Structure Identification & POC

Section (I) : Quantitative analysis of elements

After the detection of various elements in the organic compounds, the next step is the determination of
their percentage composition. The determination of the percentage of various elements is also referred
to as estimation of elements. The different methods employed for the estimation of various elements
are being discussed as below.

I-1 Estimation of carbon and hydrogen (Liebig’s method)

Carbon and hydrogen in the organic compound are estimated together by Liebig method.

Principle :
A known mass of the organic compound is heated with dry copper oxide in an atmosphere (or oxygen)
free from moisture and carbon dioxide. The carbon and hydrogen of the organic compounds are
oxidized to carbon dioxide and water respectively.
C + 2CuO  CO2 + 2Cu
2H + CuO  H2O + Cu
Carbon dioxide produced is collected in potash bulbs (containing KOH) whereas water is absorbed in
calcium chloride tube (containing CaCI2). The respective masses of CO2 and H2O are determined by
difference.
Knowing the masses of CO2 and water vapors formed and the mass of the compound taken, the
percentage of carbon and hydrogen can be calculated.

Calculations :
Let the mass of the organic compound taken = w g
Mass of water formed = x g
(Indicated by increase in the mass of U tube)
Mass of carbon dioxide formed = y g
(Indicated by increase in the mass of potash bulb)

(i) Percentage of Carbon

44 g of CO2 contains carbon = 12g
12y
y g of CO2 contains carbon = g
44
12y
Now, g of carbon is present in w g of organic compound.
44
12y
 Percentage of carbon in the organic compound = × 100
44  w

(ii) Percentage of Hydrogen

18 g of H2O contains hydrogen = 2g
2x
x g of H2O contains hydrogen = g
18
2x
Now, g of hydrogen is present in w g of organic compound.
18
2x
 Percentage of hydrogen in the organic compound = × 100
18w
12  WCO2  100 2  WH2O  100
In Short, %C = and %H =
44  Wsubs tan ce 18  Wsubs tan ce
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 Structure Identification & POC

Que. 0.378g of an organic acid gave on combustion 0.264g of carbon dioxide and 0.162g of water vapors.
Calculate the percentage of C and H in it.
Ans. Mass of organic compound = 0.378g
Mass of CO2 formed = 0.264g
Mass of H2O formed = 0.162g

(i) Percentage of carbon

44g of CO2 contains carbon = 12g
12
0.264g of CO2 contains carbon = × 0.264 = 0.072g
44
0.072
Percentage of carbon = × 100 = 19.04%
0.378
(ii) Percentage of hydrogen
18 g of H2O contains hydrogen = 2g
2
0.162 g of H2O contains hydrogen = × 0.162 = 0.018g
18
0.018
Percentage of hydrogen = × 100 = 4.76%
0.378

I-2 Estimation of nitrogen

There are two methods for the estimation of nitrogen.
(i) Duma’s Method (ii) Kjeldahl’s Method

(i) Duma’s Method

This method is applicable to nitrogenous compounds.
Principle :
A known mass of the organic compound is heated strongly with excess of copper oxide in an
atmosphere of carbon dioxide. The carbon and hydrogen are converted to CO 2 and water. Nitrogen is
set free as dinitrogen. If any oxide of nitrogen is produced, it is reduced to dinitrogen by passing over
hot reduced copper spiral. The dinitrogen is collected over the concentrated solution of potassium
hydroxide and its volume is measured at room temperature and atmospheric pressure.
The chemical reaction can be represented as :

Calculations :
Let the mass of the organic compound taken = W g
Volume of moist N2 collected = v cm3
Barometric pressure = P mm
Room temperature = T K
Pressure of water vapor’s at T K = p mm
Pressure of dry N2 = (P – p) mm
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 Structure Identification & POC

Step I. To find the volume of N2 to S.T.P.

V1 = v cm3, V2 = ?, P1 = (P – p), P2 = 760 mm, T1 = T, T2 = 273 K
P1V1 PV
= 2 2
T1 T2
P1V1 T (P  p)  273
V2 = × 2 =
T1 P2 T  760

Step II. Calculation of percentage of nitrogen

22400cm3 of N2 at S.T.P. weights = 28g
28 V2
Now amount of nitrogen present in W g of organic compound = g
22400
28 V2 100
Percentage of N in organic compound = × .
22400 W
28  VN2 (S.T.P.)  100
In Short, % N =
22400  WSubs tance

Questions based on Duma’s method :

Que. 0.25g of an organic compound gave 30cm 3 of moist dinitrogen at 288K and 745mm pressure.
Calculate the percentage of nitrogen. (Aqueous tension of 288 K = 12.7mm).
Ans. Mass of the substance = 0.25 g
Volume of moist dinitrogen = 30 cm3
Temperature = 288 K
Pressure = 745 –12.7 = 732.3 mm
Step I. To find the volume of N2 at S.T.P.
P1V1 PV
We know, = 2 2 , (P2, T2, V2 refer to S.T.P. conditions)
T1 T2
P1V1 T2 732.3  30  273
V2 =   = 27.4 cm3.
T1 P2 288  760
Step II. Calculation of percentage of nitrogen.
22400 cm3 of dinitrogen at S.T.P. Weighs = 28 g
28  274
27.4 cm3 of dinitrogen at S.T.P. Weighs =  0.034 g
22400
0.034
Percentage of nitrogen in organic compound =  100 = 13.6.
0.25
(ii) Kjeldahl’s method
This method is simpler and convenient. It is largely used for the estimation of nitrogen in food, fertilizers
and drugs. The method is however not applicable to compounds containing nitrogen in the ring like
pyridine or quinoline etc, and the compounds, containing nitro (–NO2) and diazo (–N = N–) groups.
Principle :
A known mass of the organic compound is heated with concentrated sulphuric acid. The nitrogen in the
organic compound is quantitatively converted into ammonium sulphate. The resulting liquid is then
distilled with excess of sodium hydroxide solution and the ammonia evolved is passed into a known but
excess volume of the standard acid (HCI or H2SO4). The acid left unused is estimated by titration with
some standard alkali. The amount of acid used against ammonia can thus, be known and from this, the
percentage of nitrogen in the compound can be calculated.

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Structure Identification & POC

Chemical reactions involved are :

conc.
C + H+ S CO2 + H2O + SO2
H2SO4
Organic
compound
conc.
N (NH4)2SO4
H2SO4
(NH4)2SO4 + 2NaOH Na 2SO4 + 2NH 3 + 2H2O

2NH3 + H2SO4 (NH4)2 SO4

Calculations :
Let the mass of organic compound = W g
Volume of standard acid (say HCI) taken = V cm3
Let molarity of acid = M1
Let volume of acid unused be = v1
Let volume of alkali (say NaOH) of molarity M2 used for neutralising unused acid = v2

Chemical equation for titration involved is

NaOH + HCI NaCI + H2O
unused

 According to molarity relation

M2 2 M11 M
 or 1  2 2
1 1 M1
Volume of acid used by ammonia = (V –v1) cm3
Millimoles of acid used by ammonia = (V –v1) × M1
Millimoles of NH3 formed = Millimoles of acid used up
= (V –v1) × M1
Mass of NH3 formed = Millimoles × 10–3 × Molar mass of NH3
= (V –v1) × M1 × 10–3 × 17g
(V – 1 )M1  10–3  17  14
Mass of N =
17
Mass of N = a g (say)
a  100
Percentage of N =
W
1.4  M(acid)  basicity of acid  V(acid used)
In Short % N =
WSubs tan ce

1.4  N(acid)  V(acid used)

or % N =
WSubs tance

Questions based on Kjeldahl’s method :

Que. During nitrogen estimation in an organic compounds by Kjeldahl’s method, the ammonia evolved from
0.5 g of the compound neutralised 10 ml, of 1 M H2SO4, What is the % of N in the organic compound ?
Ans. Volume of 1 M H2SO4 used by NH3 = 10 ml,
Millimoles of H2SO4 used = 10 × 1 = 10 Millimoles
Millimoles of NH3 produced = 2 × Millimoles of H2SO4
= 2 ×10 = 20 (2 moles of NH3 neutralise 1 mole of H2SO4)

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Structure Identification & POC

Mass of NH3 formed = Moles of NH3 × Molar mass = 20 × 10–3 × 17g

20  10–3  17  14
Mass of N = = 0.28g
17
0.28  100
% of N = = 56.0%.
0.5

I-3 Estimation of halogens by Carius method

Halogen is estimated as silver halides in Carius method.
In the process organic halide is treated with acidified silver nitrate solution to get silver halide which is
washed, dried and weighed.
Atomic mass of X Wt. of AgX
%X= × × 100
Molecular mass of AgX Wt. of organic halide
35.5 Wt. of AgCl
Thus, % Cl = × × 100
143.5 Wt. of organic halide
80 Wt. of AgBr
% Br = × × 100
188 Wt. of organic halide
127 Wt. of AgI
%I= × × 100
235 Wt. of organic halide

I-4 Estimation of sulphur

Sulphur is estimated as barium sulphate. In the process organic compound having sulphur is taken in
carius tube containing HNO 3 where sulphur is finally converted into sulphuric acid. This sulphuric acid is
passed through excess of BaCl2 to get BaSO4 which is washed dried & weighed.
Atomic mass of sulphur Wt. of BaSO 4
%S= × × 100
Molecular mass of BaSO4 Wt. of organic compound

32 Wt. of BaSO4
%S= × × 100
233 Wt. of organic compound

I-5 Estimation of phosphorus

A known mass of the organic compound is heated with fuming nitric acid. The phosphorus present in
the organic compound is oxidised to phosphoric acid (H 3PO4). The phosphoric acid, thus formed is
treated with magnesia mixture to get the precipitate of magnesium ammonium phosphate (MgNH 4PO4).
The precipitate is separated, dried and ignited to get magnesium pyrophosphate (Mg 2P2O7). The
chemical reactions involved are :

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Structure Identification & POC

Calculations :
Let the mass of the organic compound = W g
Mass of Mg2P2O7 obtained= x g
Now, 222 g (G.M.M.) of Mg2P2O7 Contains = 62 g phosphorous
62x
x g of Mg2P2O7 contains = g phosphorous
222
62x
Percentage of P in organic compound = × 100
222W
62  WMg2P2O7  100
% of P =
222  WSubs tance

Que. (i) In sulphur estimation, 0.157 g of organic compound gave 0.4813 g of BaSO 4. What is the percentage
of sulphur in organic compound?
(ii) 0.092 g of organic compound on heating is carius tube and subsequent ignition give 0.111g of
Mg2P2O7. Calculate the percentage of phosphorus in organic compound.
Ans. (i) Mass of BaSO4 = 0.4813g
Mass of organic compound. = 0.157g
32  WBaSO4  100 32  0.4813  100
%S= = = 42.10%
233  WSubs tance 233  0.157
(ii) Mass of organic compound = 0.092g
Mass of Mg2P2O7 = 0.111 g
62  WMg2P2O7  100 62  0.111  100
% of P = = = 33.69%
222  WSubs tance 222  0.092

I-6 Estimation of oxygen

The percentage of oxygen in an organic compound is usually found by difference between the total
percentage composition (100) and the sum of the percentages of all other elements.
However, oxygen can also be estimated directly as below.
A definite mass of an organic compound is decomposed by heating in a stream of nitrogen gas. The
mixture of gaseous products containing oxygen is passed over red-hot coke when all the oxygen is
converted to carbon monoxide. This mixture is passed through warm iodine pentoxide (I2O5) where
carbon monoxide is oxidised to carbon dioxide and producing iodine.
Compound   O2 + other gaseous products
heat

2C + O2   2CO
1373 K

I2O5 + 5CO  I2 + 5CO2

32  m1  100
% oxygen =
44  W
(m1 = mass of CO2 and W = mass of sample)

I-7 Estimation of halogen by Beilstein test

A copper wire is cleaned and heated in a Bunsen burner flame to form a coating of copper (II) oxide. It
is then dipped in the sample to be tested and once again heated in a flame. A positive is indicated by a
green flame caused by the formation of a copper halide.
This test does not detect fluorine and fluorides.

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