JEEMAIN.

GURU

PURIFICATION METHODS

  Distillation Techniques :

Typ e Conditions Examples

(A) Simple distillation (i) When liquid sample has
non volatile impurities
(ii) When boiling point
difference is 80° K or more.
(i) Mixture of chloroform
(BP = 334K) and Aniline
(BP = 457K)
(ii) Mixture of Ether (BP = 308K) &
Toluene (BP = 384K)
(iii) Hexane (342K) and Toulene(384K)

(B) Fractional distillation When BP difference is 10° (i) Crude oil in petroleum industry
(ii) Acetone (329) and Methyl alcohol(338K)

(C) Distallation under When liquid boils at higher (i) Concentration of sugar juice
reduced pressure temperature and it may (ii) Recovery of glycerol from spent lye.
(Vacuum distillation) decompose before BP is attained. (iii) Glycerol

(D) Steam distillation When the substance is immiscible (i) Aniline is separated from water
with water and steam volatile. (ii) Turpentine oil
(iii) Nitro Benzene
(iv) Bromo Benzene
(v) Naphthalene
(vi) o-Nitrophenol

SIMPLE DISTILL ATION TECHNIQUE

JEEMAIN.GURU

FR ACTIONAL DISTILL ATION

DISTILL ATION UNDER REDUCED PRESSURE

STE A M DISTILL ATION

JEEMAIN.GURU
 LASSAIGNE METHOD :
1. Nitrogen (N) : Na + C + N  NaCN
(Sodium extract)
Te st : NaCN + FeSO 4 + NaOH
 boil & cool
FeCl 3 + conc. HCl

Blue or green colour [Fe4[Fe(CN)6] 3
Prussian blue
2. 
Sulphur (S) : 2Na + S  Na2S
(Sodium extract)
Te st (1) Na 2 S
 Sodium nitro prusside
A deep voilet colour
Te st (2) Na 2S + CH 3 COOH + (CH 3 COO) 2Pb

Black colour (PbS)
3. Halogen (X) : Na + Cl  NaCl
(Sodium extract)
Te st : NaCl + HNO 3 + AgNO 3
(a) White ppt soluble in aq. NH3 confirms Cl
(b) Yellow ppt partially soluble in aq. NH3 confirms Br
(c) yellow ppt insoluble in aq. NH3 confirms I
4. Nitrogen a nd Sulphur toget her :

Na + C + N + S  NaCNS
(Sodium thiocynate)

As in test of nitrogen, instead of green or blue colour,
blood red coloration confirms presence of N and S both.
5. Phosphorous (P) :
Na 2 O 2
P 
boils, 
 Na PO
3 4


Solution in boiled with nitric acid and then treated
with ammonium molybdate (NH 4) 2 MoO 4

Formation of yellow ppt indicate presence of phosphate
hence phosphorous present in organic compounds.
 THE QUANTITATIVE ANALYSIS :
Quantitative analysis involves the estimation of percentage composition of various element by suitable method.
The molecular mass of the compound is also determined by suitable methods. The knowledge of molecular
mass and percentage composition help us to determine the molecular formula of the compound.

 ESTIM ATION OF CARBON AND H YDROGEN OR LIEBIG COMBUSTION METHOD :

Organic compound + dry, black CuO
(w g)  Heat strongly in combustion tube
mixture of oxide
 Pass through
(i) anhydrous CuSO 4
(ii) anhydrous CaCl 2
JEEMAIN.GURU
say increase in weight = a g
 Pass through
(i) KOH (aq)
(ii) Saphnolite resin
say increase in weight = b g
For % of H - The increase in weight is 'a' g due to the formation of H2O
 18 g H2O has H = 2 g
2a
 a g H2O has H  g
18
2a
Since w g organic compound has = g hydrogen.
18
2a  100
 100 g organic compound has= g hydrogen
18  w

2 weight of H 2 O formed
 % H  18  weight of subs tan ce  100

For % of C -
The increase in wt is b g due to formation of CO2
 44 g CO2 has C = 12 g
12
 b g CO2 has C = b g
44

 12 
Since w g organic compound has   b  g carbon
 44 

12 100
 100 g organic comound has b g carbon
44 w

12 weight of CO 2 formed
 % C  44  weight of subs tan ce  100

Note : This method is suitable for estimation if organic compound contains C and H only. In case if other
elements e.g., N,S, halogens are also present the organic compound will also give their oxides which on
being absorbed in KOH will increase the percentage of carbon and therefore following modification
should be made.
(a) If N is also present : The gaseous oxide mixture is first passed over heated Cu gauze which reduces all
oxides of N to N2 which are neither absorbed by H2O nor by KOH
2NO + 2Cu  N2 + 2CuO
(b) If halogens are present : A roll of silver gauze is placed at the exit end of combustion tube which retains
all the halogens on itself.
2Ag + X2  2AgX
2Ag + CuX2  2AgX + Cu
(c) If S is present : A layer of fused lead chromate is placed near the exit end, all the oxides of sulphur are
oxidised to PbSO4 & left in tube it self.
Cr+6 + 3e–  Cr+3
S+4  S+6 + 2e–
(in SO 2) (in SO 4–2 )
JEEMAIN.GURU

 GENER AL CONCEPT FOR DRYING AND DEH YDR ATING AGENTS

(1) Acidic oxides ( non metals oxides such as CO 2, NO 2, SO 2 P 2O 5 etc.) are absorbed by alkali (KOH,
NaOH, Ca(OH) 2 etc.)
(ii) Basic oxides (Na2O, K2O etc.) are dissolved in acids (H2SO4, HCl etc.)
(iii) Acidic oxides can not be dried by basic dehydrating agent (e.g CaO) but they are dried by acid dehydrat-
ing agent (e.g H2SO4, P2O5 etc). However H2S can be dried by H2SO4 because it reacts with H2SO4.
H2S + H2SO4  2H2O + S + SO2
(iv) Basic substances can not be dried by acidic dehydrating agent but are dried by basic dehydrating agent
(e.g CaO). It is because NH3 is dried by CaO but not by H2SO4.

 ESTIM ATION OF NITROGEN

(a) Duma's method :
CuO Pass over Cu gauze
Organic compound 
heated strongly  Mixture of oxides    N2+ Other oxides

(w g) 
drying agent Pass through
Dry N2    N2 + Moisture 
KOH (aq.) 

(Let Vml at N.T.P.)

 22400 ml N2 weigh at N.T.P. = 28 g

28
 V ml N2 weigh at NTP = V g
22400

28 V
since w g organic compound gives   100 g
22400 w

28 Volume of N 2 at NTP
 %N    100
22400 weight of the compound

Note : This method can be used to estimate nitrogen in all types of organic compounds.
 KJELDAHL'S METHOD :
This method is based on the principle that a nitrogenous organic compound on heating with conc. H 2SO 4
converts all its nitrogen quantitatively to ammonium sulphate ;
organic compound + conc. H2SO 4 + K 2 SO 4 + CuSO 4
(w g) (raises the B.P. of H2SO4) (catalyst)

   Heating in Kjeldahl flask

add KOH
(NH 4 )2 SO 4   NH 3 is formed
drop by drop 

Pass this gas through V1 ml of N1 H2SO4

Now titrate the H2SO4 by another alkali say of N1 H2SO4 (NH3 is absorbed here)
V2 ml of N2 ,KOH are used
Meq of H2SO 4 taken = N1V 1
Meq. of KOH used for H2SO4 = N2V2
 Meq. of H2SO4 for NH3 = N1V1 – N2V2
 Meq. of NH3 formed = (N1V1 – N2V2) or say NV)
(the difference obtained or V ml of N H2SO4 are used to absorb NH3)
JEEMAIN.GURU
WNH 3
  1000  NV
17

 WNH  17  NV
3
1000
Now  17 g NH3 has 14 g Nitrogen
17 14  17  NV
  NV g NH has g Nitrogen
1000 3 17  1000
14NV
= g Nitrogen
1000
14NV
 w g organic compound has g nitrogen
1000
14NV  100
 .100 g organic compound has g nitrogen.
w  1000
1.4NV
= g nitrogen
w
Normality of the acid  volume of the acid
 % Nitrogen  1.4  weight of the compound
Note : This method is simpler and more convenient and is mainly used for finding out the percentage of nitrogen in
food stuffs, soil, fertilizers and various agricultural products. This method cannot be used for compound having
nitro groups, azo gp. (–N = N–) and nitrogen in the ring (pyridine, quinole etc.). Since nitrogen in these
compounds is not quantitatively converted in to ammonium sulphate.

 ESTIM ATION OF SULPHUR (CARIUS METHOD) :

Organic compound + con. HNO3 + BaCl2  ppt (BaSO4) is dried and weighed say "a" g
(w g)
Furning.HNO 3 BaCl2
S   H2SO4   BaSO4 + HCl
 233 g BaSO4 has 32 g sulphur (a g)

32  a
 a g BaSO4 has g sulphur
233

32  a  100
 % of Sulphur =
233  w

32 weight of BaSO 4 formed

%S   100
233 weight of compound

 ESTIM ATION OF HALOGENS ( CARIUS METHOD) :

Organic compound + con HNO3 + AgNO3  ppt (AgX) is dried and weighed say a g

35.5 weight of AgCl

% of Cl =   100
143.3 weight of compound

80 weight of AgBr
% of Br =   100
188 weight of compound

127 weight of AgI

% of I =   100
235 weight of compound
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 ESTIM ATION OF PHOSPHORUS - (CARIUS METHOD) :
Organic compound + con. HNO3 + Magnesia mixture (MgSO4 + NH4OH + NH4Cl)
(w g)
2 MgNH4PO4  Mg2P2O7 + 2NH3 + H2O
Precipitate is dried and ignited to give magnesium pyrophosphate (Mg2P2O7) weighed say a g

62 weight of Mg 2 P2 O 7 formed
% of P    100
222 weight of compound

Atomic weight of P = 31 × 2 = 62 g
molecular weight of Mg2P 2O 7 = 222 g
 ESTIM ATION OF OXYGEN :

There is no direct formula and method for estimation of oxygen however, percentage of oxygen is calculated by

% of oxgyen = 100 – [Sum of the % of all other elements]

Note - A direct method for estimation of oxygen has been given by Alusive in 1947 known as Alusive
method.