organic chemistry – some basic principles and techniques 285

concentrated sulphuric acid. The formation bromine and a yellow precipitate, insoluble
of Prussian blue colour confirms the presence in ammonium hydroxide shows the presence
of nitrogen. Sodium cyanide first reacts of iodine.
with iron(II) sulphate and forms sodium X– + Ag+ → AgX
hexacyanidoferrate(II). On heating with X represents a halogen – Cl, Br or I.
concentrated sulphuric acid some iron(II)
If nitrogen or sulphur is also present in the
ions are oxidised to iron(III) ions which
compound, the sodium fusion extract is
react with sodium hexacyanidoferrate(II)
first boiled with concentrated nitric acid to
to produce iron(III) hexacyanidoferrate(II) decompose cyanide or sulphide of sodium
(ferriferrocyanide) which is Prussian blue in formed during Lassaigne’s test. These ions
colour. would otherwise interfere with silver nitrate
6CN– + Fe2+ → [Fe(CN)6]4– test for halogens.
3[Fe(CN)6]4– + 4Fe3+ Fe4[Fe(CN)6]3.xH2O (D) Test for Phosphorus
 Prussian blue The compound is heated with an oxidising
(B) Test for Sulphur agent (sodium peroxide). The phosphorus
(a) The sodium fusion extract is acidified present in the compound is oxidised to
with acetic acid and lead acetate is added phosphate. The solution is boiled with nitric
to it. A black precipitate of lead sulphide acid and then treated with ammonium
indicates the presence of sulphur. molybdate. A yellow colouration or precipitate
indicates the presence of phosphorus.
S2– + Pb2+ → PbS
Black Na3PO4 + 3HNO3 → H3PO4+3NaNO3
(b) On treating sodium fusion extract with H3PO4 + 12(NH4)2MoO4 + 21HNO3 →
sodium nitroprusside, appearance of Ammonium
a violet colour further indicates the molybdate
presence of sulphur. (NH4)3PO4.12MoO3 + 21NH4NO3 + 12H2O
S2– + [Fe(CN)5NO]2– → [Fe(CN)5NOS]4– Ammonium
Violet phosphomolybdate
In case, nitrogen and sulphur both are 8.10 Quantitative Analysis
present in an organic compound, sodium
Quantitative analysis of compounds is very
thiocyanate is formed. It gives blood red colour
important in organic chemistry. It helps
and no Prussian blue since there are no free
chemists in the determination of mass per
cyanide ions.
cent of elements present in a compound. You
Na + C + N + S → NaSCN
have learnt in Unit-1 that mass per cent of
Fe +SCN
3+ –
→ [Fe(SCN)]2+ elements is required for the determination of

Blood red emperical and molecular formula.
If sodium fusion is carried out with excess The percentage composition of elements
of sodium, the thiocyanate decomposes to present in an organic compound is determined
yield cyanide and sulphide. These ions give by the following methods:
their usual tests.
NaSCN + 2Na → NaCN+Na2S 8.10.1 Carbon and Hydrogen
(C) Test for Halogens Both carbon and hydrogen are estimated in
one experiment. A known mass of an organic
The sodium fusion extract is acidified with
compound is burnt in the presence of excess
nitric acid and then treated with silver nitrate.
of oxygen and copper(II) oxide. Carbon and
A white precipitate, soluble in ammonium
hydrogen in the compound are oxidised to
hydroxide shows the presence of chlorine,
carbon dioxide and water respectively.
a yellowish precipitate, sparingly soluble in
ammonium hydroxide shows the presence of CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O

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Fig.8.14 Estimation of carbon and hydrogen. Water and carbon dioxide formed on oxidation of substance
are absorbed in anhydrous calcium chloride and potassium hydroxide solutions respectively
contained in U tubes.

The mass of water produced is determined 8.10.2 Nitrogen

by passing the mixture through a weighed There are two methods for estimation of
U-tube containing anhydrous calcium chloride. nitrogen: (i) Dumas method and (ii) Kjeldahl’s
Carbon dioxide is absorbed in another U-tube method.
containing concentrated solution of potassium (i) Dumas method: The nitrogen containing
hydroxide. These tubes are connected in series organic compound, when heated with copper
(Fig. 8.14). The increase in masses of calcium oxide in an atmosphere of carbon dioxide,
chloride and potassium hydroxide gives the yields free nitrogen in addition to carbon
amounts of water and carbon dioxide from dioxide and water.
which the percentages of carbon and hydrogen
CxHyNz + (2x + y/2) CuO →
are calculated.
Let the mass of organic compound be x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
m g, mass of water and carbon dioxide
Traces of nitrogen oxides formed, if
produced be m1 and m2 g respectively;
any, are reduced to nitrogen by passing the
12 × m2 × 100 gaseous mixture over a heated copper gauze.
Percentage of carbon=
44 × m The mixture of gases so produced is collected
2 × m1 × 100 over an aqueous solution of potassium
Percentage of hydrogen = hydroxide which absorbs carbon dioxide.
18 × m Nitrogen is collected in the upper part of the
Problem 8.20 graduated tube (Fig.8.15).
On complete combustion, 0.246 g of an Let the mass of organic compound = m g
organic compound gave 0.198g of carbon Volume of nitrogen collected = V1 mL
dioxide and 0.1014g of water. Determine
Room temperature = T1K
the percentage composition of carbon
and hydrogen in the compound. 1 1 × 273
PV
Volume of nitrogen at STP =
Solution 760 × T1
12 × 0.198 × 100 (Let it be V mL)
Percentage of carbon =
44 × 0.246 Where p 1 and V 1 are the pressure and
= 21.95% volume of nitrogen, p1 is different from the
atmospheric pressure at which nitrogen gas
2 × 0.1014 × 100 is collected. The value of p1 is obtained by
Percentage of hydrogen =
18 × 0.246 the relation;
= 4.58% p1= Atmospheric pressure – Aqueous tension
22400 mL N2 at STP weighs 28 g.

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 organic chemistry – some basic principles and techniques 287

Fig. 8.15 Dumas method. The organic compound yields nitrogen gas on heating it with
copper(II) oxide in the presence of CO2 gas. The mixture of gases is collected over
potassium hydroxide solution in which CO2 is absorbed and volume of nitrogen
gas is determined.

28 × V
V mL N 2 at STP weighs = g 28 × 41.9
22400 41.9 mL of nitrogen weighs = g
22400
28 × V × 100
Percentage of nitrogen = 28 × 41.9 × 100
22400 × m Percentage of nitrogen =
22400 × 0.3
Problem 8.21 = 17.46%
In Dumas’ method for estimation of
nitrogen, 0.3g of an organic compound
gave 50mL of nitrogen collected at 300K
temperature and 715mm pressure. (ii) Kjeldahl’s method: The compound
Calculate the percentage composition containing nitrogen is heated with concentrated
of nitrogen in the compound. (Aqueous sulphuric acid. Nitrogen in the compound
tension at 300K=15 mm) gets converted to ammonium sulphate
(Fig. 8.16). The resulting acid mixture is then
Solution
heated with excess of sodium hydroxide.
Volume of nitrogen collected at 300K and The liberated ammonia gas is absorbed in
715mm pressure is 50 mL an excess of standard solution of sulphuric
Actual pressure = 715-15 =700 mm acid. The amount of ammonia produced is
273 × 700 × 50 determined by estimating the amount of
Volume of nitrogen at STP sulphuric acid consumed in the reaction. It
300 × 760
is done by estimating unreacted sulphuric
41.9 mL
acid left after the absorption of ammonia by
22,400 mL of N2 at STP weighs = 28 g titrating it with standard alkali solution. The
difference between the initial amount of acid

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Fig.8.16 Kjeldahl method. Nitrogen-containing compound is treated with concentrated H2SO4 to get
ammonium sulphate which liberates ammonia on treating with NaOH; ammonia is absorbed
in known volume of standard acid.
taken and that left after the reaction gives the 14 × M × 2(V − V1 / 2) 100
amount of acid reacted with ammonia. Percentage of N = ×
1000 m
Organic compound + H2SO4 → (NH4)2SO4
1.4 × M × 2 (V − V / 2)
Na2SO4 + 2NH3 + 2H2O =
m
2NH3 + H2SO4 → (NH4)2SO4
Kjeldahl method is not applicable to
Let the mass of organic compound taken = m g compounds containing nitrogen in nitro and
Volume of H2SO4 of molarity, M, azo groups and nitrogen present in the ring
taken = V mL (e.g. pyridine) as nitrogen of these compounds
Volume of NaOH of molarity, M, used for does not change to ammonium sulphate
titration of excess of H2SO4 = V1 mL under these conditions.
V1mL of NaOH of molarity M
Problem 8.22
= V1 /2 mL of H2SO4 of molarity M
Volume of H 2 SO 4 of molarity M unused During estimation of nitrogen present
= (V - V1/2) mL in an organic compound by Kjeldahl’s
method, the ammonia evolved from
(V- V1/2) mL of H2SO4 of molarity M 0.5 g of the compound in Kjeldahl’s
= 2(V-V1/2) mL of NH3 solution of estimation of nitrogen, neutralized 10 mL
molarity M. of 1 M H2SO4. Find out the percentage of
1000 mL of 1 M NH 3 solution contains nitrogen in the compound.
17g NH3 or 14 g of N Solution
2(V-V1/2) mL of NH3 solution of molarity M 1 M of 10 mL H2SO4=1M of 20 mL NH3
contains: 1000 mL of 1M ammonia contains 14 g
14 × M × 2(V − V1 / 2) nitrogen
gN
1000 20 mL of 1M ammonia contains

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 organic chemistry – some basic principles and techniques 289

14 × 20 Percentage of halogen
g nitrogen
1000 atomic mass of X × m1g
=
14×20×100 molecular mass of AgX
Percentage of nitrogen = = 56.0%
1000×0.5
Problem 8.23
8.10.3 Halogens In Carius method of estimation of
Carius method: A known mass of an organic halogen, 0.15 g of an organic compound
compound is heated with fuming nitric acid in gave 0.12 g of AgBr. Find out the
the presence of silver nitrate contained in a hard percentage of bromine in the compound.
glass tube known as Carius tube, (Fig.8.17) Solution
Molar mass of AgBr = 108 + 80
= 188 g mol-1
188 g AgBr contains 80 g bromine
80 × 0.12
0.12 g AgBr contains g bromine
188

80 × 0.12 × 100
Percentage of bromine =
188×0.15
= 34.04%

8.10.4 Sulphur
A known mass of an organic compound is
heated in a Carius tube with sodium peroxide
or fuming nitric acid. Sulphur present in the
compound is oxidised to sulphuric acid. It
is precipitated as barium sulphate by adding
excess of barium chloride solution in water.
The precipitate is filtered, washed, dried and
weighed. The percentage of sulphur can be
Fig. 8.17 Carius method. Halogen containing calculated from the mass of barium sulphate.
organic compound is heated with fuming
nitric acid in the presence of silver
Let the mass of organic
nitrate. compound taken = m g
and the mass of barium
in a furnace. Carbon and hydrogen present in sulphate formed = m1g
the compound are oxidised to carbon dioxide 1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur
and water. The halogen present forms the 32 × m1 × 100
corresponding silver halide (AgX). It is filtered, m1 g BaSO4 contains g sulphur
233 × m
washed, dried and weighed.
32 × m1 × 100
Let the mass of organic Percentage of sulphur =
compound taken = m g 233 × m
Mass of AgX formed = m1 g
1 mol of AgX contains 1 mol of X
Mass of halogen in m1g of AgX Problem 8.24
atomic mass of X × m1g In sulphur estimation, 0.157 g of an
= organic compound gave 0.4813 g of
molecular mass of AgX

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 290 chemistry

percentage composition (100) and the sum of

barium sulphate. What is the percentage
the percentages of all other elements. However,
of sulphur in the compound?
oxygen can also be estimated directly as follows:
Solution A definite mass of an organic compound is
Molecular mass of BaSO4 = 137+32+64 decomposed by heating in a stream of nitrogen
gas. The mixture of gaseous products containing
= 233 g
oxygen is passed over red-hot coke when all
233 g BaSO4 contains 32 g sulphur the oxygen is converted to carbon monoxide.
32 × 0.4813 This mixture is passed through warm iodine
0.4813 g BaSO4 contains g pentoxide (I2O5) when carbon monoxide is
g sulphur 233
oxidised to carbon dioxide producing iodine.
32 × 0.4813 × 100 Compound  heat
→ O2 + other gaseous
Percentage of sulphur = products
233 × 0.157
2C + O2 
1373 K
→ 2CO]× 5 (A)
= 42.10%
I2O5 + 5CO → I2 + 5CO2]× 2 (B)

8.10.5 Phosphorus On making the amount of CO produced in

A known mass of an organic compound is equation (A) equal to the amount of CO used
heated with fuming nitric acid whereupon in equation (B) by multiplying the equations
phosphorus present in the compound is (A) and (B) by 5 and 2 respectively; we find
oxidised to phosphoric acid. It is precipitated that each mole of oxygen liberated from
as ammonium phosphomolybdate, (NH4)3 the compound will produce two moles of
PO 4 .12MoO 3 , by adding ammonia and carbondioxide.
ammonium molybdate. Alter natively, Thus 88 g carbon dioxide is obtained if 32 g
phosphoric acid may be precipitated as oxygen is liberated.
MgNH4PO4 by adding magnesia mixture which Let the mass of organic compound taken be m g
on ignition yields Mg2P2O7. Mass of carbon dioxide produced be m1 g
Let the mass of organic compound taken ∴ m 1 g carbon dioxide is obtained from
= m g and mass of ammonium phospho 32 × m1
molydate = m1g g O2
88
Molar mass of (NH4)3PO4.12MoO3 = 1877g 32 × m1 × 100
∴Percentage of oxygen = %
31 × m1 × 100 88 × m
Percentage of phosphorus = %
1877 × m The percentage of oxygen can be derived
from the amount of iodine produced also.
If phosphorus is estimated as Mg2P2O7,
Presently, the estimation of elements in
62 × m1 × 100 an organic compound is carried out by using
Percentage of phosphorus = ×%
222 microquantities of substances and automatic
where, 222 u is the molar mass of Mg2P2O7, experimental techniques. The elements,
m, the mass of organic compound taken, carbon, hydrogen and nitrogen present in a
m1, the mass of Mg2P2O7 formed and 62, the compound are determined by an apparatus
mass of two phosphorus atoms present in the known as CHN elemental analyser. The
compound Mg2P2O7. analyser requires only a very small amount
of the substance (1-3 mg) and displays the
8.10.6 Oxygen values on a screen within a short time. A
The percentage of oxygen in an organic compound detailed discussion of such methods is beyond
is usually found by difference between the total the scope of this book.

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