QUALITATIVE ANALYSIS OF ELEMENTS:

1. Detection of carbon and hydrogen. Since all organic compounds contain carbon, and
majority of them also contain hydrogen, in practice carbon and hydrogen are never detected
(tested). However, if necessary these can be detected by heating a small quantity of the given
dry organic compound with dry cupric oxide. Carbon and hydrogen, present in the
compound, are oxidised to CO2 and H2O respectively which in turn can be tested by their
following reactions
2 CuO + C 
 2 Cu + CO2

Heat
CuO + 2 H   Cu + H2O

(a) Carbon dioxide turns lime water milky Ca(OH)2

Ca(OH)2 + CO2   CaCO3 + H2O
(Colourless) (from C) Milky

(b) Water turns anhydrous copper sulphate (white in colour) to hydrated copper sulphate (blue
CuSO4 + 5H2O   CuSO4 . 5H₂O
(White) (From H) Blue

2. Detection of nitrogen, sulphur and halogens. Nitrogen, sulphur and halogens are tested
from the sodium fusion extract of the organic compound, which is more commonly known
as Lassaigne's extract. For preparing Lassaigne's extract, a small quantity of the organic
compound is fused with sodium metal in a fusion tube. The red hot tube is broken in distilled
water, boiled and filtered. The filtrate is known as Lassaigne's extract or sodium extract.
Chemical reactions involved in the formation of Lassaigne's extract.
(i) When only N is present Na + C + N 
 NaCN

(ii) When only S is present 2 Na + S 

 Na2S

(iii) When both N and S are present Na + C + N + S→ NaCNS

(iv) When halogen is present Na + X 
 NaX

Lassaigne's extract, so prepared, is used for testing the presence of N, S and halogens.

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3. Detection of nitrogen. Generally, the Lassaigne's extract is alkaline in nature due to reaction
of unreacted sodium with water (2Na + 2H2O 
 2NaOH + H2). If it is not so, it is made
alkaline by adding sodium hydroxide. Now the extract is boiled with ferrous sulphate
solution, and then acidified with dil. H₂SO, and dil. HCI, appearance of green or blue colour
confirms the presence of nitrogen.
FeSO4 + 2NaOH 
 Fe(OH)2 + Na2SO4

Fe(OH)2 + 6NaCN 
 Na4 [Fe(CN)6] + 2NaOH
Sodium ferrocyanide

4 Fe3+ + 3 Na4[Fe(CN)6] 
 Fe4[Fe(CN)6]3 + 12Na+
(Formed by oxd. Of Fe2+ on Ferric ferrocyanide
Boiling in presence of O2 Prussian blue

Sometimes, Fe3+ ions are provided by adding ferric chloride solution. A less important test
for nitrogen given by certain nitrogenous compounds is evolution of NH3 by heating of the
compound with soda lime (NaOH + CaO).

CH3CONH2 + NaOH 
 CH3COONa + NH3

However, this test is not given by compounds containing –NH2, –NO, and N = N–groups.

(b) Lassaigen's test for sulphur. Sodium sulphide, if present in Lassaigne's extract can be
detected by following tests.
(i) It gives purple colour with sodium nitroprusside solution.
Na2S + Na2[Fe(CN)5(NO)]   Na4[Fe(CN)5NOS]
Sodium nitroprusside Sodium thionitroprusside
Purple colour

(ii) It gives black precipitate with lead acetate solution.

Na2S + (CH3COO)2Pb 
 2 CH3COONa + PbS
Black ppt

(c) Lassaigen's test for nitrogen and sulphur, when present together. In case the compound
contains both N and S. Sodium thiocyanate formed during fusion of organic compound with
metallic sodium reacts with Fe3+ ions to form blood red coloured, ferric thiocyanate.

Fe3+ + 3NaCNS   Fe (CNS)3 + 3Na+

Sod. thiocyanate Ferric thiocyanate
Blood red colour

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 However, note that the absence of blood red colouration does not necessarily mean that
sulphur is absent because in presence of excess of sodium, sodium thiocyanate decomposes
to form sodium cyanide and sodium sulphide.
NaCNS+ 2Na 
 NaCN + Na2S

(d) Lassaigne's test for halogens. A small portion of the sodium fusion extract' is acidified with
dil. nitric acid and then treated with silver nitrate solution. If a precipitate is formed, it
indicates the presence of a halogen; the colour of precipitate, in turn, indicates the nature of
halogen, viz.
(i) white colour soluble in NH4OH indicates chlorine.

(ii) pale yellow colour sparingly soluble in NH,OH indicates bromine and
(iii) yellow colour insoluble in ammonia indicates iodine.
NaX + AgNO3   AgX+ + NaNO3
Sod, halide
(Formed in Lassaigne's filtrate)

(In the preparation of sodium fusion extract used for the detection of halogens, fusion with
sodium may be replaced by quicklime CaO, or a mixture of Na 2CO3 and Zn dust or a mixture
of Na2CO3 and sugar. These will avoid the formation of NaCN or Na2S (in case N or S are
present) hence step involving boiling with conc. HNO3 (for the decomposition of NaCN or
Na2S) will be avoided.)

Note. Function of nitric acid. In case the compound under investigation is found to contain
nitrogen and/or sulphur, the latter two must be destroyed, prior to treatment with AgNO3,
by boiling the extract with concentrated nitric acid which decomposes sodium cyanide and
sodium sulphide (formed during sodium fusion) as volatile HCN and H₂S.
Boil
NaCN+ HNO3  NaNO3 + HCN ↑

Boil
Na2S+ 2HNO3  2NaNO3 + H2S ↑

If NaCN and Na2S are not removed, they will be forming precipitate on the addition of silver
nitrate. The precipitate of AgCN (white) and Ag2S (black) will make hindrance in the
judgement of silver halide precipitate.

NaCN (Na2S) + AgNO3 

 AgCN+ (Ag₂S↓)

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QUANTITATIVE ANALYSIS OF ELEMENTS
1. Estimation of carbon and hydrogen (Liebig's method). The method is based upon the fact
that when an organic compound is heated strongly with dry copper oxide in the presence of
oxygen or air, its carbon and hydrogen are oxidised to carbon dioxide and water vapours
respectively.
Heat
C + 2CuO   CO2 + 2Cu
Heat
2 H + CuO   H2O + Cu

The resultant H2O and CO2vapours are absorbed separately in CaCl2 and NaOH, and hence
the weights of absorbed gases (H2O and CO2) is determined.

O2

CaCl2 NaOH
Organic compound
+ CuO

 Wt. of CO2 
 44   12
Percentage of C =    100
Wt. of compound

Similarly,

 Wt. of H2O 
 18 2
Percentage of H =    100
Wt. of compound

Q 4: 0.30 gm of an organic compound containing C, H and oxygen was analysed by the

combustion method. The increase in weights of calcium chloride tube and potash bulbs
at the end of the operation was found to be 0.15 gm and 0.2 gm respectively. Calculate
the percentage composition of the compound.
Q 5: 0.4 gm of an organic compound on combustion gave 0.01 mole of CO2 and 0.005 mole of
water. Calculate the percentage of carbon and hydrogen in the compound.

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2. Estimation of nitrogen. Nitrogen is generally estimated by two methods:
(A) Duma's method and
(B) Kjeldahl's method.

(A) Duma's method. This method can be applied to all nitrogenous organic compounds.
Principle: The method is based on the fact that when an organic compound is heated with
copper oxide, its carbon, hydrogen, sulphur and nitrogen contents are converted into CO2,
H2O, SO2 and N2 respectively. In case any traces of nitrogen oxides are formed, these are
reduced back to free nitrogen by passing it over bright reduced copper gauze.
Heat
C + 2CuO   CO2 + 2 Cu
Heat
2 H + CuO   H2O + Cu
Heat
S + 2CuO   SO2 + 2 Cu
Heat
2N + CuO   N2 + Oxides of N
Heat
Oxides N + Cu   N2 + CuO

CO2, H2O, SO2 and N2 are passed through NaOH, where CO2, H2O, SO2 are absorbed and free
N2 is collected in inverted tube. From the volume of nitrogen collected over caustic potash,
percentage of nitrogen can be calculated.

 Vol. of N2 collected at N.T.P. 

 22400   28
Percentage of N =    100
Wt. of organic compound

Q 6: 0.7 gm of an organic compound containing nitrogen gave 44.8 ml of nitrogen at N.T.P.

What is the percentage of nitrogen in the compound?

Q 7: In the determination of nitrogen by Duma's method, 0.200 gm of compound gave 22.4

ml of moist nitrogen at 15°C and 776 mm pressure. Calculate the percentage of nitrogen

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 in the compound (Aq. tension at 15°C = 16 mm; 1 litre of nitrogen of N.T.P. weighs 1.25
gm).

(B) Kjeldahl's method. This method is simpler and convenient, and can be used in compounds
in which nitrogen is directly linked to carbon and hydrogen.
However, the method fails in compounds containing nitrogen joined either to other nitrogen
or to oxygen as in nitro, nitroso, azo (N = N), azoxy, diazo, hydrazones, oximes, etc. Also, The
method is not applicable to compounds containing nitrogen in ring (e.g. pyridine, quinoline
etc.)
Principle. This method is based on the fact that most of the nitrogenous compounds when
heated with concentrated sulphuric acid in a long–necked flask called Kjedahl's flask in the
presence of K2SO4 and a little CuSO4, its nitrogen is quantitatively converted into (NH4)2SO4
.
The (NH4)2SO4 so obtained is decomposed with excess of NaOH solution to give NH3 which
is absorbed in an excess of a standard HCl or H2SO4 solution. The residual mineral acid is
now titrated against a standard sodium hydroxide solution and thus the amount of HCI
consumed for the neutralisation of ammonia, and hence the amount of ammonia produced
from the known weight of the organic compound is determined.
K2SO4 ,CuSO4
Organic compound containing N + H2SO4   (NH4)2SO4
Heat
(NH4)2SO4 + 2 NaOH   Na2SO4 + 2NH3 + 2H2O
Heat
2NH3 + H2SO4   (NH4)2SO4

m.eq of NH3 = m.eq of actual acid (=V (Ml)  Normality of acid)

= m.eq of N
= m.mole of N
m.mol of N
So wt of N=  14
1000

  Vol. of acid used  Normality of acid  

   14
 1000 
Percentage of N =  100
Wt. of organic compound

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Type I. When the ammonia evolved completely neutralises the standard acid taken.

Q 8: If the ammonia obtained from 0.3 gm of an organic compound by Kjeldahl method of

analysis neuralises 25 ml of 0.12 N acid, what is percentage of nitrogen in the
compound?

Type II. When the ammonia evolved neutralises part of the standard acid and the acid left unused
is titrated against standard NaOH.
Q 9: 0.5 gm of an organic compound was treated according to Kjeldahl method. The
ammonia evolved was absorbed in 100 ml of N/2 sulphuric acid. The excess of the acid
required 60 ml. N/2 alkali solution for neutralisation. Find the percentage of nitrogen
in the compound.

Type III. When the residual acid in the conical flask is diluted to a known volume with water and
then titrated against standard alkali
Solution.
Q 10: 0.6 gm of an organic compound was Kjeldahlised and the ammonia evolved was passed
into 100 ml of seminormal H2SO4. The residual acid was diluted to 500 ml with distilled
water; 25 ml. of diluted acid required 20 ml decinormal caustic soda solution for
complete neutralisation. Calculate the percentage of nitrogen in the compound.

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3. Estimation of halogens (Carius method). Carius method is based on the fact that when an
organic compound containing halogen is heated in a sealed tube with fuming nitric acid in
presence of silver nitrate, halogen is converted to the silver halide. From the weight of the
silver halide formed, percentage of halogen in the organic compound can be calculated.

 Wt. of AgX 
 Mol. wt. of AgX   At. wt. of halogen
In general, % of halogen =    100
Weight of Substance

Note: This method does not give satisfactory results with iodine because silver iodide is
slightly soluble in nitric acid and some molecular iodine is also produced even in presence
of excess of silver nitrate. The method does not give correct result for highly halogenated
aromatic compounds.

4. Estimation of sulphur (Carius method): A weighed amount of organic substance (let it be

w gm) is heated with conc. HNO3 here its C, H and S are oxidised to CO2, H2O (steam) and
H2SO4 respectively.

Now, The contents of the Carius tube are transferred to a beaker and then treated with excess
of barium chloride solution when whole of the sulphuric acid is precipitated as barium
sulphate. From the weight of BaSO4 (say x gm), percentage of S can be calculated.

H2SO4 + BaCl2 
 BaSO4 + 2HCl

 x  32 
 233 
Percentage of S in the compound =    100
w
Q 11: 0.4 gm of an organic compound containing sulphur was heated in a Carius tube with
fuming nitric acid and the sulphuric acid formed was precipitated as BaSO4 with BaCl2 .
The weight of dry BaSO4 was 0.466. Find the percentage of sulphur in the substance.

Estimation of oxygen. There is no satisfactory method for the direct estimation of oxygen in an
organic compound. Hence, it is usually calculated by difference. In case, the sum of
percentages of all other elements present in the organic compound is less than 100, the
remainder gives the percentage of oxygen, i.e.,
% of oxygen = 100 – Sum of percentages of all other elements

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