Chem - 131

Chapter: Separation Techniques

Topics: Distillation and Solvent Extraction
 Distillation

 General distillation
 Fractional distillation
 Steam distillation

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 2

 General Distillation
 Employed for the purification of liquids from
non-volatile liquids
 The Impure liquid is boiled in a flask.
 The vapors formed in the flask are
condescend and pure liquid is collected in
another vessel
 Distillation is stopped when the temperature
starts to rise once again
 To prevent bumping some pieces of porcelain
is added in to flask.
 For liquids having B.P. ›110 oC , air
condenser is used.
 For very volatile and inflammable liquid
distillatillation flask is heated on a water-bath
 In case of very high-boiling liquids, the flask is
heated directly with a naked flame.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 3
Fractional Distillation
Fractional distillation means that a type of distillation that involves the
separation of miscible liquids having low differences in boiling points.
The fractional distillation process involves repeated distillation
(vapourization) and condensation.
Usually, the separation of a mixture into component parts takes place in
fractional distillation column.
The separation takes place when the mixture is in exposure to heat at a
particular temperature where fractions of mixture start to vaporize.
The basic principle of fractional distillation is that different liquids
evaporate and boil at various temperatures. Therefore in fractional
distillation during the heating of the mixture, the substance which has a
lower boiling point, will start to boil first and hence convert into vapours.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 4
Fractional Distillation Distillation
When the components of a mixture have When the components of a mixture have a
little difference in their boiling points, the large difference in their boiling points, they
mixture is separated by this process. are separated by simple distillation.

Apparatus is complex as compared to simple The apparatus is simple and consists of two
distillation. A fractionating column is also flasks and a condenser.
required.

Using this process, the solvent cannot be The solvent can be separated from the solute
separated from the solute. using distillation.

It does not need to be repeated many times This process is repeated several times to get
to get pure liquid. pure liquid.

For example, crude oil refining can be done For example, seawater purifying can be done
with the help of this process. with the help of this process.

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The Procedure of Fractional Distillation
 Some of the fractional distillation apparatuses in use for the process are distilling
flask, receiver, thermometer, heat source, condenser and fractionating column.
 After we set up the apparatus the mixture of liquids A and B, which are miscible
are taken, where A has greater volatility than B substance.
 The solution is put into the distilling flask, and the tip of the flask is in connection
with the fractionating column.
 The heat increases the temperature slowly. The vapours start to rise in the flask as
soon as the mixture starts to boil. The vapours come out from the volatile
component A.
 The vapours move towards the condenser through the fractionating column, where
it cools down to form a liquid which is then collected in the receiver.
 Until there is complete separation of the two mixtures vapourization and
condensation take place repeatedly throughout the process.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 6
Fractional Distillation

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Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 8
Fractional Distillation of Crude Oil
 The separation of various components of crude oil is one of the very common examples of
fractional distillation in the industry.
 Paraffin wax, diesel, lubricating oil, gasoline, kerosene, naphtha and petrol are the substances that
crude oil contains.
 The separation of these components takes place productively with the help of the distillation
process (using a distillation tower).
 Crude oil is put in the chamber and is given heat along with high-pressure steam. As a result, the
mixture starts to boil and thus the formation of vapour takes place. At this particular point, various
substances start entering the vapour phase.
 The vapour then rises up the fractional distillation column consisting of several plates.
 The plates consist of holes that allow the vapour to pass through.
 At the top of the fractionating column, the temperature is low. The components that have the
highest boiling point condense in the lower part of the column, on the other hand, the substance
with a low boiling point condenses at the top.
 From the sides of the column, the vapours or liquid fractions are removed. Later, the liquid
fractions are further in process in the condensers to cool them even more.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 9
 Fractionating Tower
 A fractionating tower is used in industry
instead of a ordinary fractionating column
used in laboratory
 Used for the refining of petroleum, distillation
of crude alcohol and distillation coal-tar
 A fractionating tower is divided into several
compartments, called ‘tray set’
 Each tray has hole, which is covered by a
bubble cap and a overflow pipe.
 Temperature falls from the bottom to top of
the tower
 At various levels of the tower a fixed
temperature is maintained by heating the
crude liquid steadily by steam coils
 At each level the vapor of high volatile
compounds go up through the holes of the
trays and vapor of low volatile compounds
condensed and go down.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 10
Fractions of crude petroleum obtained from a Fractionating Tower in Petroleum Industries

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Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 12
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 13
Advantages of Fractional Distillation
 It is a very easy process and purifies the components of a mixture
very well.
 The liquids having very little difference in boiling points can be
separated by this process.
 The fractionating column makes the separation of components easy.

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 14

Applications of Fractional Distillation
1. This process is to separate various useful fractions such as gasoline,
kerosene oil, diesel oil, lubricating oil etc. from crude oil in the petroleum
industry.
2. It is also known to separate acetone and methyl alcohol from pyroligneous
acid obtained by destructive distillation of wood.
3. It separates nitrogen, concentrate argon and oxygen from liquid air.
4. This process is used to separate thanol from fermented liquor.
5. It is useful in the process of purification of water.
6. Fractional isolation is in use for the separation of acetone and water.
7. Fractional distillation is also useful for the production of high-purity
silicon from chlorosilanes (SiHCl3). Silicon is very much in use in
semiconductors.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 15
 Steam Distillation
 Steam distillation is applied to separate the
substances that are insoluble in water and are
volatile in steam
 It is performed by using a current of steam
 Steam is generated in a steam generator
 Steam is passed through the distillation flask
 Steam pics up the volatile substances from the
mixture and passes into the condenser
 The distillate collected consist of water and the
organic substances, that can be separated by
using separating funnel.
 Stem distillation is used for the extraction of
essential oils from plants and flowers
 Also used in the manufacture of aniline and
turpentine oil
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 16
 Principle of Steam Distillation
A liquid boils when its vapor pressure is equal to the atmospheric
pressure. In steam distillation, a mixture of water and an organic liquid is
heated. The mixture boils when the combine vapor pressure of water (p1)
and that of organic liquid (p2) is equal to the atmospheric pressure (P).
i.e., P = p1 + p2.
Naturally, the boiling temperature of the mixture would be lower than
the boiling temperature of the pure organic liquid when the vapor
pressure of this liquid alone would be equal to the atmospheric pressure.
Thus in steam distillation, the liquid is distilled at a lower temperature
than its boiling point when it might decompose.

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 17

 Solvent Extraction
Nernst Distribution Law:
When a solute (X) is shaken up with two liquids (A and B) which are immiscible with
each other, but in both of which the solute is soluble, then the solute is found to
distribute itself between the two solvents in such a way so that the ratio of the
concentrations of the solute in two liquids is constant at a constant temperature.
Suppose,
Concentration of X in solvent A = C1
Concentration of X in solvent B = C2
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑋 𝑖𝑛 𝐴
Then,
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑋 𝑖𝑛 𝐵
= Constant
Or, C𝐶1 = 𝐾𝐷
2
Where, KD – Distribution/Partition Co-efficient
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 18
What is solvent extraction?
Solvent extraction is a method to separate a. compound or substance based on
its relative solubilities in to different immiscible liquids, usually water and an
organic solvent.
It is also known as liquid-liquid extraction.
It is performed on the basis of Nernst Distribution Law
Commonly used solvents are: ether, hexane, benzene, acetone, carbon
disulphide, carbon tetrachloride, dichloromethane, tributyl phosphate etc.
Examples:
1. Extraction of caffeine from its aqueous solution by dichloromethane.
2. Extraction of iodine from its aqueous solution by hexane.

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 20

 Separatory Funnel
Solvent extraction is carried out in a special glassware called separatory funnel.

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Principle of Solvent Extraction
In solvent extraction, a solute is separated from its solution
(usually aqueous) by using another suitable solvent (usually
organic) in which the solute is more soluble than in water.
When a suitable solvent is added to a solution containing
the extracting solute, the solute distributes itself between
the two liquids (solvents) according to Nernst distribution
law.
When solvent extraction is carried out in a separatory funnel
by shaking the aqueous solution with a suitable organic
solvent, most of the solute passes into organic layer. On
standing, the aqueous and organic layers separate in the
funnel. The lower aqueous layer is run out, leaving the
organic layer behind which is enriched with the solute.

Note: The grater the distribution ratio is in favor of the extracting solvent, the greater
will be the amount of extracted substance in any one operation.
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 22
 Uses of solvent extraction

 Separation of an organic substance from

an aqueous solution.
 Used in the processing of perfumes,
vegetable oil, or biodiesel.
 Solvent extraction is exclusively used in
separation and purification of uranium
and plutonium
 Also used in separation of cobalt and
nickel
 Separation and purification of rare
earth elements etc.

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 23

Multi-step Extraction:

Solvent extraction may be repeated with aqueous layer left after the
first extraction with a fresh quantity of the solvent.

In a multiple extraction, a certain quantity of solvent is used to extract

multiple times in succession. The extraction is repeated two to three
times, or perhaps more times if the compound has a low partition
coefficient in the organic solvent.

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Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 25
Total extraction in three steps = (0.29 + 0.12 + 0.05) g = 0.46 g
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 26
Multi-step extraction is more efficient than a single extraction:
Suppose,
Volume of aqueous solution = 100 ml
Organic substance in aqueous solution = W g
Volume of ether = 100 ml
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑒𝑡ℎ𝑒𝑟 𝐶𝑒𝑡ℎ𝑒𝑟
KD = = = 2
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟 𝐶𝑤𝑎𝑡𝑒𝑟

1. Using all ether in one lot:

Let, Amount of substance extracted = x g
Therefore, Substance unextracted = (W - x) g

Now, 𝐶𝑒𝑡ℎ𝑒𝑟 = 𝑥 100 gml-1 and 𝐶𝑤𝑎𝑡𝑒𝑟 = (𝑊−𝑥) 100 gmL-1

𝐶𝑒𝑡ℎ𝑒𝑟 𝑥 2
100
Therefore, KD = = (𝑊−𝑥) = 2 or, x = W g.
𝐶𝑤𝑎𝑡𝑒𝑟 100 3
i.e. 66.6% of organic substance has been extracted.

Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 27

2. Using 50 ml ether in each of two steps:
a. 1st step:
Let, amount of substance extracted = x1 g
Therefore, Substance unextracted = (W – x1) g

Now, 𝐶𝑒𝑡ℎ𝑒𝑟 = 𝑥1 50 gml-1 and 𝐶𝑤𝑎𝑡𝑒𝑟 = (𝑊−𝑥1) 100 gml-1

𝐶𝑒𝑡ℎ𝑒𝑟 𝑥1 1
50
Therefore, KD = = (𝑊−𝑥1) = 2 or, x1 = W g.
𝐶𝑤𝑎𝑡𝑒𝑟 100 2
1
i.e. 50% of organic substance has been extracted and W g left in water layer.
2
b. 2nd step:
Let, amount of substance extracted = x2 g
1
Therefore, Substance unextracted = (2 W – x2) g

Now, 𝐶𝑒𝑡ℎ𝑒𝑟 = 𝑥2 50 gml-1 and 𝐶𝑤𝑎𝑡𝑒𝑟 = (𝑊/2−𝑥2) 100 gml-1

𝐶𝑒𝑡ℎ𝑒𝑟 𝑥2 1
50
Therefore, KD = = (𝑊/2−𝑥2) = 2 or, x2 = W g. (25%)
𝐶𝑤𝑎𝑡𝑒𝑟 100 4
i.e. 25% of organic substance has been extracted. Total extraction = (50% + 25%) =
75%
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 28
Derivation of general formulation for substance left unextracted

Suppose,
Volume of aqueous solution = V ml
Organic substance in aqueous solution = W g
Volume of organic solvent for each step = L ml
1st extraction:
Let, Substance unextracted (i.e. left in water) = W1 g ; Extracted = (W – W1) g
(𝑊−𝑊1)
Here, Cwater = 𝑊1 𝑉 and Corganic = 𝐿

𝐶𝑤𝑎𝑡𝑒𝑟
Now, 𝐶𝑜𝑟𝑔𝑎𝑛𝑖𝑐
= KD

𝑊1 𝐾𝐷𝑉
or, 𝑉
(𝑊−𝑊1) = KD or, W1 = W. ………………… (1)
𝐿 𝐾𝐷𝑉+𝐿

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2nd Extraction:
Let, Substance unextracted = W2 g
Therefore, Substance extracted = (W1 – W2) g

(𝑊1−𝑊2)
Here, Cwater = 𝑊2 𝑉 and Corganic = 𝐿

𝐶𝑤𝑎𝑡𝑒𝑟
Now, = KD
𝐶𝑜𝑟𝑔𝑎𝑛𝑖𝑐

𝑊2 𝐾 𝐷𝑉
𝑉
or, (𝑊1−𝑊2) = KD or, W2 = W1. 𝐾 ………………… (2)
𝐿 𝐷
𝑉+𝐿
By putting the value of W1 from equation (1) to (2)

𝐾 𝐷𝑉 𝐾 𝐷𝑉
W2 = W.
𝐾𝐷𝑉+𝐿 𝐾𝐷𝑉+𝐿

𝐾 𝐷𝑉 2
W2 = W ( ) ……………………………………… (3)
𝐾𝐷𝑉+𝐿
𝐾 𝐷𝑉 n
In this way, after nth extraction the equation will be: Wn = W (𝐾 𝑉+𝐿)
𝐷
𝑪 𝒐𝒓𝒈𝒂𝒏𝒊𝒄 𝑽 n
Note: if we consider, = KD, then the equation will be: Wn = W (𝑲 )
𝑪 𝒘𝒂𝒕𝒆𝒓 𝑫
𝑳+𝑽
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 30
Some problems related to solvent extraction
1. The distribution co-efficient of an organic acid between benzene and water is 80. An
aqueous solution of acid containing 2.25 g in 100 mL was extracted with (i) 15 mL
benzene in one lot and (ii) thrice with 5 mL benzene each time. Calculate the amount of
acid extracted in each experiment.
2. The partition co-efficient of a substance between benzene and water is 10.1. How much
substance will remain unextracted when 250 mL of its aqueous solution containing 2.5g
of it by using 200 mL benzene in (i) a single lot and (ii) two equal portions.
3. The partition co-efficient of phenol between amyl alcohol and water is 16.1 at 25oC.
Calculated the weight of phenol extracted from 500 mL of an aqueous solution
containing 0.5 g mole/liter by shaking it twice with amyl alcohol using 100 mL each
time.
4. The distribution co-efficient of hydrogen sulphide between benzene and water is 6.0 at
25 0C. Calculate the maximum volume of benzene necessary at this temperature to
extract in a single step 80% of the hydrogen sulphide from 0.5 L of a 0.1 M aqueous
solution of it (hydrogen sulphide).
5. An aqueous solution containing 10 g of a solute per liter. When 500 mL of the solution is
shaken with 100 mL of ether, 3 g of the solute is extracted. How much more of the solute
would be extracted from [Link] solution by shaking twice with 50 mL ether each
Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 31
time?
Q. 3. The partition co-efficient of phenol between amyl alcohol and water is 16.1 at 25oC.
Calculated the weight of phenol extracted from 500 mL of an aqueous solution containing
0.5 g mole/liter by shaking it twice with amyl alcohol using 100 mL each time.

Solution:
94×0.5×500
500 mL of 0.5 M aqueous solution of phenol contains = = 23.5 g of phenol
1000
(as, 1000 mL of 1.0 M aqueous solution of phenol contains = 94 g of phenol)
We know,
Wn = W (𝐾𝐾𝑉+𝐿
𝐷𝑉
)n
𝐷

(Here, KD = 1/16.1 (0.0621), n = 2, V = 500 mL, L = 100 mL, W = 23.5 g, Wn = ?)

0.0621 ∗500 2
W2 = 23.5 (
(0.0625 ∗500)+100
)
= 1.32 g
Therefore, phenol extracted = (23.5 – 1.32) g = 22.18 g (Ans.)
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 32
Q. 4. The distribution co-efficient of hydrogen sulphide between benzene and water is 6.0 at 25 0C.
Calculate the maximum volume of benzene necessary at this temperature to extract in a single step
80% of the hydrogen sulphide from 0.5 L of a 0.1 M aqueous solution of it (hydrogen sulphide).
Solution:
0.5 L of 0.1 M aqueous solution of H2S contains = (34 x 0.5 x 0.1) g of H2S = 1.70 g H2S
(as, 1.0 L of 1.0 M aqueous solution of H2S contains = 34 g H2S)
Now, H2S extracted = (1.70 x 80%) g = (1.70 x 0.80) g = 1.36 g
Therefore, H2S unextracted = (1.70 – 1.36) g = 0.34 g
Suppose,
Benzene required = L liters
Therefore, Concentration of H2S in benzene (Cbenzene) = (1.36 𝐿 ) g/L and
Concentration of H2S in water (Cwater) = ( 0.34 0.5) g/L

We know,
1.36
𝐶𝑂𝑟𝑔𝑎𝑛𝑖𝑐 𝐶𝑏𝑒𝑛𝑧𝑒𝑛𝑒 𝐿
KD = or, KD = or, 6.0 = 0.34 or, L = 0.333 Liter (Ans.)
𝐶𝑤𝑎𝑡𝑒𝑟 𝐶𝑤𝑎𝑡𝑒𝑟 0.50
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 33
Q. 5. An aqueous solution containing 10 g of a solute per liter. When 500 mL of the solution
is shaken with 100 mL of ether, 3 g of the solute is extracted. How much more of the solute
would be extracted from the aqueous solution by shaking twice with 50 mL ether each
time?
Solution:
Solute unextracted = (5 – 3) g = 2 g
𝐶𝑒𝑡ℎ𝑒𝑟 3
0.1
KD = or, KD = 2 o r, KD = 15
𝐶𝑤𝑎𝑡𝑒𝑟 0.5
Let, in the 2nd case solute unextracted = w g
We know,
Wn = W ( 𝐾 𝐷𝑉
) n
𝐾𝐷𝑉+𝐿

(Here, KD = 1/15, n = 2, V = 500 mL, L = 50 mL, W = 2 g, Wn = W2 = ?)

1
∗ 5002 g = 0.32 g
W2 = 2 ( 1
15
)
( ∗ 500)+50
15
Therefore, solute extracted = (2.0 – 0.32) g = 1.68 g (Ans.)
Prof. Dr. Md. Rezaul Karim, Dept. of Chemistry, CUET 34