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PURIFICATION AND CHARACTERIZATION OF ORGANIC COMPOUND
METHODS OF PURIFICATION OF ORGANIC COMPOUNDS
(1) Sublimation
➢ Certain solids directly changes from solid to vapour state on heating. This process is called sublimation. The
vapour on cooling give back the solid.
➢ Difference in sublimability is the basis of this method
➢ Eg., Camphor, naphthalene, benzoic acid, anthracene
(2) Simple Crystallization
➢ It is based on fact that certain compounds are partially soluble in a solvent at room temperature and
solubility increases with increase in temperature
➢ Eg., From a mixture of sugar and common salt, sugar can be separated by using ethyl alcohol or benzene
(3) Distillation- Distillation is the process of heating
a mixture of liquids to form its vapours and
condensing the vapours to get back the liquid
[a] Simple distillation
This method is used to separate
➢ Volatile liquid from non volatile impurities
➢ Liquids having greater difference in boiling
points
➢ Examples;
(1) a mixture of chloroform (334K) and aniline
(457K)
(2) ether (307K)and toluene (383K)
[b] Fractional Distillation
➢ If the boiling point of the two components are
very close to one another, the separation can
be achieved by fractional distillation
➢ In this technique, a fractionating column is
attached with the distillation flask
➢ Examples:
(1) Separation of petroleum
(2) Acetone (329 K) and methanol (338K)
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[c] Distillation under reduced pressure
Or (Vacuum distillation)
➢ This method is for the purification of liquids
having high boiling point and which
decompose at or below their boiling point, If
the pressure is reduced, The liquid boil at
lower temperature
➢ Eg.
(1) Purification of Glycerol from spent lye
(fatty acid)
(2) Concentration of sugarcane
[d] Steam distillation
➢ Those compound which are steam volatile but
are insoluble in water can be purified by this
method.
➢ Here liquid will boil at lower temperature than
its normal boiling point due to the presence of
steam
➢ Dalton’s Law of Partial pressure is the basis of
steam distillation
➢ Eg. Isolation of Ortho nitro phenol from a
mixture containing para nitro phenol. Aniline
,
(4) Differential Extraction
This method is used for the separation of nonvolatile
organic substances (solid or liquid) from aqueous
solutions by shaking with a suitable solvent like ether,
benzene et.,
Examples
(1) Benzoic acid from water
(2) Sugar from water
(5) Chromatography
➢ Tswett introduced this physical method.
It is a technique used for the separation (Purification) of mixtures depending upon their difference in distribution
(adsorption or Partition) between two phases, one mobile phase and one stationary phase
Depending upon the nature of stationary and mobile phases, there are different types of chromatography
Chromatography Mobile phase Stationary phase Uses
Adsorption chromatography
Liquid Solid Large scale separation
(a) Column chromatography
(b) Thin-layer chromatography Liquid Solid Qualitative analysis
Qualitative and Quantitative analysis of
Partition chromatography
Liquid Liquid polar compounds like sugar,
Paper Chromatography
aminoacids
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identified from their retardation factor or retention
Adsorption chromatography
factor
➢ It is based on differential adsorption of various
Retardation factor (Rf) is the ratio of distance
components.
travelled by components to the distance travelled by
➢ Different components of a mixture will have
solvent
different adsorbing ability
Column Chromatography
In this method
Stationary phase: A solid (adsorbent) such as silica
gel, anhydrous Al 2 O3 , Magnesium oxide, starch,
charcoal etc. and
Mobile phase: A liquid.
The mixture to be separated is dissolved in a
suitable solvent and poured on the top of the
vertical column of adsorbent.
The compounds of the mixture are adsorbed in Partition Chromatography (Paper Chromatography)
different regions depending upon their affinities of It is based on continuous differential
the adsorbent. Thus different bands or zones or partitioning of components of mixture between
chromatograms are formed in the column. Th stationary and mobile phase.
The adsorbed components can be extracted Here stationary phase is a special type of paper
(eluted) with the help of a suitable solvent. called chromatographic paper contains water trapped
in it,.
The mobile phase is another liquid containing the
mixture.
It is used to separate sugars and amino acids
A strip of chromatography paper spotted at the base
with the mixture is suspended in a suitable solvent.
This solvent act as mobile phase. The solvent rises up
by capillary action. The paper selectively retains
different components. Which is then identified by Rf
Thin layer Chromatography
values
It is also an adsorption chromatography. Here
the stationary phase is a thin layer of adsorbent
(silica get, alumina) coated on a glass plate. A
solution of mixture to be separated is applied as a
small spot on the glass plate and then dipped in a
suitable solvent. As the solvent moves up the
components of the mixture also move up and get
adsorbed in different places. The various
components on the developed TLC plate can be
QUALITATIVE ANALYSIS- DETECTION OF ELEMENTS
Detection of C and H
To the given solution, cupric oxide is added The formed gas is passed through
C+ 2CuO CO2 + 2Cu; (1) Lime water, if it turn milky , presence of C is confirmed
2H + CuO → H2O + Cu (2) Anhydrous CuSO4, if it turned blue, presence of H confirmed
N, S, halogens and P are detected using Lassaigne’s extract
Lassaigne’s Test: Lassaigne’s extract: The extract of organic compound made with Na metal is called sodium fusion extract
or Lassaigne’s reagent, The elements present in the compounds are converted from covalent form into ionic by above
reaction, thereby they can be easily tested
Na+C+N → NaCN sodium cyanide; 2Na + S → Na2S Sodium sulphide
Na+X → NaX(Sodiumhalide); Na+C+N+S → NaCNS (Sodium Sulphocyanide)
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Methods/experiments Observation Name of Product
Detection of N
Fe4 Fe(CN )6 3
The extract is boiled with freshly prepared ferrous sulphate
solution and then con. H2SO4 are added
Deep Blue Or Ferric Ferrocyanide
Na + C + N NaCN
[Prussian Blue] Iron (III) hexacyano
Fe + 6CN
2+ ─ [Fe(CN)6]4─ (hexacyanofrrrate(II))
3[Fe(CN)6]4─ + 4 Fe3+→Fe4[Fe(CN)6]3 (Prussian blue) ferrate (II)
If the compound contain both N and S, then in the above Fe(SCN)3
Blood red
reaction, Ferric thiocyanate
Detection of halogen
(1) White curdy ppt (1) AgCl
A small amount of the extract is acidified with dilute nitric soluble in NH4OH (Presence of Cl2 )
acid and boiled to expel the gases. It is then cooled and a small (2) Pale Yellow ppt. (2) AgBr
amount of silver nitrate solution is added sparingly soluble in
NH4OH
(Presence of Br2 )
NaX + AgNO3→AgX + NaNO3 (3) Yellow ppt. (3) Agl
insoluble in NH4OH (Presence of I2 )
Detection of Sulphur
The extract is divided into two parts
(1) a few drops of sodium nitroprusside ( Na2 Fe(CN )5 NO ) Na4 Fe(CN )5 NOS
Violet
reagent are added [Link]
S2-+ [Fe(CN)5NO]2- → [Fe(CN)5 NOS]4-
(2) the extract is acidified with acetic acid and then lead
acetate solution is added Black
PbS
S2- + Pb2+ PbS
Detection of P
Extract of the compound is made with Na 2O2 (NH4)3PO4.12MoO3
𝑁𝑎2 𝑂2 𝑖𝑛𝐻2 𝑂 → (𝑁𝑎3 𝑃𝑂4 ) Yellow Ammonium phospho
To the extract ammonium molybdate is added. (NH4)2MoO4 molybdate
NB:- The Lassaigne’s extract has to be boiled with dil. HNO3 before the addition of AgNO3 due to the following
reason. If the compound also contains N or S, the extract will contain NaCN or Na2S also. By boiling with HNO3, these
compounds are decomposed as HCN (g) and H2S (g) respectively to avoid interference with the test for halogens.
Quantitative Analysis of Organic Compounds
Estimation of nitrogen
Estimation of Carbon and Hydrogen
1. Duma’s Method
(Leibig’s Method)
It is a method to determine the percentage of
A Known mass of organic compound heated with
nitrogen in the given compound by converting the
anhydrous cupric oxide. The resultant carbon dioxide
nitrogen present in the compound into N2 gas. It is
and water are absorbed in previously weighed KOH
calculated using the following equation
and anhydrous calcium chloride tube respectively. The
increased weight of KOH bulb and CaCl2 tube gives Percentage N2 =
28 Volume of N 2 at STP
100
the weight of carbon dioxide and water respectively. 22400 Mass of substance
[procedure:-A known mass of the given organic
The following equation is used.
compound is heated with cupric oxide in an
Percentage of Carbon
atmosphere of carbon dioxide. The released nitrogen is
12 Mass of CO 2 formed collected and the volume is measured. The volume is
= 100
44 Mass of substance then convert to STP]
Percentage of Hydrogen 2. Kjeldahl’s Method
It is a method to determine the percentage of
2 Mass of H 2 O formed
= 100 nitrogen in the given compound by converting the
18 Mass of substance
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nitrogen present in the compound into NH3 gas. It is ammonium molybdate. It is filtered washed and
calculated using the following equation weighed.
31 𝑀
V % of Phosphorus= × × 100
1.4 M 2V − 1 1877 Mass of substance
Percentage of nitrogen = 2 2. Also by converting into magnesium pyrophosphate.
W
The phosphoric acid is then treated with magnesia
Note: nitrogen present in ring, nitro compound and
mixture followed by ignition yields magnesium
azo compounds are not detected by Kjeldahl’s method
as the nitrogen of these compounds can not be
pyrophosphate (Mg 2 P2 O7 )
converted into ammonium sulphate.
Estimation of Halogen Percentage of Phosphorus = 62 M 100
222 W
A known mass of the substance is heated with
concentrate HNO 3 and crystals of AgNO3 in a carius. Estimation of Oxygen
• Usually estimated by the difference between the
The resultant silver halide is filtered was dried and
total percentage-composition (100) and the sum of
weighed.
the percentages of all other elements.
Percentage of Chlorine
• Can also be estimated directly: If an organic
35.5 Mass of AgCl
= 100 compound (of known mass) is heated in a stream
143.5 Mass of substance
of N2 gas, it gets decomposed to form O2 gas and
Percentage of Bromine
other gaseous products. It is then treatedwith I2O5
80 Mass of AgBr
= 100 gives CO2 from which we can calculate the
188 Mass of substance percentage using below equationTwo moles of
Percentage of Iodine CO2 are obtained from one mole of O2, i.e., 88 g of
127 Mass of Agl CO2 is obtained if 32 g of O2 is liberated.
= 100 32 Mass of CO2
235 Mass of substance % of Oxygen = × Mass of substance × 100
88
Estimation of Sulphur (Carius Method)
A known mass of substance is heated with
Q10. Discuss the chemistry of Lassaigne’s test for the
concentrate HNO 3 or sodium peroxide in a carius
above elements.
tube. The resultant sulphuric acid is precipitate as Q11. In the Carius method of estimation of halogen, 0.15g
barium sulphate by adding barium chloride solution. of an organic compound gave 0.12g of AgBr. Find the
It is filtered wash dried and weighed. percentage of Br in the compound.
32 Mass of BaSO 4 Q12. Different methods are used to purify organic
% Sulphur = 100
233 Mass of substance compounds. Name any three methods of purification.
Estimation of Phosphorus Q13. Explain
1. By converting into ammonium phosphomolybdate a) Kjeldahl’s method
A known mass of the organic compound heated b) Dumas method
with concentrated HNO3 in a carius tube. The Q14. On complete combustion, 0.246g of an organic
compound gave 0.198g of CO2 and 0.1014g of H2O.
resultant phosphoric acid is precipitated at ammonium Determine the percentage composition of carbon and
phosphomolybdate by heating with HNO 3 and hydrogen in the compound.