Chapter

Purification and
1 Elemental Analysis of
Organic Compounds

Purification of Organic Compounds

Purification of organic compounds can be done by
l Crystallisation Crystals obtained are in purest form of the impurity present in the
impure solid dissolves in the solvent and remains dissolved when solution is cooled.
l Sublimation Conversion of solid into vapours without formation of liquid is called
sublimation.
Sublimate Cool
Solid Vapour Solid

Compounds to be purified must have relatively high vapour pressure and the
impurities must have vapour pressure lower than the compounds to be purified.
l Distillation Liquids can be purified by distillation which is a process of vaporising
liquids and condensing the vapours as a distillate.
If liquid decomposes before boiling point, then distillation is done under reduced
pressure (when b.p. is lowered) as recovery of glycerol from spent lye.
If substance is immiscible with water steam distillation is preferred, as aniline
separated from water.
l Chromatographic Method It depends on difference in the partition coefficients
(K) of the components of a mixture between two immiscible phases mobile and
stationary. The substances being separated are transported with the mobile phase.
Cs
k=
Cm
where, Cs is the concentration of the substance in the stationary phase
and Cm in the mobile phase

Stationary phase (Adsorbent) Mobile phase (Eluent) Type

Solid Vapour Gas chromatography
Liquid Vapour Gas chromatography
Solid Liquid Adsorption chromatography column and TLC
Liquid Liquid Liquid-liquid Partition chromatography
690 Practice Book of Chemistry for JEE Main & Advanced

Halogens
Analysis of Elements
X (Cl, Br, I) AgX
(Qualitative) Atomic mass of X weight of Ag
Organic Compounds have carbon and hydrogen, other X% = 100
Molar mass of AgX w
elements X (Cl, Br, I), S, N may be present
CuO,
35.5 weight of AgCl 100
e.g., Cl% =
Organic compound CO2 + H 2O 143.5 w
CO2 turns lime water milky indicating presence of
carbon Molar Mass of Determination
H 2O turns anhydrous CuSO4 (white) blue due to the w = weight of organic compound
formation of hydrated CuSO4 H 2O. This indicates
presence of hydrogen. W = weight of solvent
Presence of X, N, S, etc., is confirmed by Lassaignes m = molar mass of organic compound
method, using sodium extract.
Cryoscopic method (based on depression in freezing
point T f )
FeSO 4 HCl
l Na + C + N NaCN Na[Fe(CN)6 ] 1000K f w
123 m=
T f W
N-present FeCl
3
K f = Molal depression constant

Fe[Fe(CN)6 ]
Prussian blue Ebulliscopic method (based on elevation in boiling point)
1000 K b w
Na + C + N + S NaCNS
3
NaCl
FeCl m=
Tb W
l
14243
N, S both
present + [Fe(CNS)]Cl2 K b = molal elevation constant
Red Silver salt method (for organic acid)
AgNO3
l Na + X NaX Yellow ppt RCOOH RCOOAg Ag
Partially soluble in
AgNO3 w1 108 g
NH3 (Br2 ) w2
AgNO3
White ppt E(Eq. wt. of silver salt) w1
=
soluble in Yellow ppt Eq. wt. of silver w2
NH3 (Cl) insoluble in NH3 (I)
E w
l Quantitative estimation Weight of organic = 1
108 w2
compound = w g
Carbon 108w1
E=
12 100 weight of CO2 w2
C CO2 C% =
12 g 44 g 44 w RCOOH = RCOOAg Ag + H
2 100 weight of H 2O = E 108 + 1 = E 107
2H H 2O H% =
2g 18
18 g Thus, equivalent weight of acid = ( E 107)
Nitrogen Molar mass of acid = Basicity ( E 107)
N NH3 Platinum salt method (for organic bases)
14 17
(neutralised by V1 mL of N1 HCl)
2HCl PtCl 4
NH3 N 1000 mL of 1 N HCl 2B 2B 2HCl B2H 2PtCl6 Pt
1.4N 1V1 B H 2PtCl6 Pt
N% = (kjeldahls method) 1242
w 43 123
2B + 410 195
2N N2 w1 g w2
28 g
22400 mL
Molar mass of platinum salt w1
V mL =
Atomic mass of platinum w2
28 V 100
N% = (Dumas method)
22400 w
Purification and Elemental Analysis of Organic Compounds 691

2B + 410 w1 Example Molar mass of an organic compound

=
195 w2 = 62 g mol1
1 195w1 C = 20%
B= 410
2 w2 H = 6.67%
where, B is the equivalent weight of base. N = 46.67%
Victor Meyer Method O = 26.66%
wRT
m= Derive Molecular Formula
pV
Elements Percentage % / atomic mass Ratio
where, V is the volume of vapour in litre collected at
pressure p atm and temperature. T K from w gram solute 20
C 20.00 = 1.66 1
12
( R = 0.0821 L atm mol 1 1
K )
6.67
H 6.67 = 6.67 4
1
Molecular Formula Determination 46.67
O 46.67 = 3.33 2
Simplest ratio 14
Elements Percentage Mole ratio r 26.66
(r/smallest value of r)
N 26.66 = 1.66 1
16
x
C x
12 Empirical formula = CH 4N 2O
H y
y Empirical formula weight = 60
1
Molar mass = 60 g mol1
z
O z Molar mass 60
16 = =1
w Empirical formula weight 60
N w
14 Thus, molecular formula = (CH 4N 2O)1
= CH 4N 2O
Format I MCQs with only ONE Correct Option
1. Prussian blue can be represented as 8. Automatic estimation of elements in organic
Fe [Fe(CN) 6] compound is done by
(a) ENTanalyser (b) CHNanalyser
x y (c) MRIanalyser (d) X-rayanalyser
Oxidation numbers of Fe atoms (indicated by x and y) 9. Phosphorus is estimated as
are (a) Mg2 P2O7 (b) Na3 PO 4 (c) P2O3 (d) P2O 5
(a) 2, 2 (b) 2, 3
(c) 3, 2 (d) 3, 3 10. CH3NH2 changes to CH3OH on reaction with HNO2 .
There is
2. In the detection of N and S both in the compound by
(a) increase in % of carbon
Lassaigne fusion test, blood red colour is due to the
(b) decrease in % of carbon
formation of
(c) increase in % of hydrogen
(a) [Fe(CNS)]+ (b) [Fe(CNS)2 ]+ (d) no change in % of carbon
(c) [Fe(CNS)3 ] (d) [Fe(CNS)]2+
11. Hydrocarbon X contains 3 g carbon per gram of
3. Sulphur is converted into Na 2S in Lassaigne fusion hydrogen. Simplest formula of the hydrocarbon X is
test. Na 2S can be detected by (a) CH (b) CH2 (c) CH3 (d) CH4
I. CH3COOH; II. (CH3COO)2 Pb, 12. Which has maximum percentage of chlorine?
III. Na2 [Fe(CN)5 NO] (a) C 6H6Cl6 (b) CH3Cl
Correct codes are (c) C 6H5Cl (d) C2 H4Cl2
(a) I, II (b) II, III
(c) I, III (d) III only 13. Which is not related to C 2H 4O2 in any respect?
(a) CH2O (b) CH4 N2O
4. When CO2 is passed into lime water, solution turns
(c) C 4 H4O 4 (d) C 4 H8O 4
milky due to formation of I but milkyness disappears
due to the formation of II. I and II are 14. Percentage of carbon increases when CH3CH2OH
(a) CaCO3 , Ca(HCO3 )2 (b) Ca(HCO3 )2 , CaCO3 changes to
(c) Ca(OH)2 , CaCO3 (d) CaCO3 , Ca(OH)2 (a) CH3CHO (b) CH3COOH
(c) CO2 (d) In all cases
5. Detection of phosphorus in the compound can be
done by its conversion into phosphate. Reagent to 15. 10 mL of a hydrocarbon on complete combustion
identify phosphate ion is gave 30 mL of CO2 and 20 mL of H2O. Molecular
(a) sodium nitroprusside formula of the hydrocarbon is
(b) ammonium molybdate (a) C3 H6 (b) C3 H4 (c) C3 H2 (d) C3 H3
(c) potassium ferrocyanide
16. 0.63 g of a dibasic acid neutralises 100 mL of 0.1 N
(d) potassium ferricyanide
NaOH solution. Molar mass of dibasic acid is
6. In Carius method for the estimation of sulphur, (a) 63 (b) 126 (c) 31.5 (d) 12.6
precipitate is of
17. Which method is not correctly matched to determine
(a) BaSO 4 (b) Ba(HSO 4 )2
molecular weight?
(c) BaS (d) Ag2S
(a) Volatile substanceVictor Meyer
7. Carius method can be used for the estimation of (b) Organic baseplatinum salt
(a) sulphur (b) halogen (c) Organic acidsilver salt
(c) Both (a) and (b) (d) None of these (d) Non-electrolyte (like sucrose)Carius
Purification and Elemental Analysis of Organic Compounds 693

18. Silver salt of a diabasic acid has 27% silver. Molar 26. Haemoglobin is a chromoprotein having 4 atoms of
mass of dibasic acid is Fe in each molecule. Analysis showed 0.35% Fe.
(a) 400 (b) 200 (c) 293 (d) 586 Hence, its molecular weight is
(a) 64000 (b) 56000
19. Molar mass of acetic acid in benzene solvent
determined using cryoscopic method is just twice of (c) 12000 (d) 1200
the theoretical value. This is due to 27. An organic compound A contain 20% C, 46.66% N,
(a) its ionisation into CH3COO and H+ ions 6.66% H. It gave NH3 gas on heating with NaOH. A
(b) its association as dimer (CH3COOH)2 by van der can be
Waals forces (a) CH3CONH2 (b) C 6H5CONH2
(c) its association as dimer (CH3COOH)2 by H-bonding (c) NH2CONH2 (d) CH3 NHCONH2
(d) that its molar mass of acetic acid is just twice of 28. The sulphur content of cystine is 26.7 per cent. Given
theoretical value is not correct that cystine contains two sulphur atoms, molecular
20. Depression in freezing point of 1 molal urea solution weight of cystine is approximately
is 0.54. Depression in freezing point when 0.18 g of a (a) 120 (b) 240 (c) 100 (d) 60
non-electrolyte is added to 10 g water is 0.054. Thus, 29. Tyrosine is one of the amino acids present in protein.
molar mass of the non-electrolyte is Its content in protein is 0.22% and its molecular
(a) 180 g mol 1 (b) 90 g mol1 weight is 181 g mol 1. Lowest molecular weight of
(c) 18 g mol1 (d) 9.0 g mol1 protein is
(a) 18100 (b) 2200 (c) 82273 (d) 18132
21. Which of the organic compounds will give red colour
in Lassaigne test? 30. Platinum salt of an organic base contains 32.5%
S platinum. Hence, equivalent weight of the base is
(Pt = 195)
(a) NaCNS (b) NH2 C NH2 (a) 95 (b) 190
O (c) 600 (d) 300
(c) NH2CNH2 (d) HO SO3Na 31. RMgBr + H2O RH (g). Gas occupies 1.4 L
per g of RH at STP. Hence, RMgBr is
HNO3 / AgNO3 (a) CH3CH2 MgBr (b) C 6H5MgBr
22. Organic compound A white ppt. (c) CH3CH2CH2 MgBr (d) CH3 MgBr
can be due to

32. RN2Cl RCl + N2 , 1 g of A gave 0.2 g of B.
A Cu B
(a) NH4Cl (b) Cl
Hence, A is
Cl (a) CH3CH2 N2Cl (b) C 6H5N2Cl
(c) CH3 N2Cl (d) None is correct
(c) Cl (d) CH3 33. Glycerol can be separated from spent-lye in soap
industry by
23. In the detection of nitrogen, blue/green colour is due (a) steam distillation
to the formation of Prussian blue. It is (b) fractional distillation
(c) distillation under reduced pressure
(a) NaFe III [Fe II (CN)6] (b) NaFe II [Fe III (CN)6]
(d) ordinary distillation
(c) Na 4[Fe(CN)6] (d) Na3 [Fe(CN)6]
34. Aniline (an aromatic base) is separated from
24. Which factor is most important in determining the water-aniline mixture by
chemistry of an organic molecule?
(a) fractional distillation
(a) The melting point (b) steam distillation
(b) The functional group (c) distillation under reduced pressure
(c) The number of branches in the carbon chain (d) None of the above
(d) The number of carbon-hydrogen bonds
35. Steam distillation is based on the fact that
25. 6 g of the organic compound on heating with NaOH vaporisation of organic liquid takes place at
gave NH3 which is neutralised by 200 mL of 1 N
(a) lower temperature than its boiling point
HCl. Percentage of nitrogen is
(b) higher temperature than its boiling point
(a) 12% (b) 60% (c) its boiling point
(c) 46.67% (d) 26.67%
(d) water and organic liquid both undergo distillation
694 Practice Book of Chemistry for JEE Main & Advanced

36. Naphthalene has some sand impurity. It can be 47. Steam distillation is useful for the purification of
purified by substances which
(a) sublimation (a) are insoluble in water
(b) steam distillation (b) are volatile in steam
(c) TLC (c) are associated with non-steam volatile impurities
(d) column chromatography (d) have all the above characteristics
37. Mixture of amino acids can be separated by 48. Chromatography technique is used for the separation
(a) sublimation of
(b) chromatography (a) small samples of mixtures
(c) distillation under steam (b) plant pigments
(d) distillation under reduced pressure (c) dyestuffs
38. Sprayer used in the detection of amino acids is (d) All of the above
(a) Iodine (b) Benedicts solution 49. Which of the following is not sublimate?
(c) Fehlings solution (d) Ninhydrin solution
(a) Naphthalene (b) Camphor
39. The relative adsorption of each component of the (c) Chlorine (d) Benzoic acid
mixture is expressed in terms of
50. A mixture of camphor and benzoic acid can be easily
(a) adsorption factor (b) retention factor
separated by
(c) co-factor (d) sorption factor
(a) sublimation
40. Adsorbent is made of in TLC. (b) extraction with solvent
(a) silica gel (b) alumina (c) fractional crystallisation
(c) Both (a) and (b) (d) None of these (d) chemical method
41. Partition coefficient of an organic compound ( A) is 20 51. A compound is decomposed at its boiling point. It
between ether and water. 5 g of ( A) in 50 mL water is can be purified by
shaken wih 50 mL ether. ( A) extracted into ether is (a) vacuum distillation (b) steam distillation
(a) 4.0 g (b) 4.2 g (c) fractional distillation (d) sublimation
(c) 4.6 g (d) 4.8 g
52. Azeotropic mixtures
42. Solubility of an organic compound is 10 g/100 mL (a) boil at different temperature
water at 20C and 60 g/100 mL water at 70C. 30 g of (b) are mixture of solids
an impure organic compound is dissolved in 50 mL (c) are constant boiling mixtures
water at 70C and cooled to 20C. Crystals formed (d) are immiscible liquids
weigh
(a) 5 g (b) 20 g 53. Absolute alcohol cannot be obtained by simple
(c) 25 g (d) 30 g fractional distillation because
(a) pure C2 H5OH is unstable
43. The most suitable method of separation of a 1 : 1 (b) C2 H5OH forms hydrogen bonds with water
mixture of ortho- and para-nitrophenol is (c) boiling point of C2 H5OH is very close to that of water
(a) sublimation (b) chromatography (d) constant boiling azeotropic mixture is formed with
(c) crystallisation (d) steam distillation water
44. Which of the following techniques is most suitable 54. In paper chromatography
for the identification of cyclohexanone from a (a) mobile phase is liquid and stationary phase is solid
mixture containing benzoic acid, cyclohexane and
(b) mobile phase is solid and stationary phase is liquid
cyclohexanone? (c) both phases are liquids
(a) Crystallisation (b) Infra-red spectroscopy (d) both phases are solids
(c) Sublimation (d) Evaporation
55. Mixture of benzene and chlorobenzene is separated
45. Which one of the following is not used for the by
purification of solid impurities? (a) sublimation (b) separating funnel
(a) Distillation (b) Sublimation (c) crystallisation (d) distillation
(c) Crystallisation (d) All of these
56. Dumas method involves the determination of
46. The process of distillation involves all of the nitrogen content in the organic coompound in the
following except form of
(a) change of state (b) boiling (a) NH3 (b) N2
(c) condensation (d) evaporation (c) NaCN (d) (NH4 )2 SO 4
Purification and Elemental Analysis of Organic Compounds 695

57. In which of the following, molar mass determined by 61. Which mixture can be separated by sublimation?
crysocopic method is different from the normal (a) Naphthalene and urea (b) Iodine and urea
value? (c) Both (a) & (b) (d) None of the above
(a) Urea (b) Benzoic acid
(c) Glucose (d) Sucrose 62. Partition coefficient of succinic acid between ether
and water 2. 100 mL of water has 4 g succinic acid. It
58. Middletons fusion method uses is to be extracted into ether. Select the correct
(a) zinc
statement(s).
(b) sodium carbonate
(c) sodium metal (a) 66.66% acid is extracted if 100 mL of ether is used at
(d) mixture of zinc and sodium carbonate one time
(b) 75.00% acid is extracted if 100 mL of ether is used in
59. Adsorption chromatography has
Absorbent Eluent two parts of 50 mL each
(a) Solid Liquid (c) 80.50% acid is extracted if 100 mL of ether is used in
(b) Liquid Solid four parts of 25 mL each
(c) Solid Solid (d) All of the above are correct statements
(d) Liquid Liquid
63. A gaseous hydrocarbon gives upon combustion
60. In Dumas method of estimation of nitrogen, 0.35 g of 0.72 g of water and 3.08 g of CO2 . The empirical
an organic compound gave 55 mL of N2 collected at formula of the hydrocarbon is [JEE Main 2013]
300 K and 715 mm pressure (aqueous tension of water
is 15 mm). Percentage of nitrogen in the compound is (a) C2 H4 (b) C3 H4
(a) 14.45 (b) 15.45 (c) 16.45 (d) 17.45 (c) C 6H5 (d) C7 H8

Format II Comprehension Based MCQs

Example 1 Read the following passage and answer the formed as TLC plate on which solution of the mixture is placed
questions given thereafter. in the form of a spot about 2 cm above one end of the TLC plate.
In the identification of organic compounds, preliminary This treated TLC plate is placed in a closed jar having a solvent.
investigation includes detection of specific elements like As the solvent moves up the plate, individual components
nitrogen, sulphur and halogens. Research scholar A as well as move up along the plate to different distances depending on the
Research scholar B prepared sodium extract for the detection of degree of adsorption and separation takes place. Rf , retention
nitrogen (as they were told). In analysis there was red colour factor, which gives relative adsorption of each component in
formation for the compound of scholar A and blue colour for the mixture is defined by equation.
the compound of scholar B. Further analysis indicated 36.84% distance moved by the spot centre from the base line
Rf =
nitrogen in A (molar mass 76 g mol1) and 46.67% nitrogen in B distance moved by the solvent from the base line
(molar mass 60 g mol1) Lid
1. Elements in the compound analysed by A could be Solvent
front
(a) C, N, S (b) C, N
(c) C, N, Cl (d) C, N, O Base line Start Start
2. Elements in the compound analysed by B could be
(a) C, N, S (b) C, N
(a) Solvent (c)
(c) C, N, Cl (d) C, N, Br TLC before (b) TLC after
development development of development
3. Red colour obtained by A can be due to the formation of TLC plate
(a) Fe(OH)3 (b) Fe(CNS)3
(c) [Fe(CNS)2 ]+ (d) [Fe(CNS)]2+ Read the above passage and answer the questions at the end of it.
1. R f value does not depend on
4. Blue colour in B can be due to the formation of (a) type of plate (b) eluent
(a) Fe[Fe(CN)6] (b) Fe[Fe(CN)6]+ (c) temperature (d) pressure
(c) Fe[Fe(CN)6]2 (d) Fe[Fe(CN)6]2+ 2. Some of the spots in TLC analysis are colourless. In
Example 2 Thin-Layer Chromatography (TLC) case of amino acids colourless spots can be made
visible by
As the name implies, adsorbent is the thin layer of silica gel or
(a) ninhydrin (b) sulphuric acid
alumina spread over a glass plate of suitable size and plate thus
(c) anthraquinone (d) quinol
696 Practice Book of Chemistry for JEE Main & Advanced

3. R f values of A and B are 0.65 and 0.42 respectively. 7. To sodium fusion extract, Cl2 water and CCl 4 were
Which of these will elute first? added and shaken well. There is violet colour in the
(a) A (b) B lower part (organic layer). This indicates the
(c) Equally (d) Cannot be decided presence of
(a) bromine (b) iodine
Example 3 Read the following passage and answer the (c) chlorine (d) bromine and iodine
questions given at the end of it. 8. Sulphur is converted into S2 on fusion with sodium
Bonding organic compounds are generally covalent. Therefore, sulphide can be detected by
like inorganic compounds, no direct method is available for the (a) lead acetatewhen black precipitate is formed
detection of elements. In sodium-fusion method covalent (b) sodium nitroprusside when purple colour is formed
bonds of hetro atoms are broken by heating of organic (c) Both (a) and (b)
compounds with sodium metal. This results in the formation of (d) None of the above
inorganic ions involving these elements; these ions can in turn
be readily identified by the inorganic qualitative methods. Example 4 A mixture contains the three compounds shown
1. Detection of elements in organic compound is done in the table below :
using sodium-fusion method which is also called
Solubility (g/100 mL)
(a) Middletons fusion method
(b) Lassaigne fusion method in H2O in ether
(c) Hofmanns method COOH
(d) Hinsbergs method
2. Instead of sodium, one can also use following in the 1. 0.31 25.0
detection of elements in organic compounds
(a) NaHCO3 (b) Na2CO3 / Zn NO2
(c) NaHCO3 / Zn (d) CaCO3 NH2
3. Which of the organic compounds will give red colour
in Lassaigne test? 2. 0.11 5.5
S
NO2
(a) NaCNS (b) NH2 C NH2 OH
O
3. 3.02 106
(c) NH2CNH2 (d) H2N SO3Na
NO2
4. In the detection of nitrogen, blue/green colour is due
1. The mixture is dissolved in small amount of ether. To
to the formation of Prussian blue. It is
III II II III
this is added an equal volume of 0.01 M HCl(aq).
(a) NaFe [Fe (CN)6] (b) NaFe [Fe (CN)6] After shaking, two layers are formedan aqueous
(c) Na 4[Fe(CN)6] (d) Na3 [Fe(CN)6] layer and an ether layer. The layers are then
5. Red colour complex ion formed on adding FeCl3 to separated. Which of the compounds will be found in
SE, when N and S both are present in organic the aqueous layer?
compounds is (a) 1 only (b) 2 only (c) 3 only (d) 2 and 3
4 2+
(a) [Fe(CN)6] (b) [Fe(CNS)] 2. To the ether layer is added an equal volume of 0.01 M
(c) [Fe(CNS)2 ]+ (d) [Fe(CN)6]3 NaOH(aq). Again, two layers are formed. After
separating them, which of the compounds will be
6. Detection of chlorine is possible without preparing found in the aqueous layer?
sodium extract in (a) 1 only (b) 3 only
NO2 (c) 1 and 3 (d) 2 and 3
(a) O2N Cl (b) CHCl3 3. This aqueous layer is evaporated to dryness leaving a
solid residue of mass 0.31 g. Ten millilitres of
NO2 aqueous acid of pH 3 are added. After stirring, the
residue is smaller. What is the identity of the
(c) CH2Cl (d) CH2 CHCH2Cl residue?
(a) 1 only (b) 2 only
(c) 3 only (d) 1 and 3
Purification and Elemental Analysis of Organic Compounds 697

Format III Matrix Matching

1. Match the element (in Column I) with the method 5. Match the compounds in Column I with their
(in Column II) used to determine its percentage. characteristic test(s)/reaction(s) given in Column II.

Column I (Element) Column II (Method) Column I (Compound) Column II (Tests)

A. Nitrogen 1. Carius method
A. H2NNH3Cl
s 1. Sodium-fusion
B. Sulphur 2. Dumas method extract of the
C. Carbon 3. Iodine method compound gives
Prussian blue colour
D. Oxygen 4. Leibigs combustion method with FeSO 4
E. Phosphorus 5. Ignition method
r s
NH3I
2. Match the compound (in Column I) with the reagent B. HO 2. Gives positive FeCl 3
used to test them (in Column II). COOH test

Column I (Compound) Column II (Reagent) 3. Gives white

r s
A. Na 2S 1. HNO 3 /AgNO 3 C. HO NH3Cl precipitate with
B. Na 3 [Fe(CN)6 ] 2. FeCl 3 AgNO 3
C. NaCNS 3. (CH3COO)2 Pb
r s
D. NaI 4. FeCl 2 D. O2N NHNH3Br 4. Reacts with
aldehydes to form
3. Match the organic substance (in Column I) with the NO2 the corresponding
method of determination of its molar mass hydrazone derivative
(in Column II).

Column I (Substance)
A. An organic acid
B. A base
C. Non-electrolyte
D. A volatile substance
Column II (Method) 6. Match the compound in Column I with the
1. Platinum-salt method characteristic tests in Column II.
2. Victor-Meyer method
Column II
3. Silver-salt method Column I (Compound) (Characteristic
4. Cryoscopic method tests)

NO2
4. Match the compound in Column I with the compond
obtained with sodium fusion test in Column II. O2N Cl 1. Gives white
A.
precipitate with
Column II AgNO 3 (aq )
NO2
(Compound
Column I (Compound)
obtained with
sodium fusion test)
B. HOH2C CH2Cl 2. Gives positive FeCl 3
test
A. H3C SO2NH2 1. [Fe(CNS)]2+ OH

O 3. Sodium fusion
2
extract of the
B. ClH2C SO3H 2. [Fe(CN)5 NO] C. Cl CNH2 compound gives
Prussian blue colour
CH2OH with FeCl 3
O

C. NH2 C NH2 3. FeIII [FeII (CN)6 ]
D. H2N OH 4. Gives red colour
with ceric
Cl
D. 4. [Ag(NH3 )2 ]+ CH2CH2Cl ammonium nitrate
O2N
698 Practice Book of Chemistry for JEE Main & Advanced

Format IV Integer Answer Type

1. Total number of atoms in empirical formula of acetic 6. Deep violet colour formed when sodium extract of
acid is . the organic compound containing sulphur is treated
2. When one mole of acetone is completely combusted with sodium nitroprusside has structure
ratio of CO2 and H2O formed is Na 2 [Fe(CN) x NOS] where x is
3. An organic compound weighing 0.203 g gave on 7. Acetic acid is converted into silver salt and 4.64 g of
combustion 0.378 g of CO2 and 0.128 g of H2O. Thus, the silver salt on decomposition gave silver g.
percentage of hydrogen is .
8. Haemoglobin (molecular weight 64000) is a
4. Magnitude of charge on Prussian blue Fe[Fe(CN) 6] is chromoprotein having x atoms of Fe in each
5. An organic compound weighing x g containing molecule. Analysis showed 0.35% Fe. Thus, x is .
46.67% nitrogen on heating with NaOH gave NH3
which is neutralised by 200 mL of 1 N HCl. Thus, x is

Check your Solutions

Format I MCQs with only ONE Correct Option 11. (d) Total amount = 3 + 1 = 4 g
moles ratio
1. (c) Fe[Fe(CN)6 ]
Prussian blue is formed when Fe 3+
salts react with % of C = 75% 6.25 1
[FeII (CN)6 ]4 % of H = 25% 25.0 4
Fe 3 + + [Fe(CN)6 ]4 FeIII [FeII (CN)6 ] Thus, formula is CH 4 .
35.5 100
Thus, x=3 12. (a) (a) C 6H 6Cl 6 (CHCl)6 Cl % =
48.5
y =2
31.5 100
2. (d) Sodium extract has = NaCNS (b) CH 3Cl Cl % =
50.5
FeCl 3 + NaCNS [Fe(CNS)]Cl 2 + NaCl 35.5 100
(c) C 6H 5Cl Cl % =
3. (b) Na 2S + (CH 3COO)2 Pb PbS + 2CH 3COONa 112.5
black 35.5 100
(d) C 2H 4Cl 2 (CH 2Cl)2 Cl % =
Na 2S + Na 2 [Fe(CN)5 NO] Na 4 [Fe(CN)5 NOS] 49.5
violet -purple 1
Cl %
4. (a) Ca(OH)2 + CO 2 CaCO 3 + H 2O Denominator (which is minimum in (a))
milky (I)
13. (c) (a) CH 2O C 2H 4O 2
CaCO 3 + H 2O + CO 2 Ca(HCO 3 )2
soluble (II)
(b) CH 4N 2O, molar mass (60)
C 2H 4O 2 , molar mass (60)
5. (b) Na 3PO 4 + 12(NH 4 )2 MoO 4 + 21HNO 3
(c) C 4H 4O 2 is not related to molar mass and also not to
(NH 4 )3 PO 4 12MoO 3 + 21NH 4NO 3 + 3NaNO 3 + 12H 2O formula
yellow ppt
(d) C 4H 8O 4 (C 2H 4O 2 )2
HNO BaCl 24 100
3
6. (a) S 2
H 2SO 4 BaSO 4 14. (a) (a) CH 3CH 2OH = = 52.17
46
24 100
7. (c) 8. (b) (b) CH 3CHO = = 54.54 (increases)
44
Mg 24 100
9. (a) PO 3
4 Mg 3 (PO 4 )2 Mg 2P2O 7 (c) CH 3COOH = = 40%
60
10. (b) CH 3NH 2 CH 3OH 12 100 24 100
(d) CO 2 = = = 27.17%
Molar mass = 31 Molar mass = 32 44 88
= 38.71% C% = 37.5%
Purification and Elemental Analysis of Organic Compounds 699

y y
Percentage of N =
1.4 NV
15. (b) C xH y + x + O 2 xCO 2 + H 2O 25. (c)
4 2 y w (compound)
x
1 mL
2 1.4 1 200
=
10 x = 30, 6
10 y = 46.67%
= 20
2 26. (a) When 0.35 g Fe = molar mass is 100
x = 3, 100 4 56
4 56 g Fe =
y =4 0.35
16. (b) Equivalent of dibasic acid = equivalent of NaOH = 64000
0.63 100 0.1 27. (c)
= % Moles Ratio Empirical formula
E 1000
C 20 1.66 1
E = 63 H 6.66 6.66 4
Molar mass = 63 2 = 126 g mol 1 CH4N2O
N 46.66 3.33 2
17. (d) O 26.67 1.66 1
Equivalent weight of silver salt Weight of silver salt NaOH/
18. (d) = A NH 3 , thus (CONH 2 ) group hence A is
Equivalent weight of silver Weight of silver
E 100 NH 2CONH 2
=
108 27 28. (b) Let molar mass of compound = 100
E = 400 Sulphur atom = 26.7%
Equivalent weight of acid = 400 107 = 283 When 26.7 g sulphur, molar mass = 100 g mol 1
Molar mass = 283 2 = 586 100 64
When 64 g sulphur, molar mass =
O - - -H O 26.7
19. (c) CH 3 C CCH 3 = 239.7
O H - - -O
29. (c) When molar mass is 100 then protein content is 0.22%
20. (a) Tf = molality K f 100
Molar mass of protein = 181
0.54 = 1 K f 0.22
K f = 0.54 molal 1 = 82273
100 K f w(solute) 30. (a) Platinum salt of a base is H 2B2PtCl 6
Also Tf =
m(solute) W(solvent) 2 B + H 2PtCl 6 H 2B2PtCl 6 Pt
1000 0.54 0.18 (410 + 2 B) 195
0.054 =
m 10 (2 B + 410) molar mass of platinum salt 100
=
m = 180 g mol 1 (195) molar mass of platinum 32.5
B = 95
21. (b) If NaCNS is formed in sodium extract then red colour is
formed. 31. (d) H 2O decomposes RMgBr forming RH
NaCNS + FeCl 3 [Fe(CNS)]Cl 2 + NaCl 1.4 L of RH at STP = 1 g
red 22.4
22.4 L of RH at STP = = 16 g
(a) Inorganic salt 1.4
Thus, RH is CH 4 .

s
22. (b) Cl + Cl Hence, RMgBr is CH 3MgBr.

Allylic carbocation
32. (b) RN 2Cl RCN + N 2
( R + 28 + 35.5) Cu 28 g
(resonance stabilised)
R + 63.5 1
Cl + Ag+ AgCl =
28 0.2
white ppt.
R = 76.5 77
(a) Also gives white ppt. but it is inorganic salt.
RN 2Cl is C 6H 5N 2Cl
23. (a) Prussian blue colour is formed.
33. (c) 34. (b) 35. (a) 36. (a) 37. (b)
Na 4 [Fe(CN)6 ]+ FeCl 3 3NaCl + NaFeIII [FeII (CN)6 ]
38. (d) 39. (b) 40. (c)
24. (b)
41. (d) Let A extracted into ether = x g
700 Practice Book of Chemistry for JEE Main & Advanced

A left in water = (5 x ) g T1 p2V2 273 700 55

V1 = = = 46.09 mL
5 x T2 p1 300 760
conc. of A in water =
50 28 46.09 100
Thus, N% = = 16.45
x 22400 0.35
conc. of A in ether =
50
61. (c) 62. (d) 63. (d)
x
CA (ether) 50 x
Given, = 20 = =
CA (water) 5 x 5 x Format II Comprehension Based MCQs
50
x = 4.8 g Ex. 1 1. (a) 2. (b) 3. (d) 4. (a)
Ex. 2 1. (d) 2. (a) 3. (b)
42. (c) Organic compound solution has been cooled to 20C.
Ex. 3 1. (b) 2. (b) 3. (b,d) 4. (a) 5. (b)
100 mL H 2O can dissolve = 10 g
50 mL H 2O can dissolve = 5 g 6. (a,c,d) 7. (b) 8. (c)
Solute taken = 30 g Ex. 4 1. (b) 2. (b) 3. (b)
Hence, solute crystallised = 25 g
43. (d) 44. (b) 45. (a) 46. (a) 47. (d) Format III Matrix Matching
48. (d) 49. (c) 50. (d) 51. (a) 52. (c) 1. A(2); B(1); C(4); D(3); (E)5
53. (d) 54. (a) 2. A(3); B(4); C(2); D(1);
55. (d) They differ in boiling point. 3. A(3); B(1); C(4); D(2)
56. (b) 4. A(1,3); B(1,2); C(3,4); D(1,2,3)
57. (b) Dimer is formed due to intermolecular H-bonding. 5. A(3,4); B(1,2); C(1,2,3); D(1,4)
Molar mass is twice the normal value. 6. A(1); B(2,4); C(3); D(3,4)
58. (d) 59. (a)
60. (c) RNH 2 + HNO 2 N 2 + H 2O Format IV Integer Answer Type
123
22400 mL at NTP
28 g
Actual pressure = 715 15 = 700 mm Questions 1 2 3 4 5 6 7 8
p1V1 p2V2 Answers 4 1 7 1 6 5 3 4
=
T1 T2
STP given