 g of
Mg2P2O7. Calculate the percentage of phosphorus in the compound.
Solution
62 Mass of Mg 2 P2 O7
Percentage of P =   100
222 Mass of org. compound
Ans. P = 46.7%
Illustration 5
A compound X gave the following results on combustion:
(i) 0.36 g gave 0.528 g CO2 and 0.324 g water.
(ii) In nitrogen estimation by Duma’s method, 0.295 g gave 56 mL of N 2 at NTP.
(iii) X is a monoacid base. Its platinichloride contains 37.39% platinum.
Find the molecular formula of the compound.
Solution
Molecular mass of the compound (acidity = 1)
1  100 
=  1   195  410   56
2  37.39 
Ans. C3H9N
Illustration 6
0.21 g of an organic substance containing C, H, O and N gave on combustion 0.462 g carbon
dioxide and 0.1215 g water. 0.104 g of it when distilled with NaOH evolved H 2SO4. Calculate the
empirical formula.
Solution
15 mL 0.05 N H2SO4  15 mL 0.05 N NH3  15 mL
1.4  0.05  15
0.05 N N2 Percentage of N2 =  10.09
0.104
Ans. C7H9NO2
Illustration 7
An organic liquid on analysis yielded the following results:
(i) The compound consisted carbon, hydrogen, nitrogen and sulphur.
(ii) On combustion, carbon and hydrogen were found to be 41.37% and 5.75% respectively.
(iii) On Kjeldahlising, ammonia obtained from 2.02 g of the substance was neutralized
completely by 23.2 mL N HCl
(iv) In the Carius estmation of sulphur, 0.1033 g of the substance resulted in the precipitation of
0.2772 g of BaSO4.
(v) 0.1015 g of the liquid when vaporized displaced 27.96 mL of dry air measured at 15°C and
750 mm pressure. Find the formula of the substance.
Solution
273 750
Volume of air at NTP = 27.96 ×   26.16 mL
288 760
22400  0.1015
The molecular mass of the substance =  86.9
26.16
Ans. Molecular formula = C3H5NS
Illustration 8
A substance on analysis gave the following data:
0.3112 g gave 0.4291 g of CO2 and 0.0585 g of water. 0.2293 g of the substance when heated with
nitric acid and silver nitrate gave 0.3969 g of bromide and chloride of silver. 0.2202 g of this
mixture of halides was found to contain 0.1435 g of silver. Find the empirical formula of the
original substance.
Solution
Let x g of AgCl be present in the 0.2202 g of the mixture of AgBr and AgCl
108x 108   0.2202  x 
So,   0.1435
143.5 188
x = 0.0954 g
Determine the amounts of AgCl and AgBr in 0.3969 g of the mixture.
x
AgCl =  0.3969  0.1720 g
0.2202
AgBr = (0.3969 – 0.1720) = 0.2249 g
35.5 0.1720
Thus, percentage of Cl =   100  18.55
143.5 0.2293
80 0.2249
and percentage of Br =   100  41.73
188 0.2293
Ans. C6H4ClBr
Illustration 9
15 mL of a gaseous hydrocarbon required 357 mL of air for complete combustion. The air
contains 21% by volume of oxygen. The volume of gaseous mixture after explosion and cooling
was found to be 327 mL. Calculate the molecular formula of the hydrocarbon.
Solution
357  21
Volume of oxygen used =  74.97  75 mL
100
Volume of residual nitrogen = (357 – 75) = 282 mL
 y y
C x H y   x   O 2 
 xCO 2  H 2 O
 4 2

 y  y
15 mL 15  x   15x Thus, 15x = 45 and 15  x    75
 4  4
Ans. C3H8
Illustration 10
An organic compound, CxH2yOy was burnt with twice the oxygen needed for complete
combustion to produce CO2 and H2O. The hot gases when cooled at 0°C and 1 atm pressure
measured 2.24 litre. The water collected during cooling was 0.9 g. the vapour pressure of pure
water at 20°C is 17.5 mm of Hg and it reduces by 0.104 mm when 50 g of organic compound is
dissolved in 1000 g of water. What is the molecular formula of the compound?
Solution

CxH2yOy + xO2 
 xCO2 + yH2O
Since 2x oxygen is taken, x is utilized and x is left unreacted.
After combustion, unreacted oxygen + carbon dioxide = 2.24 litre
or x + x = 2.24 litre
x = 1.12
= 0.05 mole CO2
Moles of water formed
0.9
y= =0.05 mole
18
Ratio x : y = 1 : 1
i.e. x = 1 and y=1
Empirical formula = CH2O
Mol. Mass is determined by applying Raoult’s law
Ans. Molecular formula C5H10O5

Practice Exercise
1. On complete combustion, 0.246 g of an organic compound gave 0.198g of carbon dioxide and
0.1014 g of water. Determine the percentage composition of carbon and hydrogen in the
compound.
2. In Dumas’ method for estimation of nitrogen, 0.3 g of an organic compound gave 50 mL of
nitrogen collected at 300 K temperature and 715 mm pressure. Calculate the percentage
composition of nitrogen in the compound. (Aqueous tension at 300 K = 15 mm)
3. During estimation of nitrogen present in an organic compound by Kjeldahl’s method, the
ammonia evolved from 0.5 g of the compound in Kjeldahl’s estimation of nitrogen,
neutralized 10 mL of 1 M H2SO4. Find out the percentage of nitrogen in the compound.
4. In Carius method of estimation of halogen, 0.15 g of an organic compound gave 0.12 g of
AgBr. Find out the percentage of bromine in the compound.
5. In sulphur estimation, 0.157 g of an organic compound gave 0.4813 g of barium sulphate.
What is the percentage of sulphur in the compound?

Answers1. 21.95% & 4.58% 2. 17.46% 3. 56% 4. 34.04% 5. 42.10%

 Miscellaneous Problems
Objective Type

Example 1
0.0833 mole of a carbohydrate of empirical formula CH2O contains 1.00 g of hydrogen. The molecular
formula of the carbohydrate is
(a) C5H10O5 (b) C3H4O3 (c) C12H22O11 (d) C6H12O6

Solution
1
1 mole of carbohydrate will contain g of hydrogen
0.0833
i.e., 12 g hydrogen
 The molecular formula of the compound will be C 6H12O6
 Ans. (d)

Example 2
The sulphur content of cystine is 26.7%. Given that cystine contains two sulphur atoms, molecular weight
of cystine is approximately
(a) 120 (b) 240 (c) 100 (d) 60

Solution
Atomic mass of sulphur = 32 amu
100
 Molecular mass of cystine =  64
26.7
= 239.7  240 amu.
 Ans. (b)

Example 3
An organic compound has carbon and hydrogen percentages in the ratio of 6 : 1, carbon and oxygen
percentages in the ratio of 3 : 4. The compound has the empirical formula
(a) CH2O (b) CH4O (c) C2H6O (d) CHO2

Solution
Ratio of percentage (C : H : O) = 6 : 1 : 8
6
C% =  100  40
15
1
H% =  100  6.67
15
O% = 53.33
Element % Atomic ratio Empirical ratio
C 40 40/12 = 3.33 3.33/3.33 = 1
H 6.67 6.67/1 = 6.67 6.67/3.33 = 2
O 53.33 53.33/16 = 3.33 3.33/3.33 = 1
 Empirical formula of the compound = CH 2O
 Ans. (a)

Example 4
Tyrosine is one of the amino acids present in protein. Its content in protein is 0.22% and its molecular
weight is 181g mol– 1. Lowest molecular mass of protein is
(a) 18100 (b) 2200 (c) 82273 (d) 18132

Solution
100
Molecular mass of protein =  181  82273
0.22
 Ans. (c)

Example 5
Analysis of an organic compound gave 74% C, 8.65% H and 17.3% N. What is the empirical formula of the
compound?
(a) C 5H 8N (b) C10H12N (c) C5H7N (d) C10H14N

Solution
Element % Atomic ratio Empirical ratio
C 74 74/12 = 6.16 6.16/1.235 = 5
H 8.65 8.65/1 = 8.65 8.65/1.235 = 7
N 17.3 17.3/14 = 1.235 1.235/1.235 = 1
 Empirical formula of the compound = C5H7N
 Ans. (c)

Example 6
The desiccants used for absorbing water during Liebig’s method for estimation of carbon and hydrogen are
(a) CaCl2 (b) Na2SO4 (c) MgSO4.7H2O (d) Mg(ClO4)2

Solution
Anhydrous CaCl2 and Mg(ClO4)2 are used as desiccants because they are efficient absorbent of water.
 Ans. (a)

Example 7
0.16 g of a dibasic organic acid required 25 cm3 of 0.1 M NaOH for complete neutralization. The molecular
mass of the acid is
(a) 45 (b) 90 (c) 64 (d) 128

SolutionN1V1 (acid) = N2V2 (base) = 0.1 × 25 = 2.5

W  1000 0.16  1000
E (acid) =   64 Molecular mass of acid = 2 × Equivalent mass =2×64=128Ans. (d)
NV 2.5
Example 8
9.9 g amide with molecular formula C4H5NxOy on heating with alkali liberated 1.7 g of ammonia. If the
percentage of oxygen is 33.33% then the ratio of ‘N’ and ‘O’ atoms in the compound is
(a) 1:1 (b) 1 : 2 (c) 2 : 3 (d) 3 : 2

Solution
Amide C4H5Nxoy will give x mol NH3.
9.9
 Molecular mass of amide =  17x  99x
1.7
14x
% Nitrogen in the amide =  100  14.14
99x
% Oxygen in the amide = 33.33
Ratio of number of atoms of ‘N’ and ‘O’
14.14 33.33
= :
14 16
=1:2
 Ans. (b)

Example 9
0.28 g of a nitrogenous compound was Kjeldahlised to produce 0.17 g of NH 3. The percentage of nitrogen in
the organic compound is
(a) 5 (b) 30 (c) 50 (d) 80

Solution
 14 
0.17 g NH3 will contain   0.17  g of nitrogen,
 17 
i.e., 0.14 g of nitrogen
Mass of nitrogen
% nitrogen =  100
Mass of compound
0.14
=  100  50%
0.28
 Ans. (c)

Subjective Type
Example 1
0.25 g of an organic compound on combustion gave 0.495 g of CO2 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,
P1V1 P2 V2

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
28  708  14.01  273  100
 100 g of the compound contains  9.60%
22400  760  292  0.159
Percentage of nitrogen = 96%
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 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 give  50.7
0.26
 Percentage of bromine = 50.7
Example 5
0.40 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
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
Calcualte 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
0.0975 596  410 186
Equivalent weight of the base =    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 CO 2 and
0.075 g of water and 0.20 g of the base gave 31.32 ml N2 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
(e) Determination of molecular weight:
The molecular weight of the base is given by

1 Weight % hexachloroplatinate salt 

B 195   410 
2 Weight % pt 
1  195  0.3  1
B  0.093  410   2 [629  410]  109.5
2
B = 109.5
Molecular weight 109.5
n  =1
Empirical weight 107

Hence, molecular formula = empirical formula = C 7H9N

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 CO2 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 = by each substance
22400 ml or 22.4 litres is occupied

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
 y y
Then C x H y   x   O 2  xCO 2  H 2 O
 4  2
 1 mole of CxHy gives = 0.05 a mol of CO2
 0.05 x = 0.05
0.05
 x 1
0.05
y y
Now, 1 mole of CxHy gives = mol of H2O  0.05 mol of CxHy will give = 0.05 mol of H2O
2 2
y
 0.05  0.10  y=4
2
16  1.12
Hence, the hydrocarbon is CH4 Weight of 1.12 litre CH4 at STP =  0.8 g
22.4
Also, CH4 + 2O2  CO2 + 2H2O
 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 & B.
Solution
Percentage of oxygen = 100 – (49.2 + 9.59 + 19.18) = 21.91
Elements Percentage composition Atomic weight Relative No. of atoms Simplest ratio
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
 Structural formula of acid B is C2H5COOH
Molecular formula of amide = C3H7NO
Hence structural formula of amide (A) is C2H5CONH2

*****
Exercise - I
Objective Type Questions
Multiple choice questions with ONE option correct
1. 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 yieded 0.35 g of barium sulphate is
(a) 14.52% (b) 16.52% (c) 18.52% (d) 19.52%
2. 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
3. Methyl ketones are usually characterized through
(a) Tollen’s test (b) Iodoform test (c) Schiff test (d) Benedict’s test
4. ClCH2COOH is heated with fuming nitric acid in the presence of AgNO3 in a Carius tube. After
filtration and washing a white precipitate is obtained. The precipitate is
(a) AgNO3 (b) Ag2O (c) AgCl (d) ClCH2COOAg
5. 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
6. 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
7. 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
8. 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
9. 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
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 N2 at 300 K and 715 mm pressure (Aquesous
tension = 15 mm)?
(a) 0.419 g (b) 0.149 g (c) 0.914 g (d) 0.941 g
11. The Prussian blue colour obtained during the test of nitrogen by Lassaigne’s test is due to the
formation of
(a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6]
(c) Fe(CN)3 (d) Na4[Fe(CN)5NOS]
12. A compound which does not give a positive test in Lassaigne’s test for nitrogen is
(a) Urea (b) Hydrazine
(c) Azobenzene (d) Phenyl hydrazine
13. Empirical formula of a compound is CH2O and its vapour density is 30. Molecular formula of the
compound is
(a) CH2O (b) C2H4O2 (c) C3H6O3 (d) C2H4O
14. Empirical formula of an organic compound is CH 2. Mass of one mole of it is 42 g. The molecular
formula of the compound is
(a) CH2 (b) C 2H 4 (c) C 3H 6 (d) C4H8
15. Insulin contains 3.4% sulphur. The minimum molecular mass of insulin is
(a) 940 (b) 560 (c) 470 (d) 350

Multiple choice questions with ONE or MORE THAN ONE option correct
1. Which of the following compounds may give blood red colouration while performing Lassaigne’s test
for nitrogen?
(a) (NH2)2CO (b) (NH2)2C = S (c) p-NMH2C6H4SO3H (d) C6H5SO3H
2. The desiccants used for absorbing water during Liebig’s method for estimation of carbon and
hydrogen are
(a) Anhydrous CaCl2 (b) Anhydrous Na2SO4 (c) MgSO4.7H2O (d) Mg(ClO4)2
3. The empirical formula of a compound is CH2. To which of the hydrocarbon series does it belong?
(a) Alkanes (b) Alkenes (c) Alkynes (d) Cycloalkanes
4. An organic compound contains about 52% carbon. It could be
(a) ethanol (b) dimethyl ether (c) acetic acid (d) phenol
5. Presence of halogen in a compound is tested by
(a) Iodoform test (b) Millon’s test (c) Silver nitrate test (d) Beilstein test
6. The weights of carbon, hydrogen and oxygen in n organic compound are in the ratio 6 : 1 : 8
respectively. The molecular formula of the compound may be
(a) CH2O (b) C2H4O2 (c) CH2O2 (d) C3H6O3
7. Which of the organic compounds will give white precipitate with AgNO 3?
(a) C6 H 5 NH 3 Cl  (b) NaCl
(c) C6H5Cl (d) 2,6,6,-Trinitrochlorobenzene
8. Select the organic compounds, which will give red colour in Lassaigne’s test?
O
||
(a) NaCNS (b) NH 2  C NH 2
S
||
(c) NH 2  C NH 2 (d) H2N SO3–Na+

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Exercise - II
Assertion & Reason, Comprehensive and Matching Type
Assertion and Reason
(a) If both A and R are true and R is the correct explanation of A.
(b) If both A and R are true but R is not the correct explanation of A
(c) If A is true but R is false.
(d) If A is false but R is true.
1. A : Lassaigne’s test can be used to detect nitrogen in hydrazine.
R: During fusion with sodium metal, nitrogen and carbon of the organic compound combine to
form sodium cyanide.
2. A : If sulphur and nitrogen are also present in organic compound along with halogen then AgNO 3
solution is added in acidified sodium fusion extract.
R: On acidification, NaCN and Na2S decmpose.
NaCN + HNO3  NaNO3 + HCN 
Na2S + 2HNO3  2NaNO3 + H2S 
3. A : Litmus is not used in Lassaigne’s test.
R : It generally forms covalent compounds.
4. A : In Victor Meyer’s method, vapour density is considered to be one-half of molecular weight.
R : Vapour density is other name of density.
5. A : Nitrogen cannot be estimated in nitrobenzene by Kjeldahl’s method.
R: Nitrobenzene evolves ammonia gas on acid treatment.

Passage Based Questions

Passage – I
Empirical formula of a substance gives the simplest whole number ratio between the atoms of the various
elements present in one molecule of the substance. Molecular formula on the other hand gives the actual
number of atoms present in one molecular of the substance.
Molecular formula = n × Empirical formula
Where n is a simple integer 1, 2, 3, ……, etc., given by the equation
Molecular mass of the compound
n=
Empiricalformula mass of the compound
Answer the following questions:
Select (a) if True and (b) if False
1. Empirical and molecular formula of a compound may be same
(a) True (b) False
2. Empirical formula of two different compounds can not be same
(a) True (b) False
3. If two compounds have the same empirical formula but different molecular formula, they have same
vapour density
(a) True (b) False
4. The two compounds having same empirical formula have same percentage composition
(a) True (b) False
5. Empirical formula of benzene is C2H2
(a) True (b) False
6. The compounds having same empirical formula must have same properties
(a) True (b) False
7. Cyclo alkanes and alkenes have same empirical formula
(a) True (b) False

Passage – II
Combustion of 0.42 g of a compound gave 0.924 g CO2 and 0.243 g H2O. Due to distillation of 0.208 g of
N
compound with NaOH, ammonia evolved required 30 mL of H2SO4 for complete neutralization.
20
Vapour density of the compound is 69.5.
Answer the following questions:
1. The compound has empirical formula
(a) C7H9O2N (b) C6H5NO2
O
||
(c) C3H7 – CONH2 (d) NH 2  C NH 2
2. Percentage composition of carbon in the compound is ………………
(a) 6.43 (b) 23.48 (c) 60 (d) 10.09
3. What is the percentage composition of nitrogen in the compound?
(a) 23.48 (b) 10.09 (c) 6.43 (d) 60
4. What is the percentage composition of hydrogen in the compound?
(a) 6.43 (b) 10.09 (c) 60 (d) 23.48
5. What is the value of ‘n’ for the given compound?
Molecular mass
where n=
Empirical formula mass
(a) 2 (b) 3 (c) 1 (d) 4
Matching Type Questions
1. Column I Column II
Property to be determined Method used for determination
(A) Molecular mass of a volatile organic solid (P) Silver salt method
(B) Molecular mass of a non-volatile organic solid (Q) Liebig method
(C) Estimation of chlorine in carbon tetrachloride (R) Platinichloride method
(D) Estimation of nitrogen in aniline (S) Victor Meyer’s method
(E) Equivalent mass of an organic acid (T) Depression in freezing point
(F) Equivalent mass of an organic base (U) Carius method
(G) Estimation of carbon and hydrogen in an (V) Kjeldahl’s method
organic compound
(a) A – P, B – Q, C – R, D – S, E – T, F – U, G – V (b) A – S, B – T, C – U, D – V, E – P, F – T, G –Q
(c) A – R, B – T, C – Q, D – U, E – S, F – V, G – P (d) A – V, B – P, C – S, D – R, E – U, F – Q, G – T

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Exercise - III
Subjective Type

1. 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.
2. A dibasic organic acid gave the following results on analysis, 0.2496 g of acid gave 0.3168 g of CO 2 and
0.0864 g of CO2 and 0.0864 g of H2O, 0.1092 g of acid is exactly neutralized by 21 ml N/10–NaOH.
Calculate the molecular formula of the acid.
3. In Kjeldahl method the gas evolved from 0.2476 g sample of protein is passed into 50 ml of HCl which
was in excess of the amount required for neutralization. A separate 25 ml sample of HCl required 21.15
ml NaOH to reach equivalence point. Calculate the percentage of nitrogen in protein.
4. 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 H 2SO4.. 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.
5. 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?
6. 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.
7. 10.57 mg of an organic compound gave an 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.
8. 6 mg of an organic compound containing phosphorus gave 11 mg of Mg2P2O7 by the usual analysis.
Calculate the percentage of phosphorus in the compound.
9. 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.
10. 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?

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Answers
Exercise - I
Only One Option is correct
1. (c) 2. (c) 3. (b) 4. (c) 5. (b)
6. (b) 7. (b) 8. (a) 9. (d) 10. (a)
11. (a) 12. (b) 13. (b) 14. (c) 15. (a)

More Than One Choice Correct

1. (b, c) 2. (a, d) 3. (b, d) 4. (a, b) 5. (c, d)
6. (a, b, d) 7. (a, d) 8. (c, d)

Exercise - II
Assertion and Reason
1. (d) 2. (a) 3. (a) 4. (c) 5. (c)

Passage – I
1. (a) 2. (b) 3. (b) 4. (a) 5. (b)
6. (b) 7. (a)
Passage – II
1. (a) 2. (c) 3. (b) 4. (a) 5. (c)

Matching Type Questions

1. (b)
Exercise - III
Subjective Type
1. C 2 H 2 O 4 , H  O  C  C O  H 2. C3H4O4 3. 16.7%
|| ||
O O

O
CHO C – NH2
NH2

4. Molecular formula = nC7H7NO = C7H7NO Structure:

5. C2H6S2 6. C2H4Cl2 7. 11.229 8. 51.20

9. C16H18N2SO4 10. C 2H 7N

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