2

MOLECULAR ANALYSIS OF.

ORGANIC COMPOUNDS

2.1 GENERAL delivery tube is immersed in lime water. The bulb of the
delivery tube contains anhydrous copper sulphate
In order to establish the correct structure of an organic (colourless). The mixture is heated very strongly. Carbon and
compound, it is necessary to know precisely its molecular hydrogen present in the organic compound are oxidised by
formula. The following steps are .involved jn the cupric oxide to carbon dioxide and water; relpectively
determination of the molecular formula of a compound. (Copper Oxide Test).
(i) Detection of elements (Qualitative analysis).
(ii) Estimation of elements (Quantitative analysis). C+2CUO ~ 2Cu+C0 2
(iii) The determination of molecular mass.
(iv) Calculation of empirical and molecular formula. H2 +CuO ~ Cu+H 20
2.2 DETECTION OF ELEMENTS Carbon dioxide turns' the lime water milky and water
(QUALITATIVE ANALYSIS) vapours turn anhydrous copper ,sulphate. blue .. Water vapours
condense on the cooler part of the tube.
Most of the organic compounds contain 2 to 5 different elements. Ca(OHh +C02 .---,---+ CaC0 3 + H 20
The principal elements present are: carbon, hydrogen and Milky
oxygen. Less commonly present elements are: nitrogen,
sulphur and halogens. In few organic compounds, phosphorus CuS04 + 5H 20. ---'---+ CuS04 ·5H 20
and metals may also be present. The order of abundance of (Colourless) (Blue)
Anhydrous Hydrated
these elements in organic compounds is given below:
Carbon -Always present If the substance under investigation is a volatile liquid or
Hydrogen -Nearly always present gas, the vapours are passed over heated copper oxide kept in
Oxygen -Generally present combustion tube and the gaseous products are tested as above.
Nitrogen, halogens, sulphur -Less commonly present If the substance under examination contains sulphur also,
Phosphorus and metals -Rarely present [Link] evolved are fust passed through an acidified-solution
of potassium dichromate which absorbs all the. sulphur
Detection of Carbon and Hydrogen dioxide and then through lime water which turns milky.
Carbon is always present in an organic compound and S +2CuO ---'---+ 2Cu +S02
hydrogen, too, is rarely absent However, the presence of these
K 2 Cr20 7 + H2 S04 + 3S02 ~ KZS04+Cr2(S04)3 + H 2 0 >
two elements is confIrmed by the given common test.
A small amount of dry organic compound mixed with [S02 like CO 2 turns lime water milky due to formation of
about eight times dry cupric oxide· is taken in a hard glass caS° 3 • .

tube. The glass tube is clamped and fItted with a delIvery tube Ca(0H)2 + S02 .---'---+ Caso l + H 20] ..
carrying a bulb in the horizontal length. The end of the

*Cupric oxide, CnO, is hygroscopic. It is always ignited before use as to ma1ce it completely dry.

"
 40 G.R.B. Organic Chemistry for Competitions.

Organic compounds (suppose to contain phosphorus) are Chemistry of the test: Lassaigne's filtrate consists of
heated with oxidising agents (like sodium peroxide, Na202)' sodium cyanide and sodium hydroxide.
The phosphorus present in the organic compound is oxidised
Na + C + N NaCN
to phosphate. '-----v----' Sodium cyanide
From organic
Detection of Nitrogen, Sulphur and Halogens compound
. These elelilentsare test~d,in ~-organic compound by 2Na + 2If20 ---7 2NaOH + H2
Lassaigne's t~[Link] organic compoimd (N, S or halogens) is Sodium hydroxide
fused with sodium metal as to convert these elements into When the filtrate is boiled with ferrous sulphate solution,
ionisabl~in()rgani<tsubS1{mces, i.e., 'nitrogen into sodium,. the following .reactions take place.
: -

cyanide: sulphtirintosodhun sulphide andhalogensirito ' FeSO" +2NaOH ---7 Fe(OHh + Na 2S0 4
sodium halides. .. . Ferrous hydroxide
(Green)
Na+C+N ~ NacN
Fe(OHh +6NaCN ---7 Na 4[Fe(CN)'6] +2NaOH
2Na+S ~ Na2S Sodium ferrocyanide
[Sodium
2Na + X 2 ~ 2NaX' (X may be Cl, Br or I) . hexacyanoferrate' (II)]
Note: .Sodium metal should be' in slight excess otherwise in At the same time some ferrous sulphate is converted to
compounds containing N and S together, sodium thiocyanate is ferric sulphate. This reacts with sodium ferrocyanide to form
. formed. With excess of sodiUm, the thiocyanate formed ferric ferrocyanide or iron (III) hexacyanoferrate (II) which
decomposes into cyanide a:ndsulphide.
gives prussian blue colour or precipitate.
Na + C + N + S ~ NaCNS
Sodium thiocyanate 3Na4[Fe(CN)6] + 2Fe2(S04)3 ~ Fe4[Fe(CN)6h + 6Na2S04
NaCNS + 2Na ~ NaCN + Na2S . Ferric ferrocyanide
(Prussian blue)
The cyanide, sulphide' or halide ions can be confirmed in In case ferric chloride (FeCI 3 ) is added, the following reac-
the aqueous solution by usual tests. The aqueous solution is tion occurs.
called Lassaigne's filtrate. .
4FecI3+3Na4[Fe(CN)6] ~ Fe4[Fe(CN)6h +12NaCI
Instead of sodium metal, mixture of sodium carbonate and
zinc can be used. It is called Middleton's fusion method. Note: (i) Sometimes when the amount of nitrogen present is small, the
Preparation or Lassalgne's filtrate: A small piece of . prussian blue is present in colloidal form and the solution
sodium of pea size is freshly cut and dried between the folds of looks I!reen.
(ii) When the alkaline solution is acidified with HCI, the yellow
filter paper. It is taken in a fusion tube (ignition tube) and
colourofferric chloride produced by the acid with ferric ions
heated gently. When it melts to a shining globule, the tube is '.
makes the blue colour to appear as green.
removed. from the flame and a small amount of organic
(iii) When the organic substance contains both N and S, sodium
compound (0.05 g of solid or 3-4 drops of liquid) is added to
thiocyanate is formed which gives a blood red colouration of
. the sodium. The tube is first gently heated till the reaction ferric sulphocyapide (or ferric thiocyanate) with ferric ions. .
ceases and then strongly till it is red hot. It is now plunged
directly into 10 to 15 mL of distilled water taken in a porcelain 3NaCNS + FeCI 3 ~ Fe(CNS)3 + 3NaCI
Ferric sulphocyanide
basin and crushed by the tip of the tongs. The contents are (Blood red in colour)
heated for five minutes and then filtered. The filtrate is known . (iv) This test fails in case of diazo compounds.
as Lassaigne's filtrate or sodium extract.
Organic compounds being covalentsnormally do not Detection of Sulphur
have ionisable groups, hence direct test is not possible. 1. Lassaigne's test: Sulphur is present in the sodium
Detection of Nitrogen extract in the· form of sodium sulphide.
2 mL ofLassaigne's filtrate (sodium extract) is taken in a S+2Na ~ Na2S
test tube and two or three drops of freshly prepared ferrous
sulphate solution are added. As the solution is alkaline (excess (When sulphur and nitrogen both are present, sodium
of sodium reacts with water to form sodium hydroxide), a thiocyanate is formed. Both are tested simultaneously with
green precipitate of ferrous hydroxide appears. The mixture is ferric chloride solution, when a blood red colouration
boiled for two minutes, cooled and acidified with, dilute appears).
sulphuric acid (H2S0 4 dissolves ferrous hydroxide). Sulphur is tested in the sodium extract in the following
Appearance of a green or prussian blue colour confirms the manner:
presence of nitrogen. Alternatively FeCl 3 and dilute HCI may (i) To a little of sodium extract, freshly prepared solution
be added. . of sodium nitroprusside is added; a deep violet colour
indicates the presence of sulphur.
Molecular Analysis of Organic Compounds 41

Na 2S + Na 2[Fe(NO)(CN)sJ ------7 Na 3[Fe(ONSNa)(CN)5) NaBr + AgN03 ------7 AgBr + NaN0 3

Sodium nitroprusside (Vioiet coloured complex) (Pale yellow ppt.)
Sodium thionitroprusside
The precipitate of AgBr is sparingly soluble in
or Na 4[Fe(CN)sNOS] ammonium hydroxide.
(Purple colour complex)
NaI + AgN03 ------7 Agi + NaN0 3
(ii) To another test portion of sodium extract, a few drops (Yellow ppt.)
of acetic acid and lead acetate are added. A black precipitate AgI is insoluble in ammonium hydroxide.
of lead sulphide is formed. 2. Chlorine water test for bromine and iodine: From
Na 2S + (CH 3COOh Pb ------7 PbS + 2CH 3COONa the colour of AgBr and AgI, it is difJicult to judge whether the
(Black ppt.) organic compound contains bromine or iodine. To confirm the
(iii) To a small portion of sodium extract, a few drops of presence of bromine or iodine, the above test is supplemented
acetic acid and cadmium acetate are added. Yellow precipitate by the chlorine water test (layer test).
of cadmium sulphide is formed. A small portion of sodium extract is acidified with dilute
HN0 3 or H 2S04 and then 1 mL of chloroform or carbon
Na 2S + (CH 3C00)zCd ------7 CdS +2CH 3COONa
(Yellow ppt.) tetrachloride is added. Now shake it vigorously with excess of
chlorine water. If chloroform layer becomes yellow or brown,
.2. Oxidation test: . Sulphur can also be tested by bromine is present and if violet, iodine· is present.
oxidation test. The organic compound is fused with fusion
mixture (a mixture of sodium carbonate and potassium 2NaBr +C1 2 ------7 2NaCI . + sr2
nitrate).. The sulphur, if present in the organic compound, is (Turns CSz layer orange)
oxidised to sodium sulphate. Br2 dissolves in CHCl 3 or CCl 4 giving yellow or brown
Na2C03 + S + 30 ------7 Na2S04 + CO2 colour (layer).
The fused mass is dissolved in water and the solution is 2NaI +C1 2 ------7 2NaCI +12
acidified with hydrochloric acid. Barium chloride solution is (Turns CSz layer violet)
. then added. The formation of a white precipitate indicates the 12 dissolves in CHCl 3 or CCl 4 giving violet colour (layer).
presence of sulphur. Note: The presence of NaCN or Na2S insodiurn .eXh-act ~~ not
Na2S04 + BaCl 2 ------7 BaS0 4 +2NaCl interfere in this test.
(White ppt.) 3. Beilstein test or copper wire test: The copper wire
Detection of Bah,gens is flattened at one end. The flattened end is heated in an
oxidising flame of the burner till it ceases to impart any green
1. Lassaigne's test: Chlorine, bromine and iodine are
or blue colour to the flame. A small quantity of organic
present in the sodium extract in the form of sodium chloride,
substance .is taken on the flattened end of the wire and
sodium bromide and sodium iodide, respectively. For the test
introduced in the flame. A green or blue colour of the flame
of halogens, it is necessary to remove sodium cyanide and
indicates the presence ofhalogen(s). The green or blue colour
sodium sulphide from the sodium extract if nitrogen and
is produced due to the interaction of halogen with copper to
sulphur are present. This is done by boiling the sodium extract
form volatile copper halides.
with concentrated nitric acid. .
Note: This test, though very sensitive, is not always reliable.
NaCN + HN0 3 ------7 NaN0 3 + HCN i Substances which do not contain halogens such as urea,
. Na2S + 2HN0 3 ------7 2NaN0 3 + H 2S i thiourea, pyridine, quinoline and purines, etc., also impart
colour to the flame. .
[lfNaCN and NaiS are not decomposed, white or black
precipitate of AgCN and Ag 2S respectively are formed with Detection of Phosphorus
silver nitrate solution,) The organic compound is fused with the fusion mixture
To the sodium extract (free from NaCN and Na2S), silver (sodium carbonate and potassium nitr<>te) or sodium peroxide.
nitrate solution is added after acidifying it with dilute nitric The phosphorus present in the organic compound is converted
acid. Appearance of white precipitate (AgCl) or pale yellow into sodium phosphate. The fused product is extracted with
precipitate (AgBr) or yellow precipitate (AgI) indicates the water and the aqueous solution obtained is boiled with
presence of chlorine, .bromine. or iodine in the organic concentrated nitric acid and ammonium molybdate. A yellow
compound, respectively. precipitate or colouration indicates the presence of
NaCI + AgN03 ------7 AgCI + NaN0 3 . phosphorus. The yellow precipitate is due to the furmation of
(White ppt.) ammonium phosphomoiybdate, (NH4) 3PO 4·12Mo0 3·
The . precipitate of AgCI dissolves in ammonium [P + Na202
Bo'l
1) Na3P04]
hydroxide.
3Na 2C0 3 +2P+50 ------7 2Na3P04+3C02

,.
 42 G.R.B. Organic Chemistry (or Competitions

Na3P04 +3HN0 3 ~ H 3 P0 4 +3NaN° 3 . 2 Y

Percentage of hydrogen = - x - x 100
H 3 P0 4 +12(NH4hMo04 +21HN0 3 ~ 18 W
(NH4hP04 . I 2MoO 3 +21NH 4N0 3 +12H 20 (b) C + 02
Ammonium phosphomolybdate . 12g
(Yellow ppt.)
44 g of CO 2 contain 12 g of~arbon
Detection or [Link]
x g of CO 2 will contain =
.
g44 x x g of carbon
There is no satisfactory qualitative method for the detection
of oxygen. However, its presence can be inferred indirectly. 12 x
Percentage of carbon = - x - x 100
(i) If the organic compound is heated alone in a dry test 44 W
tube in presence of nitrogen, the formation of water drops on
Liebig's method is most suitable in case of organic
cooler parts ofthe tube may indicate the presence of oxygen. compounds containing C, H and oxygen only. If, however, the
(ii) The presence of oxygen can be inferred by testing the organic compound contains nitrogen, halogens and sulphur
[Link] functional groups known to contain oxygen, e.g., also, some modifications are made. .
. hydroxyl (-OH), aldehydic (-CHO), carboxyl (-COOH),
1. Substances containing nitrogen: The oxidation of
and nitro (-NO 2), etc. nitrogen present in the organic compound occurs and oxides
2.3 ESTIMATION OF ELEMENTS of nitrogen (N 20' NO and N0 2) are formed. These oxides are
also absorbed by caustic potash solution along with CO 2, The
(QUANTITATIVE ANALYSIS) oxides of nitrogen are decomposed again into nitrogen by
After qualitative analysis of tflements, the next step in the placing a bright copper gauze roll near the exit end. Nitrogen
determination of molecular formula of an organic compouna is so produced is not absorbed by KOH solution;
the estimation of various elements by mass, i. e., finding the 4Cu+2N0 2 ~ 4CuO+N 2
percentage composition of the substance by mass. The various Cu+N 20 ~ CuO+N 2
methods commonly employed for the estimation of principal
elements are discussed below:
1. Substances containing halogens: Halogens present
in organic compounds form copper halides during
Estimation of Carbon and Hydrogen combustion. Copper halides are volatile and partly decompose
Carbon and hydrogen are estimated simultaneously by at high temperature forming free halogens. These halogens
Liebig's combustion method. and copper halides are absorbed in the absorption apparatus.
Principle: When a known mass of an organic This can be prevented by placing a bright silver gauze roll
compound is strongly heated with dry cupric oxide, carbon near the exit end. Non-volatile silver halides are formed.
and hydrogen present are quantitatively oxidised to carbon 2Ag+X2 ~ 2AgX
dioxide and water, respectively. The masses of carbon dioxide 2Ag+CuX 2 ~ 2AgX +Cu
and water thus formed are determined and the amounts of 3. Substances containing sulphur alone or sulphur
carbon and hydrogen in the original compound are calculated. and halogen: The sulphur present in the organic compound
A Y is oxidised to sulphur dioxide which is absorbed in potash
CxHy +(x+ yl4)02 ~ xC0 2 +-H 20 . bulbs. A layer of fused lead chromate is placed near the exit
Observations: 2 end. S02 reacts to produce nonvolatile lead sulphate.
(i) Let the mass of the organic compound be W g.
2PbCr0 4 ~ 2PbO+Cr203 +30
(ii) Increase in the mass QfU-tube = yg
PbO+S0 2 +0 ~ PbS0 4
So, Mass of water formed = y g
It also reacts with copper halides and free halogens to
Increase in the mass of potash bulbs (or form lead halides which are retained in the combustion tube.
saphnolite tube)= x g
So, Mass of carbon dioxide formed =x g SOME SOLVED PROBLEMS
Calculations :
Problem 1. 0.92 g of an organic compound containing
(a) carbon, hydrogen and oxygen was analysed by combustion
method. The increase in mass of the U-tube and the potash
18 g of water contain 2 g of hydrogen bulbs at the end of the operation was found to be 1.08 g and
yg of water will contain =~ x yg of hydrogen 1.76 g, respectively. Determine the percentage composition of
18 the compound.

•
Molecular Analysis of Organic Compounds 43

Solution: Increase in mass of U-tube =L08 g (iii) Room temperature = to C = (t + 273) K

Mass of water formed = 1.08 g (iv) Atmospheric pressure = P mm
Since, 18 g of water contain hydrogen = 2 g (v) Aqueous tension at room temperature PI mm
2 . . Pressure of dry N 2 gas formed = (p - PI) mm
1.08 g of water contain hydrogen = 18 x 1.08 g
Alternately, volume of the vapours is changed to STP
Mass of compound taken for analysis = 0.92 g values.
Calculation:
2 1.08
Percentage of hydrogen = - x - - x 100 = 13.04 Experimental values at STP
18 0.92
PI =(p- PI)mm P2 = 760mm
Increase in mass of potash bulbs = 1.76 g
VI =VrnL V2 =?
Mass of carbon dioxide formed = 1.76 g
TI = (273 + t°C) T2 =273
Since, 44 g of carbon dioxide contain carbon 12 g
760xV2 (p- PI)XV
1.76 g of carbon dioxide contain carbon = ~ xl. 76 g
Thus, -----=-=
273 (273 + t)
12 1.76 (l mol of every gaseous substance has volume 22.4 L at
Percentage of carbon = 44 x 0.92 xl 00 = 52.17 STP)
So, volume of N 2 (by gas equation)
Percentage of oxygen = 100- (per cent of C + per cent of H)
= 100- (52.17+ 13.04) V. =(p - PI ) X V x 273 =V mL
= 100- 65. 21 = 34.79 2 (t + 273) 760
Composition of the compound: C = 52.17%; H = 13.04%; Pereentage of Nitrogen:
0= 34.791'10 22400 rnL of N 2 weigh at STP = 28 g
Estimation of Nitrogen Therefore, V rnL of N 2 weigh at STP. 2;4~0 x V g
The following two methods are used for the estimation of
nitrogen in an organic substance: Percentage of nitrogen in the given compound
(i) Duma's method 28 V .
=----x-xlOO
(ii) Kjeldahl's method 22400 W
1. Duma's method: This method can be applied in 2. Kjeldahl'. method: This is a very convenient
. case of all nitrogenous compounds. method but its use is restricted. This method is suitable for
The elemental nitrogen is converted into molecular estimating nitrogen in those organic compounds in which
nitrogen and its volume is changed to STP data. nitrogen is linked to carbon and hydrogen. The method is not
2N ) N 2 (g) used in the case of nitro, azo and azoxy compounds and to the
28g 22.4L at STP . compounds containing nitrogen in the ring (e.g., pyridine
Prineiple: A nitrogenous compound of formula quinoline, isoquinoline, etc.). The method is extensively used
CxH yN z when strongly heated with cupric oxide, in the for estimating nitrogen in food, fertilizers and agricultural
atmosphere of CO 2, nitrogen. is set free along with the products. .
formation of carbon dioxide and water. Part of nitrogen may Principle: The method is based on the fact that when
be oxidised into oxides of nitrogen. When the gaseous mixture the nitrogenous compound is heated with concentrated
is passed over a roll of heated bright copper gauze, the oxides sulphuric acid in presence of copper sulphate (as catalyst) and
of nitrogen are reduced again into nitrogen. potassium sulphate solid, the nitrogen present in the
. y .z compound is quantitatively converted to ammonium sulphate.
CXHyN z +(2x+ y/2)CUO~xC02+-H20+-N2
(Exce~) 2 2 CuS04 + K2S04
+ (2x + y/2)Cu Organic compound + Conc. H 2SO i ----"-----'=----'-7)
Il
Heat
Oxide of nitrogen +Cu ~ N 2 + CUO· (NH 4 hS04
The resultant mixture is collected over concentrated The ammonium sulphate so formed is decomposed by
KOH solution in a nitrometer,. All the gases (C0 2, S02' heating with excess of alkali and the ammonia evolved. is
H 20) except nitrogen are absorbed. The volume of nitrogen absorbed in known excess volume of a standard acid (H 2SO 4)'
collected over KOH solution is measured. The excess acid left after neutralisation with anUnonia is
Observation. : estimated by back titration with standard alkali. The
(i) Mass of the organic substance taken =W g percentage of nitrogen is then calculated from the amount of
ammonia..
(ii) Volume of moist nitrogen in nitrometer =v mL
44 G,R.B. Organic Chemistry (or Competitions

Observations: N
Unused acid required = 40 mL 10 NaOH
(i) Mass of the organic compound taken = W g
(ii) Normality of the standard acid = Nt N N
40 mL - NaOH == 40 mL - H 2S0 4
(iii) Volume of the acid taken = VI mL 10 10
(iv) Volume of the acid left after NH3 absorption =V2 mL N
==20 mL 5 H 2S0 4
(Determined by titrating with standard alkali solution)
(v) Volume of NI acid used, i.e., neutralised by ammonia Acid used for absorption of ammonia
=(VI -V2 ) mL V mL N.
Calculations: Since, V mL Nl acid = V mL Nl NH3 ::: (60 20) mL 5 H 2S04

and 1000mLNNH 3 =17gNH3 ==14gnitrogen N •

17
= 40 mL 5 H 2S0 4
So VmLN I NH3 = 1000XNj xVgNH3
1.4 x
Percentage of nitrogen = W
-14- x NIx V '
g rutrogen
1000
1.4x 40
14 100 == 56%
Percentage of nitrogen = 1000 x NIx V X W 0.2x5
Problem 4. 1.216 g of an organic compound was
1.4 X Nt x V
reacted under Kjeldahl s method and the ammonia evolved
W
was absorbed in 100 mL N H 2S0 4 , The remaining acid
Problem 2. An organic compound was analysed by solution was made up to 500 mL by addition ofwater. 20 mL of
s
Duma method. 0.45 g of the compound on combustion gave
this dilute solution required 32 mL of NIIO caustic soda
48.6 mL nitrogen at 27°C and 756 mm pressure. Calculate the
solution for complete neutralisation. Calculate the percentage
percentage of nitrogen.
of nitrogen in the compound.
Solution: V. = 48.6 mL V2 =?
Solution: 20 mL dilute unreacted acid soln. required
PI =756mm P2 =760mm
N
TI =27+273 T2 =273 K =32 mL - NaOHsoln.
=300K 500 mL dilute unreacted !2id soln. required
. . PjVI P2V2
Applymg general gas equatIon, --;;- = T. ;; 32 x 500 mL N NaOH soln.
.II 2
20 10

PI VI T2 = 32 x 500 mL N NaOH
Volume of nitrogen at STP, V2 = ~. P 20 10
2
==80mL NNaOH
=
756x 48.6 273
x- 80 mL N NaOH = 80 mL N H 2 S0 4
300 760 Acid used for the neutralisation of NH 3
=43.99mL =(100-80) mL N H 2S0 4 '

Mass of organic compound = 0.45 g =20mLN H 2S0 4

. 28 V2 V
Percentage of nitrogen in the compound = 22400 x W x I 00 Percentage of nitrogen 1.4 x Nl x W

=~x 43.99 x 100 NI =1, V =20mL and W=1.216g

22400 0.45 1.41.216
xl x20 = 23.030/0
So, percentage of nitrogen 74
=12.22%
probl.:P1~! 0.2 g ofan organic compound was analysed Estimation of Halog~ns
by Kjeldahl s method. Ammonia evolved was absorbed in The estimation of halogens (Cl, Br or I) in organic
60 mL N I5H2S0 4 • Unused acid required 40 mL of N 110 compounds is usually done by Carius method.
NaOH for complete neutralisation. Find the percentage of Principle: The method is based on the fact that when
nitrogen in the compound. an organic compound containing halogen (CI, Br or I) is
Soluqon: Mass' of organic compound = 0.2 g heated in a sealed tube (Carius tube) with fuming nitric acid in
presence of excess of silver nitrate, silver halide is formed.
 Molecular Analysis of Organic Compounds 45

From the mass of silver halide formed, the percentage of the Problem 7. 0.1170g of an organic compound on
halogen can be calculated. heating with conc. RN0 3 and silver nitrate in Cariusfurnace
Calculations: Mass of the organic substance = W g gave 0.42 g of AgCl. Find the percentage of chlorine in the
compound.
Mass of the silver halide = WI g
Solution: Mass of organic compound, W = 0.1170 g
(a) Chlorine: AgCl = CI Mass of AgCl, W; = 0.42 g
,143.5 g 35.5 g
143.5 g of AgCl contains chlorine = 35.5 g AgCl = CI
143.5 g 35.5 g
W; g AgCl contains chlorine = 35.5 x W; g . 35.5 W;
143.5 Percentage of chl onne = - - x - xl 00
143.5 W '
Percentage of chlorine = 35.5 x WI x 100
143.5 W = 35.5 x 0.42 x 100=88.80%
143.5 0.1170
(b) Bromine: AgBr = Br Hmogens can also be estimated by Schiff's and Piria
188 g 80 g
method.
188 g of AgBr contains bromine = 80 g In this method the accurately weighed organic compound
is taken in a small plat~um crucible with a mixture of lime
W; g of AgBr contains bromine = ~ x W; g
188 and sodium carbonate, (CaO + Na 2C0 3). It is now heated
. 80 WI strongly and then cooled and dissolved in dilute nitric acid in a
Percentage of b romme = - x - x 100 beaker. The solution is then filtered and the halide is
188 W
precipitated with silver nitrate solution. Halogen is now
(c) Iodine: AgI = I calculated as in Carius method.
235 g 127 g
235 g of AgI contains iodine = 127 g Estimation of Sulphur
. . d· 127 Sulphur in organic compounds may be estimated by any
W; gAgI contams 10 me = - x W; g
235 one of the following method:
(a) Carius method
Percentage 0 f · 127 x -WI x 100
• = -'-
lodme (b) Messengers method
. 235 W
(c) Fusion method
Problem: 5. 0.5264 g silver bromide is ,obtained from The most common method for the estimation of sulphur is
0.5124 g ofan organic compound. Calculate the percentage of Carius method.
bromine in the compound. Principle: When anorganic compound containing
sulphur is heated with fuming nitric acid, sulphur is
Solution: Mass of organic compound, W = 0.5124 g
quantitatively oxidised to sulphuric acid. This is precipitated
Mass of silver bromide, W; = 0.5264 g as barium sulphate by adding barium chloride solution. From
AgBr = Br the amount of barium sulphate, percentage of sulphur can be
188g 80g calculated.
. 80 W; S + RN0 3 (fuming) Heat) H 2 S0 4
Percentage of bromme = - x - x 100
188 W H 2 S0 4 + BaCI 2 ) BaS0 4 +2HCI
=~ x 0.5264 xl00 = 43.71% Calculations: Mass of organic compound = W g
188 0.5124
Mass of barium sulphate = WI g
Problem 6. 0.156 g ofan organic compound on heating
with fuming RN0 3 and AgN03 gives 0.235g of Agl. BaS0 4 == S
233 g 32 g
Calculate the percentage of iodine in the compound.
233 g of barium sulphate contains sulphur = 32 g
Solution: Mass of organic compound, W =:= 0.156 g
contain~ sulphur =
~ :. ".
Mass of AgI, W; =0.23Sg W; g of barium sulphate 32 x W; g
233
AgI = I 32 W'
235 g 127 g Percentage of sulphur = - x _1 X 100
233 W
.. 127 W.
Percentage of Iodme = -, x _ I xl 00 Problem 8. On heating 0.32 g of an organic compound
235 W
with concentrated nitric acid and barium chloride, 0.932 g
= 127 x 0.235 x 100=81.41 % barium sulphate was obtained. Calculate the percentage of
235 0.156 sulphur in the given compound.,
'-.':.

L,~-
46 G.R.B. Organic Chemistry for Competitions

Seludon: Mass of organic compound, W =0.32 g passed over heated carbon at 1100°C. The oxygen combines
with carbon forming carbon monoxide.
Mass of barium sulphate, Wt =0.932g
. Pyrolysis
BaS04 === S Compound ) Oxygen + Gaseous products
233 g 32 g

Percentage of sulphur = -
32 Wt
x - x 100
°z + 2C(~aphite) 11 OO°C) 2CO
233 W The gas is then passed through a tube containing iodine
pentoxide at 175°C to liberate iodine.
= 32 x 0.932 xIOO=40%
233 0.32 5CO+IzOs ---+ I z +5CO z
By determining the amount ofCO z or I z produced, the
Esdmadon of Phosphorus percentage of oxygen in the organic compound can be
It is also estimated by Carius method. The organic calculated.
compound containing phosphorus is heated' with fuming
•
The resulting gaseous mixture (CO z and I z ) is passed
nitric acid. Phosphorus is oxidised to phosphoric acid. through potassium iodide which absorbs iodine and the COz
It is precipitated as ammonium phosphomolybdate, left is then absorbed in KOH. Knowing the increase of weight
(NH4) 3 PO 4·12Mo03 by heating it with conc. HN0 3 and then
ofKOH, i.e., the weight ofCO z , the percentage of oxygen can
adding ammonium molybdate. The yellow precipitate is
filtered, washed, dried and weighed .. be calculated.
Alternatively phosphoric acid is precipitated as magne-
sium ammonium phosphate, MgNH4P04, by the addition of
°
16g
=CO===CO z
44 g
magnesia mixture (MgS0 4 + NH 40H + NH 4CI). The
16 Olass of CO 2
magnesium ammonium phosphate -is washed, dried and Percentage of oxygen =-x x 100
ignited when it is converted to magnesium pyrophosphate 44 mass of org. oompd.
(Mg ZPZ0 7 )· NowadaYs, the estimation of elements (C, H and N) in an
organic compound is done by taking only very small (micro)
quantities (about 1-3 mg) of the substance with the help of
instrumental automatic experiment techniques (CRN
Magnesia mixture
H 3P0 4 ) MgNH4P04 elemental analyzer) and the results are obtained on a screen
Phosphoric acid (Mg2+ + NH40H) Magnesium ammonium (LED) within a short time.
phosphate
Heat ILLUSTRAnONS OF OBJEcnVE QUESTIONS
2MgNH4 P04 -~ Mg ZPZ0 7 +2NH3 +HzO
From the mass of magnesium pyrophosphate, the I. Lassaigne's test for the detection of nitrogen will fail in the
percentage of phosphorus in the compound can be calculated. case of:
(a) NH2 CONHZ (b) NHZCONHNH2 ·HCI
Caleulatlons: Mass of organic compound = W g
(c) NH2NH2 ·HCI (d) C6HsNHNH2 ·2HCI
Mass of magnesium pyrophosphate =Wt g [Ans. (c)]
Mg ZPZ 0 7 === 2P [HInt: For Lassaigne's test of nitrogen, compound must
222 g 62g contain N in addition to carbon to form NaCN in sodium
62 W . extract.]
Percentage of phosphorus = - x _1 X 100
222 W Z. The function of boiling the sodium extract with conc. HNO]
EsdOladon of Oxygen before testing for halogen is:
(a) to make the solution acidic
The usual method of determining the percentage of (b) to make the solution clear
oxygen in an· organic compound is by the method of (c) to convert Fe 2+ to Fe 3+
difference. All the elements except oxygen present in the (d) to destroy CN- and Sz- ions
organic compound are estimated and ·the total of their [Ans. (d)]
percentages is subtracted from 100 to get the percentage of [HInt : If N and S are already present, they will hinder in
oxygen. test of halogens as NaCN and Na 2 S will giv" white or black
Percentage of oxygen =100 - (Sum of the percentages precipitate with AgN03' Boiling conc. HN0 3 is thus used .
of all other elements) to remove ~and S2-. ions in the form of volatile HCN
However, a direct method for the estimation of oxygen andH 2 S.]
was discovered in 1947. This is known as Aluise's method. A 3. Sodium nitroprusside when added to an alkaline solution of
known amount of organic compound is subjected to pyrolysis sulphide ions produces a colouration : 1A.J.i'M.C lOM1
(decomposition by heat) in a stream of nitrogen. The oxygen (a) red (b) blue
and other gaseous products formed during pyrolysis are (c) brown (d) purple

.3
Molecular Analysis of Organic Compounds 47
[Ans. (d)] 2. Chemieal methods:
[HInt: Purple (deep violet) colour is due to the fonnation (i) Silver salt method for acids
of sodium thionitroprusside, Na 4 [Fe(CN)s NOS].] (ii) Platinichloride method for bases
4. In Kjeldahl's method, nitrogen present is estimated as: (iii) Volumetric method for both acids and bases
(a) N2 (b) NH3
(c) N0 2 (d) none of these 1. (i) Physical MethiHIs for Volatile Compounds
[Ans. (b)]
[HInt: In this method the nitrogen present is (a) Vidor Meyer's method: Molecular mass of
quantitatively. converted into (NH4 )2 SO 4 on. heating with volatile liquids and solids can be easily determined from the
conc. H2 SO4' The (NH4 )2 SO4 is then treated with standard application of Avogadro hypothesis according to which the
alkali solution to liberate NH3 ' which is absorbed in H2 SO4 mass of 22.4 litres or 22400 mL of the vapour of any volatile
to obtain percentage of nitrogen.] substance at NTP is equal to the molecular mass of the
5. In Kjeldahl's method, nitrogen present' is quantitatively substance.
converted to : In Victor Meyer's method, a known mass of the volatile
(a) N2 (b) (NH4}z SO4 substance is vaporised in a Victor Meyer's tube, The vapours
(c) N0 2 (d) none of these fonned displace an equal volume of air into a graduated tube.
[Ans. (b)] The volume of air collected in graduated tube is measured
6. In Kjeldahl's method of estimation of nitrogen, K2 SO4 acts under experimental conditions. This volume is converted to
as: NTP conditions.
(a) an oxidising agent (b) catalytic agent Calculations: Mass of the organic substance =W g
(c) hydrolysing agent (d) boiling point elevator
[Ans. (d)] Let the volume of the air displaced be VI mL
[Hint: Addition ofK 2S04 increases the boiling point of Temperature =TI K
H 2 S04 ,] Pressure (after deducting aqueous tension) PI mm
7. Positive Beilstein test shows that: Let the volume at NTP be =V2 mL
(a) halogens are surely present
(b) halogens are absent Applying gas equation,
(c) halogens may be present PI XVI 273
Vz x-
(d) none of the above 11 760
[Ans. (c)]
[Hint: Beilstein test is also given by some other 22400 mL of vapours weigh at .NTP = M (mol. mass)
_ compounds such as urea, pyridine thiourea and organic V2 mL of vapours weigh at NTP =W g
acids, etc., which imparts colour to the flame.] W .
8. In an organic compound, the phosphorus is estimated as:
22400 mL of vapours weigh at NTP - x 22400:: M
V2
(AFMC 2010)
(a) Mg 2 Pz 0 7 (b) Mg 3 (P0 4 h or Vapour density of substance
(c) H 3 P04 (d) P2 0 S Mass of I mL of vapours at NTP
[Ans. (a)]
Mass of 1 mL of hydrogen at NTP
2.4 DETERMINATION OF MOLECULAR MASS . W/V
or V.D.= 2
0.00009
The molecular mass of the organic compounds can be
determined by various methods. The methods may be divided W
or V.D.=-~·--
into two groups: V2 xO.000Q9
1. Physical methods: These are of two types: 2W
[Link]<;. M=2xV.D.=----
(I) For volatile compounds V2 xO.00009
(a) Victor Meyer's method Note: Alternately volume of the vapours is changed to STP values.
(b) Duma's method (l mol of every gaseous substance has volume 22.4 L at STP)
(c) Hofinann's method s
Problem 9. In a Victor Meyer determination, the
(Ii) For non-volatile compounds following observations have been made:
(a) Ebullioscopic method or elevation in boiling Mass of compound =0.17 g
point method
Volume of air collected =34.2 mL
(b) Cryoscopic method or depression in freezing
P9int method Temperature =15° C
Atmospheric pressure =750 mm
 48 G.R.B. Organic Chemistry for Competitzons

Vapour pressure of water at 15 0 C = 13 mm.

V2 = volume of vapours at NTP = (W3 - ffJ. ) X PI x 273]
Calculate the vapour density and molecular mass of the [ . ~ .. 7~

. compound.
Problem 10. A Duma s bulb full of air weighs 22.567 g
Solution: Given
at 20°C and 755 mm pressure. Full of vapours of a substance
VI =34.2mL V2 =1 at l20°C and the same pressure, it weighs 22.8617 g. The
NTP
PI = (750 -13) = 737 nnn P2 =760nnn capacity of the bulb is 200 mL. Find out the mo{ecular mass of
) conditions
TI = (l5 +273) =288 K T2 =237K the substance. [Density of air =0.00129 g/mL]
By gas equation, Solution: Given
V = 737x 34.2 x 273 =31.4376 mL VI = volume of bulb = 200 mL V2 = ?
288 760 NTP
2 TI =(20+273)=293K T2 =273K
) conditions
W 0.17 PI = 755 nnn P 2 = 760 nnn
Vapour density = =------ 60.08
V2 x 0.00009 31.4376 x 0.00009 So V2 = Volume of bulb at NTP
Mol. mass = 2 x Vapour density = 2 x 60.08 = 120.16 200x 755 273 18
- - - x - = 5.122mL
(b) Duma's method: The apparatus consists ofa glass 293 760
bulb of about 250 mL capacity with a narrow outlet tube. It is Mass of air = V2 x 0.00129= 185.122x 0.00129
cleaned, dried and weighed at the room temperature. A few
=0.2388g
mL of the organic substance (liquid) is placed in the bulb. The
bulb is now placed in a bath and clamped. The bath consists of Mass of empty bulb = (22.567 - 0.2388)
a liquid having 30-40 0 e higher boiling point than that of the = 22.3282 g
substance whose molecular mass is to be determined. The bath
Mass of vapours = (22.8617 - 22.3282)
is now heated to about 20 0 e higher than the boiling point of
the substance kept inside the bulb. When whole of the = 0.5335 g
substance inside the bulb has vaporised and no more vapours Let the volume of vapours at NTP be V.
come out, the mouth of the bulb is sealed with a blow pipe
flame. The bulb is now taken out of the bath, cleaned and V = 200 x 755 x 273 =138 mL
dried from outside. It is now weighed. The volume of the bulb 393 760
is determined by breaking the enq of the sealed mouth under mass of vapours
Mol. mass of the substance = x 22400
water and weighing the bulb full of water along with broken vol. of vapours at NTP
pieces of glass. ;'
Calculations : = 0.5335 x 22400= 86.59
138
(i) Mass of bulb + air = ffJ. g
(c) Hofmann's method: The method is applied to
(ii) Mass of bulb + vapours = ~ g those substances which are not stable at their boiling points,
(iii) Mass of bulb + water = ~ g but which may be volatilised without decomposition under
Mass of water in bulb = (W3 - ffJ. ) g reduced pressure. A known mass of the substance is vaporised
So Voluine of bulb = (W3 - ffJ. ) mL above a mercury column in a barometric tube and the volume
(iv) Room temperature = TI K and pressure after . of the vapour formed is recorded. It is then reduced to NTP
deducting vapour pressure of water = PI nnn conditions. The molecular mass of the organic substance can
Volume of the air in the bulb at NTP be calculated by the application of following relationship:
mass of the substance 22400
= (~ - ffJ. ) X PI x 273 = V mL 1
M [Link]= x
TI 760 I
volume of the vapours at NTP

So Mass of air = VI xO.00129 (ii) Physical Methods for Non-volatile Substances

(density of air at NTP= 0.00129 g / mL) The molecular mass of a non-volatile organic compound
can be determined by noting either the elevation in boiling
(v) Temperature of the bath =T2 K .point of the solvent (Ebullioscopic method) or the depression
in freezing point of the solvent (Cryoscopic method)
Hence, Mass of empty bulb = (ffJ. - VI x 0.00129) g produced by dissolving a definite mass of the substance in a
So Mass of vapour = [~ - (ffJ. - VI x 0.00129)] g knoWn mass of the solvent. The molecular mass of the
Mol. mass of the substance compound can be calculated from the following mathematical
[~ - (ffJ. -VI xO.00129)] relationships:
= x 22400
V2
48 G.R.B. Organic Chemistry for Competitions

Vapour pressure of water at 15° C = 13 mm , (W3 - Wj ) X PI

[ V2 = volume of vapours at NTP = x273]
-
Calculate the vapour density and molecular mass of the T2 760
compound.
Problem 10. A Duma s bulb full of air weighs 22.567 g
Solution: Given at 20°C and 755 mm pressure. Full of vapours of a substance
VI =34.2mL V2 =1 at 120°C and the sam'e pressure. it weighs 22.8617 g. The
NTP
PI = (750 -13) = 737 nnn P2 = 760nnn capacity ofthe bulb is 200 mL. fInd Ollt the mo(ecular mass of
) conditions
TI =(15+273)=288K T2 =237K the substance. [Density of air =0.00129 g/mL]
By gas equation, Solution : Given
V = 737x 34.2 x 273 =31.4376 mL VI = volume of bulb = 200 mL V2 = ?
288 760 NTP
2 TI = (20+273) =293 K T2 =273 K
) conditions
W 0.17 PI = 755 nnn P2 = 760 nnn
Vapour density = = = 60.08
V2 xO.00009 31.4376x 0.00009 So V2 = Volume of bulb at NTP
Mol. mass = 2 x Vapour density = 2 x 60.08 = 120.16 =200x 755 x 273 = 185.122 mL
(b) Duma's method: The apparatus consists of a glass 293 760
bulb of about 250 mL capacity with a narrow outlet tube. It is Mass of air = V2 x 0.00129= l85.122x 0.00129
cleaned, dried and weighed at the room temperature. A few
=0.2388g
mL of the organic substance (liquid) is placed in the bulb. The
bulb is now placed in a bath and clamped. The bath consists of Mass of empty bulb = (22.567 - 0.2388)
a liquid having 30--40° C higher boiling point than that of the = 22.3282 g
substance whose molecular mass is to be determined. The bath
Mass of vapours = (22.8617 - 22.3282)
is now heated to about 20°C higher than the boiling point of
the substance kept inside the bulb. When whole of the = 0.5335 g
substance inside the bulb has vaporised and no more vapours Let the volume of vapours at NTP be V.
come out, the mouth of the bulb is sealed with a blow pipe
V = 200x 755 x 273 =138 mL
flame. The bulb is now taken out of the bath, cleaned and
dried from outside. It is now weighed. The volume of the bulb 393 760
is determined by breaking the end of the sealed mouth under mass of vapours
Mol. mass of the substance = x 22400
water and weighing the bulb full of water along with broken vol. of vapours at NTP
pieces of glass. ,,'
Calculations: = 0.5335 x 22400= 86.59
138
(i) Mass of bulb + air = Wj g
(c) Hofmann's method: The method is applied to
(ii) Mass of bulb + vapours = Wz g those substances which are not stable at their boiling points,
(iii) Mass of bulb + water = W3 g but which may be volatilised without decomposition under
Mass of water in bulb = (W) - Wj ) g reduced pressure. A known mass of the substance is vaporised
So Volume of bulb = (W3 - Wj )mL above a mercurycolurnn in a barometric tube and the volume
(iv) Room temperature = TI K and pressure after of the vapour formed is recorded. It is then reduced to NTP
deducting vapour pressure of water = PI nnn conditions. The molecular mass of the organic substance can
Volume of the air in the bulb at NTP be calculated by the application of following relationship:
mass of the substance
(W) - Wj ) X PI 273 Mol. mass = x 22400
= x-=VI mL volume of the vapours at NTP
TI 760
So Mass of air = VI xO.00129 (ii) Physical Methods for Non-volatile Substances
(density of air at NTP= 0.00129 g / mL) The molecular mass of a non-volatile organic compound
can be determined by noting either the elevation in boiling
point ofthe solvent (Ebullioscopic method) or the depression
(v) Temperature of the bath = T2 K
in freezing point of the solvent (Cryoscopic method)
Hence, Mass ofemptybulb=(Wj -VI xO.00129)g produced by dissolving a definite mass of the substance in a
So Mass ofvapour=[W2 -(Wj -VI xO.00129)]g knoWn mass of the solvent. The molecular mass of the
Mol. mass of the substance compound can be calculated from the following mathematical
[Wz - (Wj -VI xO.00129)] relationships:
= ><22400
V2
Molecular Analysis of Organic Compounds 49

(a) Elevation in boiling point: mass of silver salt w

=-
. 1000Kb Xw Eq. mass of silver x
Mo I. mass;;;: ---"---
Wxl1T
or Eq. mass of silver salt =~ x 108
where x
Kb = Molal elevation constant of the solvent Let the equivalent mass of the acid be E. In the
w= Mass of-the compound preparation of silver salt, a hydrogen atom of the carboxylic
W = Mass of the solvent group is replaced by a silver atom.
I1T = Elevation in boiling point of the solvent Thus, Equivalent mass of silver sa'it = E -1 + 108
(determined experimentally). =E +107
w
(b) Depression in freezing point: Thus, E + 107 ;;;: - xl 08
1000K j Xw x
Mol. mass == - - - - -
Wxl1T or E =[; x 108 -107]
where
K j = Molal depression constant of the solvent If n be the basicity of the acid, then
w == Mass of the compound .
W = Mass of the solvent
Mol. mass of the acid = [ : x 108 - 107] x n
I1T == Depression in freezing point' of the solvent
(determined experimentally) Problem H. 0.38 g of a silver salt of a dibasic acid on
ignition gave 0.27 g 'ofsilver. Calculate the molecular mass of
2. Chemical Methods the acid.
(i) Silver salt method for acids: It is based on the fact Solution: Mass of silver salt;;;: 0.38 g
that silver salt of an organic acid on. heating gives residue of Mass of silver = 0.27 g
· metallic silver.
Eq. mass of silver salt Mass of silver salt
RCOOAg Heat) Ag
Eq. mass of silver Mass of silver
Silver salt Silver
(residue)
Eq. mass of silver salt 0.38 x 108 -
From the mass of silver salt taken and the mass of the 0.27
silver residue obtained, the equivalent mass of the silver salt 0.38 .
can be calculated. . or E +107=-·-· x 108 (E ;;;: Eq. mass of acid) ..
0.27
Equivalent mass of silver salt Mass of silver salt
Equivalent mass of silver Mass of silver or E =[0.38 x 108 - 107J =45
0.27
Knowing the equivalent mass of silver salt, the equivalent
· mass of the acid can be obtained. The molecular mass of an .
Mol. mass of the acid Eq. mass x basicity =45 x 2 ;;;: 90
acid can be determined with the help of the following (ii) Platinichloride method for bases: OrgarllC bases
relationship: combine with chloroplatinic acid, H 2 PtC1 6 , to form insoluble
platinichlorides, which, on ignition, leave-a [Link]
Mol. mass of the acid· Equivalent mass of the acid x basi~ity
platinum. Knowing the mass of platinum salt and the mass of
Procedure: . The organic acid is treated with excess of metallic platinum, the molecular mass of the platinum salt can
'NH40H. The ammonium salt is formed which remains in be determined. Let Brepresents one molecule of the base. If
dissolved form. . the base is mono-acidic, the formula of the double salt will be
RCOOH +NH 40H ---7 RCOONH 4 + H 20 B2 H 2 PtCl 6 ,
The umeacted ammonia is boiled off. The neutral solution
is then treated with silver ni~ate ·solution. The precipitated . 2B Hel) 2B. HCI PtCl 4 ) B2 H 2 PtC1 6
· silver salt i~ filtered, washed and dried.
B zH z PtCl 6 Heat) Pt
RCOONH 4 + AgN03 . ---7 RCOOAg + NH 4N03 Double salt Platinum (residue)
A known mass of silver salt (about 0.2 g) is heated in a (2B'+ 410) . (195)
platinlim crucible when metallic silvcds obtained as residue. Molecular mass of the salt M&SS of platinum salt
It is weighed.
,Atomic mass of platinum Mass ofplatinun~
Calculations !
(i) . Mass of silver salt taken =w g Let E be the equivalent masS of the base.
(ii) . Mass of metallic silver =x g
 50 G.R.B. Organic Chemistry for Competitions

MolecUlar mass of the salt = 2E + 2 + 195 + 213 volume ofthe acid solution used, the mass of the organic base
=2E +410 which will require 1000 mL of a normal acid solution for
2E + 410 w MaSs'ofplatinum salt complete neutralisation can be calculated. This mass will be
So, =-= the equivalent mass of the base.
195 x Mass of platinum
,
1000 mL N acid solution == One gram equivalent of the base
I

2E = [ : x 195 - 410] One gram equiv;lent of the acid

MolecUlar mass of the base = Eq. mass x acidity

.
E=!2 [wx x 195 - 410]
Problem 13. 1.575 g ofan organic acid was dissolved in
250 mL of water. 20 mL of this solution required 16 mL of N/8
Mol. ~'of the base = Eq. mass x acidity of the base alkali solution for cf!mplete neutralisation. If the basicity of
. the acid is two, find its molecular mass.
=Exn
Solution:
where n is the acidity of the base.
16 mL N /8 alkali solution == 20 mL of acid solution
Problem 12. 0.49 g of the chloroplatinate of a diacid
2 mL 1 N alkali solution == 20 mL of acid solution
base gave on ignition 0.195 g of platinum. Calculate the
molecular mass of the base. 2 x 250 mL 1 N alkali solution == 250 mL of acid sOlution
20
Solution:
25 mL 1 Nalkali solution == 1.575 g acid
Mol. mass of chloroplatinate Mass of chloroplatinate taken
At. massofplatinum Mass of platinum left 1000 mL 1 N alkali solution == 1.575 xl 000 g acid'
25
0.49 Eq. mass of the acid = 63 g acid
=0~195 MoL mass of the acid = 63 x 2 = 126
Let B be the equivalent mass of the base. Problem 14. 2.65 g of a diacidic base was dissolved in
2B + 410 0.49- . .' N
=-- 500 mL of water. 20 mL of this solution required 12 mL of -
195 0.195 6
Hel solution. Calculate the equivalent mass and molecular
or '2B = [. 0.49 x 195 - 410] =80 mass of the base. .
0.195 .
Solution:
or B=40
Mol. mass of the base = Eq. mass x acidity = 40 x 2 = 80 12 mL N Hel solution == 20 mL of base solution
6
(iii) Volumetric method for acids and bases: The or 2 mL 1 N Hel solution == 20 mL of base solution
molecular mass of an. acid can be determined by dissolving a
known mass of the acid in water and titrating the solution or 2.
20
x 500 mL 1 N Hel solution == 500 mL of base solution
against a standard solution of an alkali using phenolphthalein
or 50 mL 1 N Hel solution == 2.65 g of base
as indicator. Knowing the volume of alkali solution used, the
mass of the acid, which will require 1000 mL of a nonnal 1000 mL 1 N Hel solution == 2.65 xl 000 = 53 g base
alkali solution for complete neutralisation can be calculated. 50
This mass of the' acid will be its equivalent mass. Eq. mass of the base = 53
J000 mL 1 N alkali solution, == One gram equivalent of the acid Mol. mass of the base = Eq. mass x acidity = 53 x 2 = 106
Qne grain equi~alent of alkali
ILLUSTRATIONS OF OBJECTIVE QUESTIONS
Calculafjolis: .Suppose wg of the organic acid requires
.9. Molecular mass of a volatile organic solid can be
V inL N 1 alkali solution for complete neutralisation. determined by:
V mL N 1 aIkali solution == w g acid (a) silver chloride method (b) platinichloride method
(c) Victor Meyer's method (d) Kjeldahl's method
So, lPOOmL Nl alkalisolution w xl000g acid [Ans. (c)]
. . . VxN 1 10. Molecular mass of a non-volatile organic solid can be
== one gram equivalent acid deteimined by:
(a) Victor Meyer's method
Equivalent mass of the a~id == w x 1000'
, -. VxN (b) elevation in boiling point
.. ,. .' • . . 1
(c) silver salt method
Thus, MolecUlar mass of theacid=Eq. mass x basicity (d) depression in freezing point
In the case of organic bases, the khO\tmnlasS of the base is [Ans. (b) and (d)]
titrated
.
against
- . of ~ acid. Knowing the
a standard solutio.
.

-'
Molecular Analysis o{Or~anic Compounds 51

11. Equivalent mass of an organic acid can be determined by: Thus, the simplest formula of a substance capable of
(a) silver salt method (b) cryoscopic method expressing its percentage composition can be called its
(c) ebullioscopic method (d) platinichloride method empirical formula.
[Ans. (a)] Calculation of empirical formula: Empirical formula
U. Equivalent mass of an organic base can be determined by: is calculated from the percentage composition. The steps
(a) silver salt method involved in the calculation are as follows: .
(b) depression in freezing point Step 1: The percentage of each eli~ment is divided by
(c) elevation in boiling point its atomic mass. This gives the relative number of different
(d) platinichloride method atonis present in the molecule.
[Ans. (d)]
Step 2: The relative numbers of different atoms
2.5 EMPIRICAL FORMULA AND MOLECULAR obtained in Step I are divided by the lowest one amongst them
as to get simple ratio of atoms present in the molecule. .
FORMULA
Step 3: .The values obtained in Step 2 mayor may not
The empirical formula of a compound is the simplest be whole numbers. In case one or more values are fractional,
formula which expresses the simple whole number ratio of these are multiplied by a suitable integer to get" simplest ratio
the atoms of constituent elements present in the molecule. in whole numbers. Minor fractions are neglected.
For example, CH 20 is the empirical formula of acetic acid. It Step 4: . The symbols of each element .present are
expresses that the simplest whole number ratio between written side by side in a line with the number of atoms as
carbon, hydrogen and oxygen atoms present in one molecule determined in Step 2 or Step 3 as subscripts to the lower
of acetic acid is I :2 : l. The empirical fOmiula does not tell us corner of each. This gives the empirical or simplest formula.
the exact number of various atoms of different elements Knowing the empirical formula, the molecular formula
present in one molecule of the substance. However, the exact can be ascertained if the molecular mass of the substance is
number of atoms of different elements present in one molecule known. It may be the same as the empirical formula of the
is always a simple multiple of ratio of atoms in the empirical substance or an exact multiple of it.
formula. The formula which gives the actual number of
Molecular formula;;;: n X (Empirical formula)
atoms of various eh~inents present in tbe molecule of the
substance is termed the molecular formula. The value of 'n' can be determined if molecular mass of
Thus, Molecular formula =n X [Empirical formula] the substance is known.
where n is a whole number. Molecular mass
n=--------
Molecular formula of acetic acid = 2 x Empirical formula Empirical formula mass
=2xCH 20 An alternative method of molecular formula·
=C 2H 40 2(CH 3COOH) determination. ..
In this method, molecular formula can be determined
The value of'n' can be obtained by dividing the molecular
without determining empirical formula. It is very simple
mass by empirical formula mass. . .
method and comparatively less time taking.
Molecular mass Following relation is used to calculate number of moles of .
n=--------
Empirical formula mass an element in the compound.:". ..Jtt.~

For example, Number of moles of element

% of element Molecular mass
Molecular mass of acetic acid = 60 = 100 x-------- Atomic mass of ele~nt
and Empirical formula mass (CH 20) = (12 +2 +16) 30
60 Problem 15. An organic compound contains 40% C,
n=-=2 6.66% H and rest oxygen. Its vapour density is 30. Calculate·.
30
its empirical and molecular formulas.
The percentage composition of the compound can be
calculated from its empirical formula. For example: Solution: Calculation of empirical formula:
Empirical formula of acetic acid =CH 20
EmpiricaIformula mass = (12 + 2 + 16) =30 At .Ittlatlw
Blmbtl'
12
Percentage of C = -:- X 100 40.00
111188
. ,htom.
30 40 . 3.33 ~ 1
. 2 Carbon 40.0 12 -=3.33 3.33
Percentage of H = - x 100 = 6.66 12
30 ~==6.66
. Hydrogen 6.66
16 1
Percentage of 0 = 30 xl 00 = 53.34 53.34 ~3.3± =3.33 .
Oxygen 16
52 G.R.B. Organic Chemistz for Competitions .

Empirical formula = CH20 =53.75 g acid

Empirical fonnula mass {12 +2 +16) = 30 Eq. mass of the acid = 53.75
Mol. mass=2x V.D. 2 x30 Mol. mass of the acid = Eq. mass x basicity
=60 :: 53.75x2 =107.50
n = Mol. mass = 60 =2 n:: Mol. mass = 107.50 "" 1
Emp. mass 30 Emp. mass 104.0
Molecular formula = 2 x (Empirical formula) Molecular formula = C 3 H40 4
=2.~x (CH 20) = C2 H 40 2
Problem 17. An organic compound contains C = 48%,
=
H 8%. 0.48 g of the compound was Kjeldahlised and the
Alternatively liberated ammonia required 19.2 mL N 12 H 2S0 4 , Find the
Number of moles of carbon empirical formula of the compound.
% of carbon . Molecular mass . 1.4 x N xv,
= 100 x---------------- Solution: Percentage of mtrogen :: ~ I
Atomic mass of eleJ;OOHt
40 60 . W = Mass of organic compound = 0.48 g
=-x-=2· I
100. 12 NI :2=0.5, VI =19.2mL
Number of moles ;(if hydrogen
1.4xO.5xI9.2 28
% of hydrogen Molecular mass P ercentage 0 f N :: ==
= 100
x-----------------
Atomic mass of hydrogen
0.48
Percentage of oxygen = 100 - (48 + 8 + 28) = 16
= 6.66 x 60 =4 Calculation of empirical formul~
100 I
RelativeSlmple~t
Number of moles of oxygen Element' Percentage At. ,mailS numb~rof' .. [Link]
% of oxygen Molecular mass [Link]· atoms,
= 100
.. .
x----------
Atomic mass of oxygen
, I :'"

. 53.34 60 .. Carbon '48.0 12 48 =4

12
'" i=4
1
=--x--=2
100 16
Hydrogen 8.0 8=8 ~=8
Molecular formula =C 2 H 40 2 1 1
'Problem 1~. A dibasic organic. acid gave the following 28.0 14 28 =2 2=2
Nitrogen 14 1
results: C= 34.62%' H '= 3.84%. 0.1076 g of this acid
. consumes 20mL of 0.1 N NaOH for complete neutralisation. 16 .
Oxygen 16.0 16 -=1 !=1
.
Find out-the molecular formul'!..,ofthe acid.. 16 1

Solution : .. ' Cal~ulation of eml2irical formula : Problem 18. Haemoglobin is a chromoprotein having
four atoms of Fe in each molecule. AnalysiS showed 0.35%
Jlemeot ~t Relative number8lmplest ratio
Percentage mass of atoms. . ofatoms Fe. Whatis the molecular weight of haemoglobin?
. Solution: Atomic mass of iron =56 amu
34.62 12 34.62 =2.88 . 2.88 ~ I X 3 = 3 ' Mass of iron in a molecule of haemoglobin
12, ' 2.88
. ..,. = 56 x 4 = 224 anru
'Hydrogen 3.84 1 3.84 = 3.84 3.[Link] 1.33 x 3 =4
1 2.88 ': 0.35 amu of Fe is present in 100 amu of haemoglobin
61.54 .16 .61.54 = 3.84 3.84 = 1.33 x3= 4 :. 224 amu of Fe will be present in 100 x 224 amu. of
Oxygen (by difference) . 16 2.88 . 0.35
. Empiri~al fopnula of the acid = C 3 H 40 4 . .... haemoglobin, i.e., 64000 amu
Thus; molecular mass of haemoglobin = 64000 amu
. 'Empiricalf~rmulamasS=" (3 x 12)+ (~ ~ l)'if- (4 x 16}
=104, '
2.6 MOLECULAR FORMULA OF GASEOUS
Calculation of molecular mass: HYDROCARBONS
, 20mLO.l NNaOHso..1075g,acid
20xO.l mL I, N NaOH =O.I075g acid . The molecular formula of g~seous hydrocarbons caribe'
'. " . '0.1075 ; - . determined even without knowing their percentage
So·,·1000mL1 N NaOH= 20 Xl000g acid composition. A .known volume of hydrocarbon is taken in
, xO.l eudiometer tpbe and exploded wit~ an excess of known
 Molecular Analysis of Organic Compounds 53

volume of oxygen. The carbon and hydrogen of the 25 mL On adding a concentrated solution of potassium
hydrocarbon are oxidised to carbon dioxide and water hydroxide, the volume -forther diminished to 15 mL, the
respectively according to the following general reaction : residual gas being pure 'oxygen. All volumes have been

+(X+~)02 ~ ~
reduced to NTP. Calculate the molecular formula of the
CxHy xC0 2 + H 20 hydrocarbon gas. .
Solution: Letthe formula of the hydrocarbon beCxHy-
After explosion, the tube is allowed to cool to. room
temperature. The volume of the gaseous mixture is reco~ded. Its combustion can be shown by the following equation:
The volume corresponds to unreacted oxygen ang carbon
dioxide. The volume of carbon dioxide is determined by the CxHy + (X+~)02 ~ xC0 2 +fH 20
decrease in volume of the gaseous mixture when caustic
potash solution is introduced into the eudiometer tube. The 1 vol. x vo!'
caustic potash solution absorbs whole of carbon dioxide. The
gas left behind is the unreacted oxygen. Volume of oxygen 5 mL S(x + i) mL 5x vol.
used is then calculated by subtracting the volume ofunreacted
oxygen from the total volume of the oxygen taken initially. Volume of carbon dioxide produced = (25 - 15) = 10 mL
The molecular formula of the hydrocarbon can be 5x =10 .
evaluated by knowing (i) the volume of gaseous hydrocarbon or x=2
taken, (U) the volume of oxygen used, and (iii) the volume of Volume of oxygen used = (30 -15) = 15 mL
carbon dioxide produced.
y] Y15
ILLUSTRATIONS OF OBJECTIVE QUESTIONS [ 4 =15
5 x+ or x+ 4 ="5=3

13. An organic compound has C and H percentage in the ratio 2+ y =3

°
6: 1and C and percentage in the ratio 3: 4. The compound
is:
or

Y
4

(a) HCHO (b) CH3 0H or -=3-2=1

4
(c) CH3 CH2 0H (d) (COOHh
or y=4
[Ans. (a)]
°
lBint : % ratio of C: H is 6: I and % ratio of C: is 3: 4.
Thus, the molecular formula of the hydrocarbon C 2H 4
°
So, % ratio of C: H: is 6: I: 8.
Therefore, % ofC comes to be 3.33, % ofH is 6.66 and % of
Problem 20. 10 mL of a gaseous hydrocarbon was
exploded with oxygen. After· explosion, there was· a •
° °
is 3.33. Simplest ratio of C: H: is I: 2: 1, i.e., CH 2 0.]
14. A hydrocarbon (X) was found to have a molecular weight
contraction of 20 mL in volume. On shaking the residual
gaseous mixture with KOH, there was afurther concentration
of 80-85. A 10.02 mg sample took up 8.40 mL of H2 gas of20 mL in volume. Calculate the molecular formula. All the
measured at O°C and 760 rom pressure. Ozonolysis of (X) volumes were recorded at same temperature and pressure.
yields only HCHO and OHC--CHO. Wh'at was
Solution: Let the formula of the hydrocarbon ~eCXHy.
hydrocarbon?
(a) C6 Hg (b) C6 HIO The combustion of the hydrocarbon can be shown as :

(x+~)o~ ~
(c) C6 H12 (d) C6 HI4
[Ans. (a)] i.e., Hexa-I,3,5-triene CxHy + xC0 2 +fH 20

t (H2C=CH-CH=CH-CH=CH2 )
lBint : Moles of H2 taken up
3
IOxmL
: 8.40 X 10- == 3.75 X 10-4
The first reduction in volume after explosion
22.4
Moles of compound:
10.02 x 10-3
22.4
: 1.253 x 10-4 : 10 + 10 [x + : J-lOx =20
Thus, moles of H2 taken up by 1 mole of compound
: 3.75 X 10-4 =3 =10+. lOy
4
=20
1.253 X 10-4
10x4
Therefore, molecules has three double bonds and it may be Thus, y==--=4
10
hexa-l ,3 ,5-triene.]
Volume of carbon dioxide produced =20 mL
Problem 19. :;'mL of a gas containing only carbon and
Thus, lOx == 20
hydrogen were mixed with an excess OJ 'oxygen (30 mL) and 20
the mixture exploded by means of an electric spark. After the x=-=2
10
explosion, the volume of ihe mixed gases remaining was-
... . Henc,e, the molecular formula. of the hydrocarbon: C2 H4
":
. \
54 G.R.B. Organic Chemistry for Competitions

2.7 MODERN METHODS OF STRUCTURE Most ofthese ions carry a unit positive charge. The parent
ELUCIDATION molecular ion possess so much excess energy that' they often
brea~ up to give new smaller positive ions called fragment
Several new techniques have been designed during the ions through various bond cleavages.
last three or four decades which help in complete elucidation ABC+
of the structure of an organic compound. These techniques not
only help in determination of the molecular mass and various .ABC electric beam-E AB+C+
functional groups present in the molecule but also help to A+BC+
detemrine the complete three-dimensional structure of the . For example, a molecule of 2,2-dimethyl propane
molecule including bond length and bond angle, etc. These (neo-pentane) may break up as:
methods are broadly divided into two groups:
CH 3
. roscopic methods: These methods are based
either on the absorption or radiation or the emission of I
(CH3)4C or CH 3 -C-CH 3 C SHt2 +e-,
radiation. The molecular mass is easily determined by the use
of Mass spectrometry. The infrared(IR), ultraviolet (UV),
I Parent ion
(Mass 72)
CH 3
and nuclear magnetic resonance (NMR) techniques are used 2,2-Dimethyl propane (CSH12)
these days to detect the presence of functional groups in the
molecule. C4H; (Mass 57)
~hifraction methods: X-ray diffraction, neutron CSH12 C 3 H; (Mass = 43)
diffraction and electron diffraction techniques are
commonly used to determine the three-dimensional structure. - E C 2 H; (Mass = 29)
These methods also help in the measurement of bond lengths . Energy required to knock ion from an electron (ionisation
and bond angles. potential) is only about 10-15 eY. Since, energy of the
electron in practice is approximately 50-75 eV, the molecular
. Mass Spectrometry ion is fonned with an excess energy which is large enough to
Mass spectrometry is the most accurate method for further break it down into a mixture of neutral and positively
determining the molecular mass of a compound and its charged fragments. '
elemental composition like molecular formula and molecular Each kind of ion has a particular mass-to-charge ratio or
structure of an unknown compound. When the vapour of a mlZ value. For most of the ions, the charge (Z) is (i- 1), so that
compound in high vacuum is bombarded with a moving beam mlZ usually represents the mass of the ion. All positive ions
of high energy electrons (::::. 70eV), ionisation of some are accelerated in an electric field and then passed through a
molecule occurs with the formation of a radical cation. magnetic field when these get separated. Ions having the same
Molecule+e- ~ (Moleculet +2e- mass to charge ratio are, thus collected into beams.
(M) Radical cation (or M+) Gases, liquids or solids may be used in the determination
of mass spectra.

4
Molecular Analysis of Organic Compounds 55

IMPORTANT POINTS TO REMEMBER (SU,MMARY)

Qualitative analysis of a pure organic compound is carried Percentage of halogens (X) (Carius method)
out for detection of elements present in it. Atomic mass of X
~-----------------
Nitrogen, sulphur, halogens and phosphorus are detected (108 + Atomic mass of X)
by Lassaigne's test. Carbon and hydrogen are estimated by
determining the amounts of carbon dioxide and water x Mass of AgX formed x 100
produced (Liebig's method). Nitrogen is estimated by Mass of the compound
Duma's or Kjeldahl'smethod and halogens by Carius [For CI (X =35.5), Br (X =80), I (X = 127)]
method. Sulphur and phosphorus are estimated by oxidising
Percentage of sulphur (Carius method)
them to sulphuric and phosphoric acids respectively (Carius
method). , = 32 x Mass of BaS0 4 formed xl00 '
Relations for the estimation of elements in organic . 233 Mass of the compound .
compounds: Percentage of phosphorus (Carius method)
Percentage of carbon (Liebig's method) = 62 x Mass of Mg 2 P20 7 formed xloo
12 Mass of CO 2 formed 00 222 Mass of the compound '
=-x xl
44 Mass of the compound
The percentage of oxygen is usually determined by
Percentage of hydrogen (Liebig's method) difference between the total percentage (loo) and the sum of
2 Mass of H 20 formed percentages of all other elements present.
=-x xlOO Molecular mass determination can be done by the
18 Mass of the compound
following methods:
Percentage of nitrogen (Duma's method) (a) For volatile com- (i) Victor Meyer's method
28 Volume of N 2 at NTP pounds
x' x 100 (ii) Duma's method
22,400 Mass of the compound
(iii) Hofmann's method
Percentage of nitrogen (Kjeldahl's method)
1.4 x Normality of acid used x Volume of acid used (b) For non-volatile (i) Elevation in boiling point method
compounds
Mass of ,the compound (ii) Depression in freezing point method
(c) Chemical methods (i) Silver siilt'method for acids
(ii) Platinichloride method for bases
(iii) Volumetric methods for both acids
and bases
56~ ____________________________~__~ ___________~__________~Gw.R&,~Bl,~Q~r~ga~nwz~cjCJh~e~mll~~t~ry~gfo~rjC~o~mw~~e~ti~U~Q~ns

E,'Ul:,.:.:~~;=;:;::;;;;';;;:;;::::;:;;:; rg.u.f:s. T10l'!§ i;;;-r:;;~!;--;'::::',;:::;~-';;;:;'::!:;";::~;--1

" VERY~HORT [Link].R TYP,~ (v) When an organic compound is heated with dry cupric
1, Fill in the blanks: oxide and the gases evolved are
passed through
lime water which rums milky, the gas may be
(a) Lassaigne's test can be applied for the detection of
......, sulphur and ...... in organic Compounds. . .. ,... or ..... .
(w) If nitrogen and sulphur both are present in an organic
(b) In the Lassaigne's test, the sulphur present in the
organic compound is converted into , ... , . compound and it is fused with sodium. The sodium
(c) In the Lassaigne's test, the nitrogen present in the compound formed is ..... .
(x) The percentage of carbon in CH 4 is ..... .
organic compound is converted into ..... .
(d) The formation of violet colour by the addition of (y) Equivalent mass of a base
sodium nitroprusside to the Lassaigne's solution is the
indication of, ..... element in the organic compound.
=i[ ..............
2 Mass of platinum
x 195-410 1
J
(e) In the Kjeldahl's process, the nitrogen present in the
(z) The basicity ofthe acid is ...... if its molecular mass
organic compound is changed into ...... by heating
is 104 and equivalent mass is 52.
the compound with concentrated H 2 S04 ,
2. State whether the following statements are True or False:
(f) In Lassaigne's test for halogens, concentrated HN03 is
(a) All organic compounds contain carbon and hydrogen
used to destroy . . , . , . and .. , , , .
both.
(g) In Carius method, sulphur is oxidised to ...... with
(b) Carbon and hydrogen are detected simultaneously in
,fuming nitric acid.
an organic compound by Liebig method
(h) In Duma's method, the nitrogen present in an organic
(c) Beilstein test is reliable test for halogens in organic
compound is released as ...... gas.
compounds.
(i) To determine the amount of halogen in an organic
(d) Sulphur is estimated by Carius method as barium
compound, the compound is heated with fuming
SUlphate.
HN0 3 in presence of ..... .
(e) Mol. mass of an acid = Equivalent mass x acidity.
G) In the Lassaigne's solution with nitrogen present in the
organic compound, ferrous sulphate solution is added
(f) Victor Meyer's method is used for the determination of
molecular mass of a non-volatile compound.
and then boiled. It is neutralised with dilute H 2 S04 , A
(g) Duma's method can be' applied for estimation of
bright. , .... solution is formed.
nitrogen in all nitrogenous organic compounds.
(k) . Molecular· mass of the base = Equivalent mass X
(h) Ared solution is obtained when ferric chloride solution
is added to sodium extract. It indicates both nitrogen
(I) Equivalent mass of the acid
and sulphur are present in the organic compound.
_(MaSSOf ...... ) (i) In Lassaigne's test of nitrogen, the fmal product
- MassofSl' lver
' x108-107
formed is sodium ferrocyanide.
G) Kjeld~l's method IS applicable to all nitrogenous
(m) 1000 mL 1 N alkali solution = ...... of the acid.
organic compounds.
(n) Molecular mass of a gaseous liydrocarbon can be
(k) Phosphorus is estimated by Carius method as
determined even without knowing its percentage
magnesium pyrophosphate.
composition by . . . . . . .
(I) Ordinary CUO is used in Liebig's combustion method
(0) Empirical formula indicates ...... present in one
for estimation of carbon and hydrogen in organic
molecule of a compound.-
compounds.
(P) Molecular formula indicates ...... of each of the
(m) An organic base, B, whose acidity is one when
constihlent elements present in one molecule.
combines with H 2 PtCl 6 forms insoluble compound of
'. (q) Molecular formula =n X empirical formula
formula B2 H 2 PtC1 6 .
where n=':":':":":': (n) Molecular mass .
.. 1 '" . = n, 'where n is always a whole
E mpmca lormula mass .
(r) Empirical formula of C6H6 is . . . . .. .
number.
. (s) Empirical formula ofC6H 12 0 6 is ..... .
(0) Silver salt methOd is a chemical method for the
(t) The vapour density ofNH2 CONH 2 is . . . . .. .
determination of equivalent mass of organic bases.
(u) ~e sodium extract of an organic compound on boiling
(P) Estimation of oxygen in an organic compound can be
With .RN0? and treatment with ammonium molybdate
made by Aluise method;
solution gives a yellow precipitate. It indicates the
(q) In the Carius method, the sealed Carius tube
presC''1ce of ...... in the compound.
. containing organic compound, fuming nitric acid and
,

J
Molecular Analysis ofOrganic Compounds 57

silver nitrate is heated at 300°C for six hours in the (g) Estimation of carbon 7. Kjeldahl's method
estimation of halogens. and hydrogen in an
(r) In Kjeldahl's method, during digestion of the organic organic compound
compound with conc. H 2S04, potassium sulphate and 5. Complete the following:
sodiuni' sulphate are also added.
H+
(s) An organic compound containing nitrogen, on heating (i) (CH 3COOhPb+Na 2S ~ ...... + ..... .
strongly with H2 SO4 gives ammonium sulphate which
(ii) Fe3+ + 3NaCNS ~ ...... + ..... .
on treatment with excess ofNaOH liberates ammonia.
(t) The simplest formula that shows the ratio of the atoms (iii) NaI + AgN03 ~ ...... + ..... .
of the various elements present in the molecule is (iv) 4FeCl 3 + 3Na4Fe(CN)6 ~ ...... + ..... .
called the molecular formula. (v) FeS0 4 + 6NaCN ~ ...... + ..... .
(u) The molecular mass of a non-volatile organic com-
(vi) Na2S+Na2Fe(CNhNO ~ ..... .
pound is determined either by the Victor Meyer's.
method or Duma's method. (vii) (NH4 h S04 + 2NaOH ~ ...... + ...... + .... ..
(v) The gas displaced in Victor Meyer's method is air.. (viii) 5CO+I20 5 ~ •••.•. + ..... .
(w) The gas estimated in Duma's method is nitrogen. (ix) RCOONH4 + AgN03 ~ ...... + ..... .
(x) A Lassaigne's solution is boiled with dilute HN0 3 ,
cooled and AgN03 .added. It gives a yellow precipi- (x) CxHy +(X+~)02 ~ ...... + ..... .
tate, sparingly soluble in ammonia. This indicates the
presence of iodine in the organic compound. ~ SH"OaT AN,SWER TYPE
(y) A black precipitate is formed when lead acetate 6. Describe the following:
solution is added to acidified sodium extract of an
(i)' Chemistry of Lassaigne's test for the detection of
organic compound containing sulphur.
. nitrogen in an organic compound.
(z) Copper wire is used in Beilstein test.
(ii) Chemistry of Lassaigne's test for the detection of
3. Give reasons:
sulphur in an organic compound.
(i) During the test for nitrogen in Lassaigne's filtrate,
(iii) Chemistry of Lassaigne's test for the detection of
sometimes red colouration is' obtained when ferric
halogens in an organic compound.
chloride is added.
(iv) Chemistry of Kj~ldahl's method for the estimation of
(ii) Why is sodium extract made acidic with acetic acid
nitrogen in an organic compound.
before the addition oflead acetate in the test of sulphur?
(v) Platinichloride method of determination of molecular
(iii)' In the test of nitrogen, freshly prepared solution of
mass of an organic base.
ferrous sulphate is always used.
(vi) Silver salt method of determination of molecular
(iv) During the test for halogens, why is sodium extract
mass of an organic acid.
first boiled with a few drops of conc. HN0 3 ? (vii) Principle of Duma's method for the estimation of
(v) Why the organic compound is fused with sodium metal nitrogen in an organic compound
during detection of nitrogen, sulphur, halogens, etc.? (viii) Liebig method for the estimation of carbon and
(vi) What is the role of copper sulphate and potassium hydrogen in an organic compound.
sulphate in Kjeldahl's process for the estimation of (ix) Carius method for the estimation of sulphur in an
nitrogen in an organic compound?
organic compound.
(vii) Is Beilstein test a satisfactory test for detection of
(x) Carius method for the estimation of halogens in an
halogens?
organic compound.
4. Match the following:
fl.'operty to be Method used for (xi) How is molecular formula of a hydrocarbon derived
determined determination by eudiometry?
(xii) The difference between empirical and molecular
(a) Molecular mass of a I. Silver sMt method formula and the relationship between them.
volatile organic solid (xiii) Layer test for bromine ana iodine in an organic
(b) Molecular mass of a non- 2. Liebig method compound.
volatile organic solid (xiv) Aluise's method for the estimation of oxygen in an
(c) Estimation of chlorine 3. Platinichloride method organic compound.
in carbon tetrachloride (xv) Beilstein test or copper wire test.
(d) Estimation of nitrogen 4. Victor Meyer's method
""".. j:_liiliMANSWERS·:ish· - =!t'_':,'1,~~
in l;Uliline
.
1. (a) nitrogen; halogens; (b) sodium su1phide', (c) sodium cyanide;s..
(e) Equivalent mass of an 5. Depression in freezing
. u1 hate' (f) HCN and H 2 ,
organic acid point (d) sulphur; (e) ammoruum s p. ' d' (k) acidity"
(f) Equivalent mass of an 6; Carius method (g) H 2S04; (h) nitrogen; (i) AgN0 3; (j) blu~coIO:. (0) simp';
(I) silver salt; (rn) equivalent mass; (n) eu orne •her ..
organic base ratio of atoms of constituent elements; (P) actual num
58 G.R.B. Organic Chemistry for Competitions

(q) Molecular mass . (r) CH; (s) CH 20; (t) 30; (ii) Lead acetate is hydrolysed by NaOH present in sodium ex-
Empirical formula mass' tract. It is neutralised first with acetic acid before the addi-
(u) phosphorus; (v) CO 2 , S02; (w) NaCNS; (x) 75; (y) mass of tion of lead acetate.
platinum salt; (z) two. (iii) Ferrous sulphate gets hydrolysed if its solution is stored.
2. (a) False-hydrogen is not always present; (b) True; (iv) As to decompose NaCN or NazSifpresent in the sodium extract.
(c) False-sometimes the test fails; (d) True; (v) As to convert nitrogen, sulphur or halogens present in an or-
(e) False-molecular mass of an acid = equivalent ganic compound into ionisable substances.
mass x basicity; (t) False-used for a volatile compound; (vi) Copper sulphate acts as a catalyst white potassium sulphate
(g) True; (h) True; (0 False-the fmal product formed is raises the boiling point of H 2S04,
ferri-ferro cyanide; (j) False-not applicable to pyridine, (vii) It is not always reliable. Substances such as urea, thiourea,
compounds containing N-N, N-O, etc. bonds; (k) True; pyridine, organic acids, etc., also impart colour to flame.
.(1) False-dry CuO is used; (m) True; (n) True; (0) False-for 4. (a-4); (b-5); (c-<i); (d-7); (e-l); (f-3); (g-2) .
the determination of equivalent mass of organic acids; (P) True; 5; (i) 2CH 3COONa + PbS 0:) Fe(CNS)3 + 3Na+
(q) True; (r) False-potassium sulphate and copper sulphate are
(iii) AgI + NaN0 3 (iv) Fe4[Fe(CNk;h+ 12NaCI
added; (s) True; (t) False-is called empirical formula;
(v) Na4[Fe(CNk;] + Na2S04 (vi) Na4[Fe(CN)sNOS]
(u) False-determined by either elevation in boiling point method
(vii) 2NH3 + Na 2S0 4 + 2H 20 (viii) 12 + 5C02
or depression in freezing point method; (v) True; (w) True;
(x) False-indicates the presence of bromine; (y) True; (z) True. (ix) RCOOAg + NH4N03 (x) xC0 z + ~ H20
3. (i) When nitrogen and sulphur both are present in an organic 2
compound, sodium thiocyanate is formed which gives red
colouration with FeC1 3•

r~::<:::::::' ::i::" NUMERICAL PROBLEMS FOR PRACTICE It;

;

1. 0.45 g of an organic compound gave on combustion 0.792 g 6. 0.33 mole cholesterol gives 9 mole CO 2 on combustion. It
of CO 2 and 0.324 g of water. 0.24 g of the same substance was observed that cholesterol contains 83.85% C; 12% H
was Kjeldahlised and the ammonia fonned was absorbed in and 4.15% 0. Find its molecular fonnula and molecular
50 mL of 0.25 N H 2S04 , The excess of acid required mass.
77.0 mL of 0.1 N NaOH for complete neutralisation. IAns. C z7 H 4P; 386)
Calculate the empirical fonnula of the compound.
7. An automobile antifreeze consists of 38.7% carbon; 9.7%
(Ans. C4HsNzOl
hydrogen and remaining oxygen by weight. When 0.93 g of
2. A compound contains 40% C, 6.66%. Hand 53.33% 0.
it are vaporised at 200°C and 1 atm pressure, 582 mL of
An examination reveals that 9.0 g of the compound
vapour are formed. Find molecular fonnula of antifreeze.
dissolved in 500 g of water raises the boiling point of
(Ans. C zHp zl
water by 0.051°C. What is the molecular fonnula of the
8. The compound [Pd(CxHyN z )](CI0 4 h contains 30.15%
compound? [Kf =0.51Kmor l kg]
carbon and 5.06% hydrogen. The compound
(Ans. CJllz061
3. Tyrosine is one of the amino acids present in protein. Its [Pd(CXHyN z )](SCN)2 contains 40.46% carbon and 5.94%
content in the protein is 0.22% and its molecular weight is hydrogen. Calculate x, y, Z.
181 g mol-l. What is the lowest molecular weight of the IAns. x=14,y=ZS,z=4)
protein? 9. Methyl orange, an acid base indicator, is the sodium salt of
(Ans. 82272) an acid that contains C, H, N, S and oxygen. Quantitative
4. A molecule was known by its mode of synthesis to contain analysis gave C = 51.4%, H = 4.3%, N = 12.8%, S = 9.8%
10 atoms of carbon per molecule, along with unknown and Na = 7.0%. What is the empirical fonnula of methyl
number of chlorine, hydrogen and oxygen. Analysis orange?
indicates that it contains 60.5% carbon, 5.55% hydrogen, IAns. CI4HI4N3S03Nal
16.1% oxygen and 17.9% chlorine. Derive molecular 10. The sulphur content of cystine is 26.7%. Given that cystine
formula. contains two sulphur atoms, what is the molecular weight of
(Ans. CloHnO:zCI) . cystine?
5. A w~lding fuel gas con~carbon and hydrogen only. IAns. 239.7 g)
Bummg a small sample of It m oxygen gives 3.38 g carbon (Bint: Atomic mass of sulphur is 32, hence for two sulphur
dioxide, 0.690 g of water and no other products. A volume atoms, the molecular formula will have 64 g sulphur.
of 10 litre (measured at STP) of this welding gas is found to Thus, if 26.7 g sulphur, then molecular weight = toO g.
weigh 11.6 g. Calculate (i) empirical formula (ii) molar and if 64 g sulphur is present, molecular weight
mass of the gas (iii) molecular formula. 100x64 .
= ~-- = 239.7 g morl]
[Ans. (i) CH z (Ii) 26 (iii) CzH z) 26.7

1m!'
 MolecularAnalysis o/Organic Compounds 59
;:-""~ ~ ~

_~~~~08JEClIVE
- < - , • .. • - ,

'.
OUESIIOIS I,,~

.-
_. _ _ _ _~~.~:

-"- ' - '--~---~~-;

SET I ! This set contains the questions with single correct answer. (a) nitrogen 0 (b) phosphorus 0
1. Carbon and hydrogen are estimated in organic compounds by: (c) sulphur 0 (d) chlorine 0
(a) Kjeldahl's method 0 (b) Duma's method 0 11. Which of the following compounds gives blood red
(c) Liebig's method 0 (d) Carius method 0 colouration when its Lassaigne's extract is treated with
2. Lassaigne's test is used for the detection of: alkali and ferric chloride? [DPMT 2009]
(a) carbon only 0 (a) Thiourea 0 (b) Benzamide 0
(c) Phenyl hydrazine 0 (d) Diphenyl sulphide 0
(b) hydrogen only "\ • 0
12. Copper wire test of halogens is known as:
(c) oxygen only 0
(a) Liebig's test 0 (b) Lassaigne's test 0
(d) nitrogen, sulphur and halogens 0 (c) Fusion test 0 (d) Beilstein's test 0
l. In Lassaigne's test, the organic compound is fused with 13. Duma's method involves the determination of nitrogen
sodium metal as to: .
content in the organic compound in the form of :
(a) hydrolyse the compound 0 [BBU 2005]
(b) form a sodium derivative 0 (a) NH3 0 (b) N2 0
(c) convert nitrogen, sulphur or halogens if present into
soluble ionic sodium compound 0 (c) NaCN 0 (d) (NH4)2S04 0
(d) burn the compound 0 14. In Lassaigne's solutio!1. pink/violet colouration is produced
4. Nitrogen containing organic compound when fused with when sodium nitroprusside solution is added. It indicates
sodium metal forms: [CET (Karnataka) 2006) the presence of:
(a) NaN0 2 0 (b) NaCN 0 (a) sulphur 0 (b) nitrogen 0
(c) chlorine 0 (d) none of these 0
(c)NaNH 2 0 (d) NaNC 0 IS. An organic compound on heating with CuO produces CO2
S. The sodium extract of an
organic compound on treatment but no water. It may b~ ,
with FeS04 solution, FeCl 3 and RCI gives a red solution.
The organic compound contains:
(a) CR4 0 (b) C2RsI 0
(a) both nitrogen and sulphur 0 (c) CRCl 3 J 0 (d) CCl 4 0
(b) nitrogen only . 0 16. In an organic compound, Kjeldahl's method is used for the
(c) sulphur only 0 estimation of:
(d) halogen 0 (a) halogens 0 (b) sulphur 0
6. The prussian blue colour obtained during the test of (c) nitrogen 0 (d) oxygen 0
nitrogen by Lassaigne's test is due to the formation of: 17. In Lassaigne's test for the detection of halogens, the sodium
[AIEEE 2004; AFMC 2010) . fusion extract is fIrst boiled with concentrated nitric acid.
This is : [PET (Kerala) 2010)
(a) Fe4[Fe(CN)6h 0 (b) Na3[Fe(CN)6] 0
(a) to remove silver halides 0
. (c) Fe(CN)3 0 (d) Na4[Fe(CN)sNOS] 0 (b) to decompose Na2Sand NaCN, ifpresent 0
7. Which of the following sodium compound/compounds are

,
(c) to dissolve Ag 2S 0
formed "when an organic compound containing both
nitrogen and sulphur is fused with sodium? (d) to dissolve A-gCN, if formed 0
(e) because Ag 2S and AgCN are insoluble in nitric acid
(a) Cyanide and sulphide 0 (b) Thiocyanate 0
o

, (c) Sulphite and cyanide 0 (d) Nitrate and sulphide 0

8. Wh~ N and S both are present in an organic compound, the
sodium extract with FeCI 3 gives:
. (a) green colour'
(c) yellow colour
0 (b) blue colour
0 (d) red colour
0
0
18. In Kjeldahl's method of estimation of nitrogen, copper
sulphate acts as:
(a) an oxidising agent
(c) a catalytic agent
IUPSEE 2008]
0 (b) a reducing agent
0 (d). a hydrolysing agent 0
0

19. In the Duma's method for the estimation of nitrogen in an

9. The sodium extract of an organic compound on acidification organic compound, nitrogen is determined in the form of:
with acetic acid and addition of lead acetate solution gives a
(a) gaseous nitrogen 0 (b) gaseous ammonia 0
black precipitate. The organic compound contains:
(c) ammonium sulphate 0 (d) sodium cyanide 0
(a) nitrogen 0 (b) halogen 0 20. An organic compound whiCh produces a bluish green
(c) sulphur . 0 (d) phosphorus 0 coloured flame on heating in presence of copper is :
10.' The Sodium extract oian organic compound on boiling with (eET (Karnataka) 2006)
F1N03 and addition of ammonium molybdate solution gives
a yellow precipitate. The compound contains:
 60 G.R.B. Organic Chemistry (or Competitions

(a) benzaldehyde 0 (b) benzoic acid 0 31. In the estimation of carbon and hydrogen, if the substance
(c) aniline 0 (d) chlorobenzene 0 also contains both halogen and SUlphur, then near the exit, it
21. In organic compounds, halogens are estimated by: is placed:
(a) Carius method 0 (b) Liebig's method 0 (a) a roll of silver 0
(c) Kjeldahl's method 0 (d) Duma's method 0 (b) a layer of lead chromate 0
22. In the estimation of sulphur in an organic compound, (c) a bright copper gauge spiral 0
fuming nitric acid is used to convert sulphur into: (d) none of the above 0
(a) S02 0 (b) H 2S 0 32. In carbon and hydrogen estimation, the saphnolite (a resin)
(c) H Z S0 3 0 (d) H 2 S04 0 absorbs:
23. Schiff's and Piria method is used for the estimation of: (a) N2 0 (b) water vapours 0
(a) nitrogen 0 (b) sulphur 0 (c) both COz and H 20 0 (d) only CO2 0
(c) halogens 0 (d) oxygen 0 33. Catalyst used in Kjeldahl's method for the estimation of
24. Prussian blue colour is obtained by mixing together aqueous nitrogen is:
solution ofFe 3+ salt with: tCET (J&"K) ~OO11 (a) sodium 0 (b) magnesium 0
(a) ferricyanide 0 (b) ferrocyanide 0 (c) mercury 0 (d) copper 0
(c) hydrogen cyanide 0 (d) sodium cyanide 0 34. Formula which represents a simple ratio of atoms of
2S. The blood red colour in the combination test of nitrogen and different elements present in a molecule of the substance is
sulphur in organic compound is due to the formation of: called:
(a) ferric sulpho cyanide 0 (a) molecular formula 0 (b) empirical formula 0
(b) ferric acetate [J (c) structural formula 0 (d) none of these 0
(c) ferrous sulpho cyanide 0 3S. An organic compound contains carbon, hydrogen and
(d) ferric cyanide 0 oxygen. Its elemental analysis gave C, 38.71% and H,
9.67%. The empirical formula of the compound would be:
26. The violet colour obtained during the test of sulphur by
, (CME (M~~ a_I
,'M'f
Lassaigne's test is due to the formation of:

(a) Naz[Fe(CN)sS]
(K~ftliij 1M\ CM(; (V@U{)f'@) 1-1
0 (b) Na2[Fe(CN)sNO] 0
(a) CHzO
(c) CH 3 0
0 (b) CH4 0
0 (d) CHO
0
0
36. An alkaloid contains 17.28% of nitrogen aiid its molecular
(c) Naz[Fe(CN)6] 0 (d) Na4[Fe(CNhNOS] 0
mass is 162. The number of nitrogen atoms present in one
27. Chloro acetic acid is heated with fuming nitric acid in molecule of alkaloid is: ('''\\jiD CiT (bg.) I . ,
presence of AgN03 in Carius tube. After filtration and (a) 3 0 (b) 2 0
washing, a white precipitate is obtained. This precipitate is:
(c) 5 0 (d) 4 0
(a) AgN03 0 (b) Ag 20 0 37. A hydrocarbon contains 10.5 g carbon and 1 g hydrogen. Its
(c) AgCI 0 (d) CICHzCOOAg 0 0.36 g has I litre volume at 1 atm and 1270 C, the
28. Mark the incorrect statement in nitrogen Kjeldahl's method hydrocarbon is: (U'.ftAT ""l
of estimation: (a) C6H7 0 (b) C 7Hg 0
(a) nitrogen gas is collected over caustic potash solution
. 0 (c) CSH6 0 (d) None of these 0
38. Which of the following reagents is used for the separation
(b) potassium sulphate is used as boiling point elevator of
H 2 S04 0
of acetaldehyde from acetophenone? . 'An~ I..)
(a) NH 20H 0 (b) NaOHIz 0
(c) copper sulphate or mercury acts as a catalyst 0
(d) nitrogen is quantitatively decomposed to give
(c) NaHS0 3 0 (d) C6 H sNHNH z 0
ammonium sulphate 0 39. The formula of gas is [CO]x' If its vapour density is 70, the
29. In the estimation of carbon and hydrogen, if the substance value of x will be: tOCll ~l
also contains nitrogen, then near the exit, it is placed: (a) 2.5 0 (b) 3.0 0
(a) a roll of silver 0 (c) 5.0 0 (d) 6.0 0
(b) a bright copper gauge spiral 0 40. The ammonia evolved from the treatment of 0.30 g of an
(c) ammonium sulphate 0 organic compound for the estimation of nitrogen was passed
(d) a layer of lead chromate 0 in 100 mL of 0.1 M sulphuric acid. The excess of acid
30. In the estimation of carbon and hydrogen, if the substance
" required 20 mL of 0.5 M sodium hydroxide solution for
also contains halogens, then near the exjt, it is placed:
complete neutralization. The organic compound is:
(a) a roll of silver 0
~liU*,,'
(b) a layer oflead chromate 0
(c) both, a roll of silver and a layer of lead chromate 0
(a) urea o (b) thiourea 0
(d) a bright copper gauge spIral 0
(c) acetamide o (d) benzamide 0

Iiiiir---'--------------_______________________--'-
Molecular Analysis of Organic Compounds 61.

41. How will you separate a solution (miscible) of benzene 49. Match the fo!19wing:
+ CHCl 3? (AFMC 200S) Property to be Metbod used for
(a) Sublimation 0 (b) Filtration 0 determined determination
(c) Distillation 0 (d) Crystallisation 0
42. An organic compound having molecular mass 60 is found to (A) Estimation of carbon and hydrogen (i) Lassaigne's test
contain C = 20%, H = 6.67% and N = 46.67% while rest is in an organic compound
oxygen. On heating it gives NH3 along with a solid residue. (B) Estimation of nitrogen in aniline (H) Carius method
The solid residue gives violet colour with alkaline copper (C) Estimation of chlorine in carbon (Hi) Liebig's method
sulphate solution. The compound is: tetrachloride
. (AIEEE 2005; PMT (Kenta) 2008) (D) Detection of nitrogen, sulphur and (iv) Kjeldahl's method
(a) CH3NCO 0 (b) CH3 CONH2 0 halogens .
(c) (NH4 hCO 0 (d) CH3CH2 CONH2 0
ABC D
43. A compound containing only carbon, hydrogen and oxygen,
(a) (i) (ii) (iii) (iv)
has a molecular weight of 44. On complete oxidation it is
converted into a compound of molecular weight 60. The (b) (iv) (iii) (i) (ii)
original compound is: (KCET 200S) (c) (ii) (i) (iv) (iii)
(a) an aldehyde 0 (b) an acid 0 (d) (iii) (iv) (ii) (i)
(c) an alcohol 0 (d) an ether 0 SO. Match the following:
(A) Equivalent mass of an organic acid (i) Depression in
44. 29.5 mg of an organic compound containing nitrogen was freezing point
digested according to Kjeldahl's method aildthe evolved
(B) Equivalent mass of an organic base (ii) Victor Meyer's
ammonia was absorbed in 20 ml of 0.1 MHCI solution. The
method
excess of acid required 15 mlofO,1 MNaOH solution for
(C) Molecular mass of a volatile or- (iii) Platinichloride
complete neutralisation, The percentage of nitrogen in the
gamc solid method
compound is': (AIEEE 2010)
(a) 29,S 0 (b) 59.0 0 (D) Molecular mass of a non-volatile (iv) Silver .salt method
organic solid
(c) 23.7 0 (d) 47.4 0
45~ An aromatic hydrocarbon with empirical formula C SH.4 on B C D
A
treatment with concentrated H2 SO 4 gave a monosulphonic (a) (iv) (iii) (ii) (i)
acid. 0.104 g of the acid required 10 ml of N/20 NaOH for (b) (i) (ii) (iii) (iv)
complete neutralisation. The molecular formula of (c) (iii) (i) (iv) (ii)
hydrocarbon is: (PET (Kerala) 2007]
(d) (ii) (iv) (i) (iii)
(a) CSH4 0 (b) ClOHg 0
SET II: This set contains the questions with one or more correct
(c) CI5 H 12 0 (d) C2o H16 0 answers.
(e) C 1s H 20 0 51. Which of the following compo,unds may give blood red
46. When 20 g ofnaphthoic acid (CII Hg O2 )is dissolved in 50 g colouration while performing Lassaigne's test for nitrogen?
of benzene (K f = 1.72 K kg mol-I), a freezing point (a) (NH2)2CO 0 (b) (NH2hC=S 0
depression of 2K is observed. The van't Hoff factor (0 is: (c) p-NH2 C6H4 S0 3H 0 (d) C6HsS03H 0
(lIT 2007) 52. The desiccants used for absorbing water during Liebig's
(a) 0.5 0 (b) I 0 method for estimation of carbon and hydrogen are:
~2 0003 0 (a) Anhydrous CaCl 2 0 (b) Anhydrous Na2S04 0
47. Sodium fusion extract, obtained from aniline, on treatment
with iron (II) sulphate and H2 SO4 in presence of air gives a
(c) MgS04 ·7H20 0 (d) Mg(CI0 4 h 0
prussian blue precipitate. The blue colour is due to the 53. The empirical formula of a compound is CH 2. To which of
formation of: [liT 2007) the hydrocarbon series does it belong?
(a) Fe4[Fe(CN)6h 0 (b) Fe3 [Fe(CN)6h 0 (a) Alkanes· 0 (b) Alkenes 0
(c) Fe4[Fe(CN)6h' 0 (d) Fe3[Fe(CN)6h 0 (c) Alkynds 0 (d) Cydoalkanes 0
48. CamphOr is often used in molecular mass determination . 54. An organic compound contains about 52% carbon. Ii could
because: (UGET (Meet) 2007) be:
(a) it is readily available 0 (a) ethanol 0 (b) dimethyl ether 0
(b) it, has a very high cryoscopic constant 0 . , (c) acetic acid 0 (d) phenol 0
(c) it is volatile 0 55. Presence of halogen in a compound is tested by:
(d) it is solvent for organic substances 0 (a) Iodoform test 0 (b) Millon's test 0
(c) Silver nitrate test 0 (d) Beilstein test 0
62 G.R.B. Organic Chemistry for Comvetitions

56. The weights of carbon, hydrogen and oxygen in an organic (c) C6H 5 CI o
compound are in the ratio 6: 1 : 8 respectively. The (d) 2,6,6-Trinitrochlorobenzene o
molecular formula of the compound may be: , 58. Violet coloured complex obtained in the detection of
(a) CHzO D (b) CZH40Z 0 sulphur is: [AFMe 2010]
(c) CHzOz 0 (d) C3 H 6 0 3 (a) Naz[Fe(NO)(CN)sl D
57. Which of the organic compounds will give white precipitate (b) Na3[Fe(ONSNa)(CN,s] D
with AgN03?
(c) Na4[Fe(CN)sNOS] o
(a) C6HSNH;CI- 0
(d) both (b) and (c) Cl
(b) NaCI 0

Section A : liT Type Questions Section B : AIIMS Type Questions

These questions consist of an Assertion (A) and the Choose the correet answer:
Reason (R). Use the following keys to choose the appropriate (a) If both (A) and (R) are correct and (R) is the correct
answer: explanation of (A).
(a) If both assertion and reason are correct and reason is (b) If both (A) and (R) are correct but(R) is not the correct
the correct explanation of the assertion. explanation of (A).
(b) If both assertion and reason are correct but reason is (c) If (A) is correct but (R) is incorrect.
not the correct explanation of the assertion. (d) If both (A) and (R) are incorrect.
(c) If assertion is correct but reason is incorrect. 7. (A) p-NHzC6H s S0 3H gives blood red colouration while
(d) If assertion is incorrect but reason is correct. performing Lassaigne's test for nitrogen.
1. (A) Lassaigne's test can be used to detect nitrogen in (R) Sodium fusion extract containing NaCNS gives blood
hydrazine. red colour on treatment with FeC1 3.
(R) During fusion with sodium metal, nitrogen and carbon 8. (A) Lassaigne's test is not shown by diazonium
of the organic compound combine to form sodium compounds.
cyanide. (R) Diazonium compounds lose N2 on heating before they
2. (A) If sulphur and nitrogen are also present in organic combine with fused sodium.
compound along with halogen then AgN03 solution is 9. (A) Iftwo compounds have the same empirical formula but
added in acidified sodium fusion extract.
different molecular formula, they have same vapour
(R) On acidification, NaCN and Na zS decompose.
density.
NaCN + HN03 ---+ NaN03 + HCNt (R) glmL is the unit of vapour density.
NazS + 2HN03 ---+ 2NaN03 + Hz st 10. (A) Duma's method is more applicable to nitrogen
3. (A) Litmus is not used in Lassaigne's test. containing organic compounds than KjeJdahl's
(R) It generally forms covalent compounds. method.
4. (A) In' Victor Meyer's method, vapour density is (R) Kjeldahl's method does not give satisfactory results for
considered to be one-half of molecular weight. compounds in which nitrogen is linked to oxygen.
(R) Vapour density is other name of density. U. (A) Hydrazine contains nitrogen but does not give
5. (A) Nitrogen cannot be estimated in nitrobenzene by Lassaigne's test for nitrogen.
Kjeldahl's method. (R) Hydrazine reacts with fused sodium to give H2 gas. .
(R) Nitrobenzene evolves ammonia gas on acid treatment. 12. (A) Sodium fusion extract of a compound gives black
6. (A) All compounds containing an odd number of nitrogen precipitate with lead acetate.
atoms have odd masses and those which contain even (R) Sulphur containing compounds form NaiS in sodium
number of nitrogen atoms have even masses. fusion extract.
(R) Nitrogen rule can be applied to 1)oth aliphatic and
aromatic compounds.
Molecular Analysis of Organic Compounds 63

,ANSWERSJ
OBJECTIVE QUESTIONS
1. (c) 2. (d) 3. (c) 4. (b) 5. (a) 6. (a) 7. (b) 8. (d) 9. (c) 10. (b)
11. (a) 12. (d) 13. (b) 14. (a) 15. (d) 16. (c) 17. (b) 18. (c) 19. (a) 20. (d)
21. (a) 22. (d) 23. (c) 24. (b) 25. (a) 26. (d) 27. (c) 28. (a) 29. (b) 30. (c)
31. (b) 32. (d) 33. (c) 34. (b) 35. (c) 36. (b) 37. (b) 38. (c) 39. (c) 40. (a)
41. (c) 42. (c) 43. (a) 44. (c) 45. (c) 46. (a) 47. (a) 48. (c) 49. (d) 50. (a)
51. (b,c) 52. (a,d) 53. (b,d) 54. (a,b) 55. (c,d) 56. (a,b,d) 57. (a,d) 58. (d)

ASSERTION-REASON TYPE QUESTIONS

"

1. (d) 2. (a) 3. (a) 4. (c) 5. (c) 6. (b) 7. (a) 8. (a) 9. (d) 10. (b)
11. (a) 12. (b)
 64 G.R.B. Organic Chemistry for Competitions

1. Which among the following is not correctly matched with 7. 9.9 g amide with molecular formula C4H sN x O y on heating
their colour? with alkali liberated 1.7 g of ammonia. If the pe1:Centage of
Compound Colour oxygen is 33.33% then the ratio of 'N' and '0' atoms in the
(a) Na4[Fe(CN)sNOS] purple o compound is:
(b) Fe4[Fe(CN)6h blue 0 (a) 1 : 1 0 (b) I : 2 0
(c) Fe(CNSh blood red 0 (c) 2 : 3 0 (d) 3 : 2 0
[Hint: Amide C4HS NxO y will give x mol NH 3•
(d) AgCI light yellow 0
2. In case, nitrogen and sulphur both are present in an organic :. Molecular mass of amide = 9.9 x 17x 99x
1.7
compound, sodium thiocyanate is formed. If sodium fusion
is carried out with excess of sodium, sodium thiocyanate % Nitrogen in the amide = 14x x 100= 14.14
decomposes. Which of the following compounds is/are 99x
present in the extract after decomposition? % Oxygen in the amide = 33.33
(a) NaCN 0 (b) Na2S 0 Ratio of number of atoms of 'N' and '0'
(c) Both 0 (d) None of these 0 = 14.14 : 33.33 = I: 2]
3. 0.0833 mole of a carbohydrate of empirical formula CHzO 14 16
contains 1.00 g of hydrogen. The molecular formula of the 8. Lassaigne's test is not shown by diazonium salts because
carbohydrate is: . . they:
(a) CSHlOOS 0 (b) C3H40 3 0 (a) form NH3 gas on heating much before the reaction with
(c) C12H22011 0 (d) C6H12 0 6 0 sodium . 0
1 (b) form N2 gas on heating much before the reaction with
[Hint: 'I mole of carbohydrate will contain --gof
0.0833 sodium D
hydrogen, i.e., 12 g hydrogen.
(c) are highly volatile and evaporate before the reaction
:. The molecular formula of the compound will be C6H 120 6] with sodium 0
4. Select the organic compounds, which will give red colour in (d) all of the above D
Lassaigne's test? 9. 0.28 g of a nitrogenous compound was Kjeldahlised to
(a) NaCNS 0 produce 0.17 g of NH 3 . The percentage of nitrogen in the
organic compound is:
~
(b) NH2-C-NH2 0
(a) 5
(c) 50
D (b) 30
(d) 80 o
0
0
S [Hint: 0.17 g NH3 will contain (!~ x 0.17) g of nitrogen, i.e.,
11
(c) NH2-C-NH2 o 0.14 g of nitrogen
. Mass of
% Nitrogen = ~~~~~~ x 100
(d) H2N-{ )-S03Na+ . Mass of compound
o
= 0.14 x 100 50%]
5. The desiccants used for absorbing water during Liebig's 0.28
method for estimation of carbon and hydrogen are:
10. Kjeldahl's method cannot be used for estimation of nitrogen
(a) CaCl 2 0 (b) Na2S04 0 in:
(c) MgS04 ,7H20 0 (d) Mg(CI04 )2 0 (I) C6H s CONH2
[Hint: . Anhydrous CaCl 2 and Mg(CI04)2 are used as desiccants (II) Pyridine
because they are efficient absorben~ of water.] (III) C6Hs-N=N-C6Hs (IV) C6HsNHCOCH3
6. Kjeldahl's method can not be used for estimation of (a) I, III 0 (b) II, III 0
nitrogen in: (c) III, IV 0 (d) I, II D
(a) pyridine o (b) azobenzene o
(c) nitrobenzene o
(d) all of these D

ANSWERS: BRAIN STORMING PROBLEMS 1--------------------:----,

1. (d) 2. (6) 3. (d) 4. (c,d) 5. (a,d) ,6. (d) 7. (b) 8.. (b) 9. (c) 10. (b)

•
G.R.B. Organic Chemistry for Cmnpetitions

LINKED COMPREHENSION TYPE QUESTIONS

Passage 1 2. Percehtage composition of carbon in the compound is .: ..

Empirical formula. of a substance gives the sitnplest whole (a) 6.43 (b) 23.48
number ratio between the atoms of thevarlous elements present (c) 6 0 , (d) 10.09
in one molecule of the substance. Molecular formula on the other 3. what is the percentage composition of nitrogen in the
hand gives the actual number of atoms prestntin one molecule of compound?
the substance. (a) 23.48' (b) 10.09
Molecular formula == n x Empirical formula , (c) 6.43 (d) 60 .
where n is a simple integer 1,2, 3, ... , etc., given by the 4. What is tbepercentage composition of hydrogen in the
equation; co'tnpound?
Molecular mass of the compound (a) 6.43 (b) 10.09
n=--~~----------~~----~ (c) 60 (d) 23.48
Empirical formula mass of the compound
5. What is the value of 'n' for the given compound?
Answer the following questions : Molecular mass
where n = ---:.'----------
Select (a) if True and (b) if False. Empirical formula mass
1. Empirical and molecular formula of a compound may be " (a) 2 (b) 3
same. , '. ','" ,,-,:' , ."'(¢) L (d) 4
True (a) , " :l<'aISe(b} ""', ' , .' ,'
2. Empirical formula of two difterelltcomp~ds cannot be ' ..' Passage 3
. ..
,,·ti.9~g~f~~~c compound gave on comb~stion:
,... ",,~ ~.

same. . . : ' . '.:~

True ( a ) ' . , , ' Fat~e '(b), , . ,.,'. ",.' "(i)';LSS4gt'Oi ',' (ii) 0.648g H 2 0 , ,
3. If two compounds have the,-aame empirical. formula but :Wben O.:!4g bf the substance was Kjeldahlised and the
different molecular formula, they have same vapour aenSity.
True (a) False (b) animoW~~fo~e'd ~ absorbed in 50cm3 of N H 2 S0 4 - The
.: .•. ' . . . 4" .,",
4. The two compounds having Same empirical fOlmulahave .exc~s-acid, required 77cttJ? Of N/IONaOH for complete
same percentage composition, ,
True (a) False (b)
neu:[Link].' MolecUlar mass, of the corilpounc! is estima~ed to
'be 100. " , ,
Empirical fohnula of benzene is C2 Hz .:~
5.
True (a) False,',,(b) , ,
<. A1lswe~ the following questions:
, 1. thecorilpoiind has maximum percentage composition of
6. The compounds having same [Link]'le . 'which oftlie following elements?
same properties. , , {a) C' , (b) H

7.
True (a) False (b)
Cyclo alkanes and alkenes have same empirical formula.
(c)N, (d) °
2. What is the petcentlge' composition of carbon in the
True (a) False (b) compound?'
Passage 2 (a) 16% (b) 8%
(~)28% . (d) 48% .
Combustion of 0.42 g of a compound gave 0.924 g CO 2 ahd
3. Percentage composition of nitrogen in the compound will
0.243 g H 2 O. Due to. distillation of 0.208 g of compound with ~: " "

N
NaOH, ammonia evolved required 30 ml.:of H S04 for (a) 16 (b) 61
, , ' " 20 2- ,
'.(c) 6 ' , (d) 28
complete neutralization. Vapour density of the coriipoUnd is -69.5.' 4. Which among the following is the empirical formula of the
Answer the following questions: compound?
1. The compound has empirical formula: (a) CgH:4N02 (b) C 4 H g N 2 0
(a) C 7 H 9 0 2 N (b) C6 HSN02 (c) C 4 H gNO (d) C g H 4 NO'
will
(c) C 3 H 7-CONH2
°II
(d) NHr -;;.·C-NH 2
5. Molecular formula of the compound
(a) CgH 4 N0 2
be:
(I:» C4 H gN 2 0
(c)' C4 H g NO (d) CgH4NO

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ANSWERS: LINKED COMPREHENSION TYPE QUESTIONS!-
Passage 1 1. (a) 2~ (b) 3. (b) 4. (a) 5. (b) 6. (b) 7. (a),
Passage 2 1. (a) 2. (c) 3. (b) 4. (a) 5. ,(c)
Passage 3 1. (a) 2. (d) 3. (d) 4. (b) 5. (b)