ISOLATION AND PURIFICATION OF ORGANIC COMPOUNDS

Compiled by Olayanju Dare S.

Chemistry, UNIMED, Ondo
Isolation/extraction
Solid-liquid extraction:
For very soluble solid, simple stirring or shaking of a suspension of the solid in the liquid, followed by
gravity filtration to remove insoluble impurities.
Use of Soxhlet extractor: This is used for isolating/extracting less soluble substances, or material trapped
in an insoluble matrix

Soxhlet Extractor
The device boils the extraction liquid, condenses it so that it can come into contact with the solid, and
siphons the liquid back into the boiling flask. The extraction process continues (continuous extraction)
until boiling is ceased.
The extraction solvent is enriched with the desired compound over time.
Liquid-liquid extraction
Used to separate a component from one liquid phase into another.
For most extractions, one phase is an aqueous solution and the other an immiscible organic liquid.
The two phases are shaken together gently in a Separatory funnel, allowed to separate, and separated from
each other by allowing the lower, more dense, phase to drain through the stopcock into an Erlenmeyer
flask.
 Separatory Funnel
The less dense phase is usually poured out through the top of the funnel to avoid contamination.
Multiple extractions can be performed by returning/leaving the phase to be extracted in the funnel for
additional extractions with the other solvent.
Methods OF purification OF Organic compounds
Various methods adopted in the purification of organic compounds depend on the nature of the compound
and the impurity present in it.
These include:
(i) Sublimation
(ii) Crystallisation
(iii) Distillation (simple distillation, fractional distillation, distillation under reduced pressure,
steam distillation)
(iv) Differential extraction
(v) Chromatography
Sublimation:
When some solid substances are heated, they change from solid to vapour state without passing through
the liquid state.
Sublimation technique relies on this above principle.
The method is used to separate sublimable compounds from non-sublimable impurities.
Crystallisation/Recrystallization
It is one of the techniques used in the purification of solid organic compounds.
It makes use of the advantages of the difference in the solubilities of the compound and the impurities in a
suitable solvent.
The impure compound is dissolved in a solvent in which it is sparingly soluble at room temperature but
appreciably soluble at higher temperature.
The solution is concentrated to get a nearly saturated solution.
On cooling the solution, pure compound crystallises out and is removed by filtration.
The filtrate will then contain impurities and small quantity of the compound.
If the compound is highly soluble in one solvent and very little in another solvent, crystallisation can be
carried out using mixture of these solvents.
Impurities, which impart colour to the solution are removed by adsorbing over activated charcoal.
Repeated crystallization becomes necessary for the purification of compounds containing impurities of
comparable solubilities.
The solvent for this techniques must have some qualities which include:

 The substance must be insoluble in the solvent at room temperature

 The substance must be very soluble in the solvent at its boiling point
 The solvent should have a fairly low boiling point
 The solvent must dissolve the substance but must not react with it
 At cooling, the compound must settle out in well-formed crystals
 At room temperature, a good solvent must dissolve the impurities.

Simple Distillation
This is used to separate;
(i) volatile liquids from nonvolatile impurities; and
(ii) the liquids having sufficient difference in their boiling points.
In this technique, a liquid substance is heated to its boiling point. The liquid vaporizes and is condensed
back into liquid in a condenser column.
Note:

 When the boiling point is above 160 oC, an air condenser may be used.
 Water condenser is used when the boiling point is lower than 160 oC.
 For volatile low boiling compound such as ether, dichloromethane, methanol or chloroform, cold
water passing through the condenser will help in recovering good percentage of the distillate.

Simple distillation: The vapours of a substance formed are condensed and the liquid is collected in conical
flask.
Fractional Distillation: This is used in separating liquids of closer boiling points. In the technique,
vapours of a liquid mixture are passed through a fractionating column (packed with inert material such as
glass beads) before condensation. Vapours of the higher boiling point liquid condenses prior to that of the
lower boiling point liquid.
Each successive condensation and vaporization unit in the fractionating column is called a theoretical
plate.
A technological applications of fractional distillation is the separation of different fractions of crude oil in
petroleum industry

Set-up for fractional distillation

Distillation under reduced pressure/ Vacuum Distillation
This is for the purification of liquids of very high boiling points and those, which decompose at or below
their boiling points.
Such liquids are made to boil at a temperature lower than their normal boiling points by reducing the
pressure on their surface.
A liquid boils at a temperature at which its vapour pressure is equal to the external pressure.
The pressure is reduced with the help of a water pump or vacuum pump.
For example, glycerol can be separated from spent-lye in soap industry using this method.
 Set up for the distillation under reduced pressure

Steam Distillation:
This method is used to separate substances which are steam volatile and are immiscible with water.
In the method, steam from a steam generator is passed through a heated flask containing the liquid to be
distilled.
The mixture of steam and the volatile organic compound is condensed and collected.
The compound is later separated from water using a separating funnel.
In steam distillation, the liquid boils when the sum of vapour pressures due to the organic liquid (P1) and
that due to water (P2) equals that of atmospheric pressure (P), i.e. P = P1+ P2.
Since P1 is lower than P, the organic liquid vaporises at lower temperature than its boiling point.
Thus, if one of the substances in the mixture is water and the other, a water insoluble substance, then the
mixture will boil close to but below, 373K (100 oC).
A mixture of water and the substance is then obtained which can be separated by using a separating funnel.
Aniline is separated by this technique from aniline – water mixture.
 Set-up for steam distillation

Differential extraction:
Differential extraction is carried out in a separatory funnel.

For organic compound that is less soluble in the organic solvent, a very large quantity of solvent would
only extract a very small quantity of the compound using this approach.
In such case, continuous extraction (discussed above) is the most suitable in which the same solvent is
repeatedly used in the extraction of the compound.
The organic solvent is later removed by distillation or by evaporation to get back the compound
Chromatography:
Chromatography is used to separate mixtures into their components, purify compounds and to test the
purity of compounds.
The name chromatography is from Greek word chroma, for colour as the method was first used for the
separation of coloured substances found in plants.
In this technique, the mixture of substances is applied onto a stationary phase, which may be a solid or a
liquid.
A pure solvent, a mixture of solvents, or a gas is allowed to move slowly over the stationary phase.
The components of the mixture get gradually separated from one another.
The moving phase is called the mobile phase.
Categories of Chromatography with respect to the principle involved include:
(a) Adsorption chromatography
(b) Partition chromatography.

Adsorption Chromatography:
Adsorption chromatography is based on the fact that different compounds adsorb on an adsorbent to
different degrees.
Commonly used adsorbents are silica gel and alumina.
When a mobile phase is allowed to move over a stationary phase (adsorbent), the components of the
mixture move by varying distances over the stationary phase.
Two main types of chromatographic techniques based on the principle of differential adsorption are;
i. Column chromatography, and
ii. Thin layer chromatography.

Column Chromatography:
This involves separating a mixture over a column of adsorbent (stationary phase) packed in a glass tube.
The column is fitted with a stopcock at its lower end.
The mixture to be separated into its constituents is placed on the top of the adsorbent column packed in a
glass tube.
An appropriate eluant which is a liquid or a mixture of liquids is allowed to flow down the column
slowly.
Depending on the affinity of the different compounds in the mixture for the adsorbent, the constituents of
the mixture are completely separated.
The most readily adsorbed substances (of strongest affinity for the adsorbent) are retained near the top
and others come down to various distances in the column.
Thin Layer Chromatography:
Thin layer chromatography (TLC) involves separation of substances of a mixture over a thin layer of an
adsorbent coated on glass plate.
A thin layer (about 0.2mm thick) of an adsorbent (silica gel or alumina) is spread over a glass plate of
suitable size.
The plate is known as thin layer chromatography plate or chromaplate.
The solution of the mixture to be separated is applied as a small spot about 2 cm above one end of the
TLC plate.
The glass plate is then placed in a closed jar containing the eluant.
As the eluant rises up the plate, the components of the mixture move up along with the eluant to different
distances depending on their degree of adsorption and separation takes place.
The relative adsorption of each component of the mixture is expressed in terms of its retardation/retention
factor i.e. Rf value.
Distance moved by the substance from base line (x)
Rf = Distance moved by the solvent from base line (y)

The spots of coloured compounds are visible on TLC plate due to their original colour.
The spots of colourless compounds, which are invisible to the eye but fluoresce in ultraviolet light, can be
detected by putting the plate under ultraviolet light.
Another detection technique is to place the plate in a covered jar containing a few crystals of iodine. Spots
of compounds, which adsorb iodine, will show up as brown spots.
Sometimes an appropriate reagent may also be sprayed on the plate.
For example, amino acids may be detected by spraying the plate with ninhydrin solution.
Partition Chromatography:
Partition chromatography is based on continuous differential partitioning of components of a mixture
between stationary and mobile phases.
Paper chromatography is a type of partition chromatography. In paper chromatography, a special quality
paper known as chromatography paper is used. Chromatography paper contains water trapped in it, which
acts as the stationary phase.
A strip of chromatography paper spotted at the base with the solution of the mixture is suspended in a
suitable solvent or a mixture of solvents. This solvent acts as the mobile phase. The solvent rises up the
paper by capillary action and flows over the spot. The paper selectively retains different components
according to their differing partition in the two phases.
The paper strip so developed is known as a chromatogram. The spots of the separated coloured
compounds are visible at different heights from the position of initial spot on the chromatogram.
The spots of the separated colourless compounds may be observed either under ultraviolet light or by the
use of an appropriate spray reagent as discussed earlier.

Finally, the purity of the compound is then ascertain by determining its melting point (if solid) or boiling
point (if liquid).
Most pure compounds have sharp melting points (for solids) and boiling points (for liquids).
Modern approaches to checking the purity of an organic compound now based on different types of
chromatographic and spectroscopic techniques.

Qualitative analysis of Organic Compounds

Detection of carbon and hydrogen
Heat the compound with copper (II) oxide. Carbon in it is oxidized to carbon dioxide (tested with lime-
water to give turbidity) and hydrogen to water (turns blue when tested with anhydrous copper sulphate).
C + 2CuO →2Cu + CO2
Δ
2H + CuO → Cu + H2O
Δ
 CO2 + Ca(OH)2 → CaCO3↓ + H2O
CO2 + Ca(OH)2 → CaCO3↓ + H2O
5H2O + CuSO4 → CuSO4.5H2O
White Blue
Detection of Other elements
Nitrogen, sulphur, halogens and phosphorus present are detected by “lassaigne’s test”.
This involves the conversion of these elements from covalent form into the ionic form by fusing the
compound with sodium metal as given by the following equations;

Cyanide, sulphide and halide of sodium formed are extracted from the fused mass by boiling it with
distilled water. This extract is known as sodium fusion extract.
Test for Nitrogen
Boil the sodium fusion extract with iron(II) sulphate and then acidified with concentrated sulphuric acid.
The formation of Prussian blue colour confirms the presence of nitrogen.
Sodium cyanide first reacts with iron(II)sulphate and forms sodium hexacyanidoferrate(II).
On heating with concentrated sulphuric acid some iron(II) ions are oxidised to iron(III) ions which react
with sodium hexacyanidoferrate(II) to produce iron(III) hexacyanidoferrate(II) (ferriferrocyanide) which
gives the Prussian blue colour.

Test for Sulphur

(a) Acidified the sodium fusion extract with acetic acid and then add lead acetate to it.
Formation of black precipitate of lead sulphide indicates the presence of sulphur.
S2– + Pb2+ → PbS
Black
(b) Treat the sodium fusion extract with sodium nitroprusside, appearance of a violet colour indicates the
presence of sulphur.
S2– + [Fe(CN)5NO]2– → [Fe(CN)5NOS]4–
Violet
If nitrogen and sulphur are present in the compound, sodium thiocyanate is formed which gives blood red
colour with no Prussian blue as there are no free cyanide ions.
Na + C + N + S → NaSCN
Fe3+ +SCN– → [Fe(SCN)]2+
Blood red
However, if excess sodium is used in the sodium fusion, the thiocyanate decomposes to yield cyanide and
sulphide.
NaSCN + 2Na → NaCN+Na2S
These ions (CN- and S2-) then give their usual tests.

Test for Halogens

Acidify the sodium fusion extract with nitric acid and then treat the resulting solution with silver nitrate.
A white precipitate, soluble in ammonium hydroxide will give the presence of chlorine. A yellowish
precipitate, sparingly soluble in ammonium hydroxide will indicate the presence of bromine
A yellow precipitate, insoluble in ammonium hydroxide will reveal the presence of iodine.
X– + Ag+ → AgX
X = Cl, Br or I.
If nitrogen or sulphur is present in addition to the halogens, then there is need to first boil the sodium
fusion extract with concentrated nitric acid so as to decompose sodium cyanide or sulphide formed during
Lassaigne’s test. Otherwise, ions from these elements will interfere with silver nitrate test for the
halogens.

Test for Phosphorus

Phosphorus present is first oxidized to phosphate by heating the compound with an oxidizing agent
(sodium peroxide). The solution formed is boiled with nitric acid and then treated with ammonium
molybdate.
A yellow colouration or precipitate indicates the presence of phosphorus.
Na3PO4 + 3HNO3 → H3PO4+3NaNO3
H3PO4 + 12(NH4)2MoO4 + 21HNO3 → (NH4)3PO4.12MoO3 + 21NH4NO3 +12H2O
Ammonium molybdate Ammonium phosphomolybdate

Quantitative analysis
The percentage composition of elements (which can be used to determine the empirical and molecular
formula of compound) present in an organic compound is determined using the following methods:
Carbon and Hydrogen
A known mass of an organic compound is burnt in the presence of excess of oxygen and copper(II)
oxide.
Carbon and hydrogen in the compound are oxidized to carbon dioxide and water, respectively.
CxHy + (x + y/4) O2 → x CO2 + (y/2) H2O

Set-Up for the estimation of carbon and hydrogen.

 Note: Water and carbon dioxide formed on oxidation of substance are absorbed in anhydrous calcium
chloride and potassium hydroxide solutions respectively contained in U tubes.
The mass of water produced is determined by passing the mixture through a weighed U-tube containing
anhydrous calcium chloride.
Carbon dioxide is absorbed by concentrated solution of potassium hydroxide in another U-tube.
The increase in masses of calcium chloride and potassium hydroxide gives the amounts of water and
carbon dioxide. The percentages of carbon and hydrogen are calculated from this gain in weight.
Calculation:
Let the mass of organic compound = m g
Mass of water = m1 g
Mass of carbon dioxide produced = m2 g
12 𝑥 𝑚2 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛 =
44 𝑥 𝑚
2 𝑥 𝑚1 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 =
18 𝑥 𝑚
Worked Example:
On complete combustion, 0.246 g of an organic compound gave 0.198g of carbon dioxide and 0.1014g of
water. Determine the percentage composition of carbon and hydrogen in the compound.
Solution
Mass of the compound = 0.246 g
Mass of CO2 = 0.198 g
Mass of water = 0.1014 g
12 𝑥 0.198 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛 = = 21.95 %
44 𝑥 0.246
2 𝑥 0.1014𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 = = 4.58 %
18 𝑥 0.246
Nitrogen
(i) Dumas method: The nitrogen containing organic compound is heated with copper oxide in an
atmosphere of carbon dioxide to yield free nitrogen in addition to carbon dioxide and water.
Cx Hy Nz + (2x + y/2) CuO → x CO2 + y/2 H2O + z/2 N2 + (2x + y/2) Cu
Traces of nitrogen oxides formed, if any, are reduced to nitrogen by passing the gaseous mixture over a
heated copper gauze.
The mixture of gases produced is collected over an aqueous solution of potassium hydroxide which
absorbs carbon dioxide.
Nitrogen is collected in the upper part of the graduated tube.
Calculation
Let the mass of organic compound = m g
Volume of nitrogen collected = V1 mL
Room temperature = T1K
𝑃1 𝑉1 𝑥 273
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑎𝑡 𝑆𝑇𝑃 = 𝑚𝐿
760 𝑥 𝑇1

Where P1 and V1 are the pressure and volume of nitrogen.

P1= Atmospheric pressure – Aqueous tension
22400 mL N2 at STP = 28 g in weight.
28𝑥 𝑉
𝑉 𝑚𝐿 𝑜𝑓 𝑁2 𝑎𝑡 𝑆𝑇𝑃 = 𝑔 𝑖𝑛 𝑤𝑒𝑖𝑔ℎ𝑡
22400
28𝑥 𝑉 𝑥 100
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 =
22400 𝑥 𝑚

Set-up for Dumas Method

Worked Example
In Dumas’ method for estimation of nitrogen, 0.3g of an organic compound gave 50 mL of nitrogen
collected at 300K temperature and 715mm pressure. Calculate the percentage composition of nitrogen in
the compound. (Aqueous tension at 300K=15 mm).
Solution
Mass of organic compound = 0.3 g
Volume of Nitrogen = 50 mL
Room Temperature = 300 K
Pressure of Nitrogen = 715 – 15 = 700 mm
700 𝑥 50 𝑥 273
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑎𝑡 𝑆𝑇𝑃 = = 41.9 𝑚𝐿
760 𝑥 300
22400 mL of N2 at STP = 28 g in weight
28𝑥 41.9
41.9 𝑚𝐿 𝑜𝑓 𝑁2 𝑎𝑡 𝑆𝑇𝑃 =
22400
28𝑥 41.9 𝑥 100
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 = = 17.46 %
22400 𝑥 𝑚
(iii) Kjeldahl’s method: The compound containing nitrogen is heated with concentrated sulphuric acid.
Nitrogen in the compound is converted to ammonium sulphate. The resulting mixture is heated with
excess sodium hydroxide. Ammonia gas liberated is absorbed in an excess standard solution of
sulphuric acid. The amount of ammonia produced is then determined by estimating the amount of
unreacted sulphuric acid after the absorption of ammonia. This is done by titrating it with standard
alkali solution. The difference between the initial amount of acid taken and that left after the reaction
gives the amount of acid that reacted with the ammonia.

Organic compound + H2SO4 → (NH4)2SO4

(NH4)2SO4 + 2NaOH → Na2SO4 + 2NH3 + 2H2O
2NH3 + H2SO4 → (NH4)2SO4
Calculation
Let the mass of organic compound taken = m g
Volume of H2SO4 of molarity, M, taken = V mL
Volume of NaOH of molarity, M, used for titration of excess of H2SO4 = V1 mL
V1 mL of NaOH of molarity M ≡ V1 /2 mL of H2SO4 of molarity M
Volume of H2SO4 of molarity M used in absorbing NH3 = (V – V1/2) mL
(V- V1/2) mL of H2SO4 of molarity M ≡ 2(V-V1/2) mL of NH3 solution of molarity M.
Therefore;
1000 mL of 1 M NH3 solution ≡ 17g NH3 or 14 g of N
2(V-V1/2) mL of NH3 solution of molarity M ≡ (14 x M x 2(V – V1/2))/1000 g of N
𝑉
𝑉 14 𝑥 𝑀 𝑥 2(𝑉− 1 )
2 (V − 21 ) mL of 𝑁𝐻3 solution of molarity M = 1000
2
𝑔 𝑜𝑓 𝑁

𝑉
14 𝑥 𝑀 𝑥 2(𝑉 − 21 ) 100
Percentage of N = 𝑥
1000 𝑚
 𝑉
1.4 𝑥 𝑀 𝑥 2(𝑉 − 21 )
Percentage of N =
𝑚
Note: Kjeldahl method cannot be used on compounds containing nitrogen in nitro and azo groups as well
as nitrogen present in a ring (e.g. pyridine). Nitrogen of these compounds cannot be converted to
ammonium sulphate under the operating conditions of the method.
Worked Example
During estimation of nitrogen present in an organic compound by Kjeldahl’s method, the ammonia
evolved from 0.5 g of the compound in Kjeldahl’s estimation of nitrogen, neutralized 10 mL of 1 M
H2SO4. Find out the percentage of nitrogen in the compound.
Solution
Mass of the compound = 0.5 g
1 M of 10 mL H2SO4 = 1M of 20 mL NH3
1000 mL of 1M ammonia ≡ 14 g nitrogen
14 𝑥 20
20 𝑚𝐿 𝑜𝑓 1 𝑀 𝑎𝑚𝑚𝑜𝑛𝑖𝑎 = 𝑔 𝑜𝑓 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛
1000
14 𝑥 20 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑁 = = 56.0 %
1000 𝑥 0.5
Halogens
Carius method: A known mass of an organic compound is heated with fuming nitric acid in the presence
of silver nitrate in a hard glass tube, known as Carius tube, in a furnace.

Set-up for Carius method

Carbon and hydrogen in the compound are oxidised to carbon dioxide and water. The halogen present
forms the corresponding silver halide (AgX). The AgX formed is then filtered, washed, dried and
weighed.
Calculation
Let the mass of organic compound = m g
Mass of AgX formed = m1 g
1 mol of AgX ≡1 mol of X
𝐴𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑋 𝑥 𝑚1
Mass of halogen in 𝑚1 g of AgX =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔𝑋
𝐴𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑋 𝑥 𝑚1 𝑥 100
Mass of halogen in 𝑚1 g of AgX =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔𝑋 𝑥 𝑚
Worked Example
In Carius method of estimation of halogen, 0.15 g of an organic compound gave 0.12 g of AgBr. Find out
the percentage of bromine in the compound.
Solution
Mass of the compound = 0.15 g
Mass of AgBr produced = 0.12 g
Molar mass of AgBr = 108 + 80 = 188 g mol-1
188 g AgBr ≡ 80 g bromine
80 𝑥 0.12
Mass of halogen in 0.12 g of AgX =
188
80 𝑥 0.12 𝑥 100
Percentage of Br = = 34.04 %
188 𝑥 0.15
Sulphur

A known mass of an organic compound is heated in a Carius tube with sodium peroxide or fuming nitric
acid. Sulphur present in the compound is oxidised to sulphuric acid and precipitated as barium sulphate
on addition of excess barium chloride solution. The precipitate is filtered, washed, dried and weighed.
The percentage of sulphur is estimated from the mass of barium sulphate formed.

Calculation

Let the mass of organic compound = m g

Mass of barium sulphate formed = m1g

1 mol of BaSO4 = 233 g BaSO4 = 32 g sulphur

32 𝑥 𝑚1
𝑚1 𝑔 𝐵𝑎𝑆𝑂4 ≡ 𝑔 𝑠𝑢𝑙𝑝ℎ𝑢𝑟
233
32 𝑥 𝑚1 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑠𝑢𝑙𝑝ℎ𝑢𝑟 =
233 𝑥 𝑚
Worked example

In sulphur estimation, 0.157 g of an organic compound gave 0.4813 g of barium sulphate. What is the
percentage of sulphur in the compound?

Solution

Mass of the compound = 0.157 g

Mass of BaSO4 = 0.4813 g

Molecular mass of BaSO4 = 137+32+64 = 233 g

233 g BaSO4 ≡ 32 g sulphur

32 𝑥 0.4813
0.4813 𝑔 𝐵𝑎𝑆𝑂4 ≡ 𝑔 𝑠𝑢𝑙𝑝ℎ𝑢𝑟
233
32 𝑥 0.4813 x 100
Percentage of S𝑢𝑙𝑝ℎ𝑢𝑟 = = 42.10 %
233 𝑥 0.157
Phosphorus

A known mass of an organic compound is heated with fuming nitric acid. Phosphorus present is oxidised
to phosphoric acid in the process. This is then precipitated as ammonium phosphomolybdate,
(NH4)3PO4.12MoO3 upon the addition of ammonia and ammonium molybdate.

Alternatively, phosphoric acid may be precipitated as MgNH4PO4 by adding magnesia mixture which on
ignition yields Mg2P2O7.

Calculation

Let the mass of organic compound taken = m g

mass of ammonium phosphomolydate = m1 g

Molar mass of (NH4)3PO4.12MoO3 = 1877 g/mol

Molar mass of phosphorus = 31 g/mol

31 𝑥 𝑚1 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑝ℎ𝑜𝑠𝑝ℎ𝑜𝑟𝑢𝑠 = %
1877 𝑥 𝑚

If phosphorus is estimated as Mg2P2O7

62 𝑥 𝑚1 𝑥 100
𝑃𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑝ℎ𝑜𝑠𝑝ℎ𝑜𝑟𝑢𝑠 =
222 𝑥 𝑚
Where;

Molar mass of Mg2P2O7 = 222 u

Mass of organic compound = m

Mass of Mg2P2O7 formed = m1

Atomic mass of two atoms of phosphorus present in Mg2P2O7 = 62

Oxygen

% of oxygen in an organic compound can be obtained using;

% of oxygen = 100 – sum of the percentages of all other elements.

OR

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 and all the oxygen is
converted to carbon monoxide.

The mixture is then passed through warm iodine pentoxide (I2O5). In the process, carbon monoxide is
oxidised to carbon dioxide with the liberation of iodine
Heat O2 + other gaseous products
Compound
1373 K
2C + O2 2CO
I2O5 + 5CO I2 + 5CO2

Balancing the last two equations for equal amount of CO, we have;

10C + 5O2 10CO

2I2O5 + 10CO 2I2 + 10CO2

From the equation, 1mole of oxygen liberated from the compound produces two moles of
carbondioxide (i.e. 5:10 ≡ 1:2).

If the mass of CO2 produced = m1 g

Mass of the organic compound = m g

Then;

88 g CO2 ≡ 32 g of oxygen from the compound

32 x 𝑚1
m1 g of CO2 ≡ g of oxygen from the compound
88
32 x 𝑚1 𝑥 100
% mass of oxygen = 88 𝑚

One could also calculate the percentage of oxygen in the compound from the amount of iodine
produced.

The elements, carbon, hydrogen and nitrogen present in a compound can also be determined using an
apparatus known as CHN elemental analyser.
The analyser only makes use of a very small amount of the substance and displays the values on a screen
within a short time.