QUALITATIVE &

QUANTITATIVE ANALYSIS
 QUALITATIVE ANALYSIS

Qualitative analysis :Detection of element present in compound :-

 QUALITATIVE ANALYSIS

(1) Detection of Nitrogen, Sulphur and halogen :-[Lassaigne's Test]

➢Preparation of lassaigne's solution or sodium extract:

Compound is heated with sodium in combustion tube and poured in cold water
and heated for some time it gives lassaigne's solution or sodium extract.
In lassaigne solution elements present in compound get converted from
covalent to ionic.
e.g Na + C + N ⎯⎯
→ NaCN
Na + S ⎯⎯
→ Na2S
Na + X ⎯⎯
→ NaX (Ionic)
 QUALITATIVE ANALYSIS

(A) Test of Nitrogen : Sodium extract is boiled with FeSO4 which gives sodium
hexacyano ferrate (II). Now few amount of FeCl3 is added which gives prussian blue
coloured ferroferri cyanide that shows presence of Nitrogen.

6 NaCN + FeSO4 ⎯⎯
→ Na4[Fe(CN)6] + Na2SO4

Na4[Fe(CN)6] + FeCl3 ⎯⎯
→ Fe4[Fe(CN)6]3 + NaCl
Prussian blue colour
 QUALITATIVE ANALYSIS

Que. Hydrazine does not give Lassaigne's test, Why?

Sol. In the Lassaigne's test, nitrogen is converted to cyanide by combining

with carbon of the compound Hydrazine does not contain carbon and hence
cyanide cannot form.

Que. Why diazonium salts do not show positive Lassaigne's test for
nitrogen ?

Sol: Diazonium salts are unstable and lose nitrogen as N2 gas on heating.
Hence during fusion, no sodium cyanide is formed in Lassaigne's extract
due to the loss of nitrogen.
 QUALITATIVE ANALYSIS

(B) Test of sulphur : Sulphur is present in form of Na2S

(i) Sodium Extract is acidified with lead acetate is added to it which gives black
ppt of PbS and shows the presence of Sulphur
Na2S + (CH3COO)2Pb ⎯⎯
→ 2CH3COONa +PbS(Black)

(ii) Nitroprusside test:

Sodium extract + Sodium Nitroprusside Violet colour
Na2S + Na2[Fe(CN)5NO] ⎯⎯
→ Na4 [Fe(CN)5 NOS] (Violet colour)
In case of nitrogen and sulphur both are present in organic compound,
Sodium thiocyanate is formed.
⎯⎯→ NaSCN
Na + C + N + S
SCN + FeCl3 ⎯⎯
→ Fe(SCN)
 QUALITATIVE ANALYSIS

(C) Test of halogen:

NaX + AgNO3 ⎯⎯
→ AgX + NaNO3
AgX

AgCl AgBr AgI

 White ppt  Pale Yellow ppt  Yellow ppt
(Soluble in NH 4 OH) (Sparingly soluble (Insoluble
in NH 4 OH) in NH 4 OH)
 QUANTITATIVE ANALYSIS
Quantitative analysis
1. Estimation of carbon and hydrogen : [Leibigs method]
Calculation of % of C and H :-
For H H2O  2H
18gm 2gm
2 m
Precentage of hydrogen in W gm organic substance = % of H =   100
18 W
For C CO2  C
44 gm 12 gm

% of C in W gm organic substance = % of C = 12  m  100

44 W
 QUANTITATIVE ANALYSIS

2. Estimation of Nitrogen :
These are two method for the estimation of nitrogen
(i) Duma's method [in form of N2]
(ii) Kjeldhal's method [in form of NH3]
 QUANTITATIVE ANALYSIS

(1) Duma's method :

Organic compound is heated with CuO to give free Nitrogen, CO2 and H2O.
y z
Cx Hy Nz + CuO ⎯⎯
→ x CO2 + H2O + N2 + Cu
2
2
Now the above mixture is collected over Aq. KOH in nitrometertube which
absorb all the gases except N2. Now volume of nitrogen is calculated at STP.

P1 V1 P2 V2
= V1 = Volume of N2 gas.
T1 T2
P1 = Pressure of N2 – Aqueous tension
T1 = Room temperature
P1 V1  273
V2 =
T1  760
 QUANTITATIVE ANALYSIS

Calculation of % of Nitrogen

\ 22400 ml of N2 at STP weight = 28 gm

28
V ml of N2 at STP weight =  V gm
22400

% of Nitrogen in W gm organic substance = % of N = 28 V

  100
22400 W
 QUANTITATIVE ANALYSIS
(2) Kjeldhal's method :
Organic substance + H2SO4 ⎯⎯
→ (NH4)2SO4
(NH4)2SO4 + NaOH ⎯⎯
→ Na2SO4 + 2NH3 + H2O
NH3 + H2SO4 ⎯⎯
→ (NH4)2SO4

If Normality of H2SO4 taken = N1

Volume of H2SO4 taken = V1

If Normality of NaOH used = N2

Volume of NaOH used = V2

\ Milli equivalent of H2SO4 used for neutralisation of produced NH3 = (N1V1 – N2V2)
Which is equal to the milli equivalent of NH3
 QUANTITATIVE ANALYSIS

\ 1000 ml of 1N NH3contain 14 gm Nitrogen.

14
\ (N1V1 – N2V2) ml of 1N NH3 contain × (N1V1 – N2V2) gm Nitrogen.
1000

If mass of organic substance is W g.

Then % of N =
14 ( N V − N2 V2 )  100
 1 1
1000 W

1.4
 ( N1 V1 − N 2 V2 )
1.4
% of N = or % of N=  NV
W W

N = Normality of H2SO4 V = Volume of H2SO4 used in neutralisation.

 QUANTITATIVE ANALYSIS

Kjeldhal's method is not applicable to compounds containing nitro (–NO2 ),

azo group (–N=N–) and nitrogen present in the ring(pyridine) because
nitrogen present in these compounds is not quantitatively converted in to
ammonium sulphate.
 QUANTITATIVE ANALYSIS

3. Carius method:
➢ Estimation of halogen
 QUANTITATIVE ANALYSIS

➢ Estimation of sulphur
 QUANTITATIVE ANALYSIS

Q.1 0.3960 gm of an organic compound on combustion gives 0.792 gm CO2 and

0.324 gm of H2O. Calculate the % of C and H?
12 Wt. of CO 2
% of C = × ××100
44 Wt. of compound

12 0.792
× × 100 = 54.55%
44 0.396

2 Wt. of H 2 O
% of H = × Wt. of compound × 100
18

2 0.324
× × 100 = 9.09%
18 0.396
 QUANTITATIVE ANALYSIS
Q.2) 0.25 gm of an organic compound at NTP gives 31 ml of N2 gas by Duma's
method. Find out of % of N ?

28 V
% of N = × × 100
22400 W

28 31
× × 100 = 15.5%
22400 0.25
 P1 V1  273 QUANTITATIVE ANALYSIS
V2 =
T1  760 Q. In Duma's method estimation of nitrogen, 0.3g of an organic compound
gave 50 ml of nitrogen collected at 300 K temperature and 715 mm pressure.
28 V Calculate the percentage composition of nitrogen in the compound.
% of N =   100
22400 W (Aqueous tension at 300K = 15 mm)
Ans. Volume of nitrogen collected at 300K and 715 mm pressure is 50 ml
Actual pressure = 715 – 15 = 700 mm
273  700  50
Volume of nitrogen at STP = = 41.9ml
300  760

Percentage of nitrogen = 28  41.9  100 = 17.46%

22400  0.3
 QUANTITATIVE ANALYSIS

Q. 30 ml 0.25 N H2SO4 are used in neutralizing NH3 obtained from 0.75 gm of

an organic compound in Kjeldhal's method find out % of N in the compound?

1.4
% of N=  NV
W