Solvent extraction

Solution: A solution is a single phase homogenous system, containing one or more

components.

Ex, sugar in water, alcohol in water, oil in oil, salt in water etc.

Solvent: The component of solution which is in larger proportion referred as solvent.

Solute: The component of solution which is present in minor proportion.

A solution in water is called as aqueous solution. (Sugar dissolved in water or salt dissolved
in water). Whereas solution in a solvent other than water is called organic or non-aqueous
solution (iodine in carbon tetra chloride).

Solvent Extraction: it is a method of physical separation of mixture. The technique is

simple, rapid and convenient which is applicable for organic as well as aqueous materials. It
gives good accuracy even at trace level.

The liquid-liquid extraction is a technique in which solution (usually aqueous) is brought into
contact with second immiscible solvent (usually organic solvent) in order to bring out transfer
of solute in second. This is based on Nernst distribution law.

❖ Nernst Distribution Law:

In 1872 Berthelot and Jungfleish stated this law which is as follow, “when a solute
distributes itself between two immiscible solvents in such a way that the ratio of the
concentrations at equilibrium is constant at a particular Temperature.”

If C1 and C2 represent the concentration of the solute in solvent 1 and solvent 2

respectively, then at any given temperature.

𝑪𝟏
K=
𝑪𝟐
K=KD
‘K’ is known as partition coefficient

*Validity of distribution law: The two essential prerequisites for validity of law.

1. Constant temperature.
2. If the solute exists in the same molecular state in both solvents.

In many cases the solute undergoes dissociation or association. In such cases the
distribution law is modified. Distribution ratio/ Distribution Constant is denoted by
‘D’.
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝑺𝒐𝒍𝒗𝒆𝒏𝒕 𝟏
D=
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕𝟐

• Association of solute in one of the solvents.

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 ❖ Application of Distribution law in solvent extraction.
A solute passes from aqueous solution to organic solvent. As organic solvent has low
boiling point, evaporation of solvent is easy.
According to distribution law solute extracted by organic solvent gets distributed
between 2 liquids in a finite ratio at a given temperature. If Co and Cw are
concentration of solute in two liquids then K= Co/Cw.
∴Co is concentration in organic solvent.
Cw is concentration in water or in aqueous.

1. Batch extraction
It is a simplest and most commonly used solvent extraction technique when
distribution ratio of solvent is high. Solute to be extracted from aqueous layer is taken
in separating funnel having stopper at top. A known volume of organic solvent is
added and mixture is shaken to bring two layers in intimate contact. Stopper of funnel
is opened in between to release pressure developed due to organic solvent.

After sufficient shaking system left undisturbed to settle two layers to separate.
Depending the density of organic layer it occupies either upper layer or the lower layer.
Generally Benzene or ethers form upper layer whereas CHCl3 forms lower layer. If solvent
(organic solvent) is heavier than aqueous then it can be withdrawn by opening stopcock after

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reaching equilibrium. But for lighter organic solvent modified separating funnel is used in
which solvent is taken out from top of funnel.

As we know,

solute in g
Concentration= mass weight/ volume=
Volume in cc

solute in gram
Concentration of organic solvent Co= Volume of organic solvent Vo

solute in gram
Concentration of Aqueous solvent Cw= Volume of water Vw

Consider total amount of solute ‘a’ is taken and dissolved completely in Aqueous
solvent (Water) of Volume ‘Vw’ . Now for extraction organic solvent of volume ‘Vo’
is taken and shaken well, so that some amount of solute can transfer/distribute into
organic solvent.
Aqueous solution= Vw cm3 containing ‘a’ gram of solute .Equilibrated with Vo cm3
of organic solvent.
Concentration of organic solution = Co
Concentration of aqueous solution = Cw

𝐶𝑜
∴D=
𝐶𝑤

Total amount of solute = a gram.

After first extraction we do not know how much amount of solute is distributed in
organic solute. But whatever remained in aqueous solution is W1
∴ Extracted solute = a- w1
a−w1
. ∴ Concentration of organic layer = g/cm3
Vo

W1
∴ Concentration of Aqueous layer = g/cm3.
Vw

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 a−w1
𝐶𝑜 Vo a−w1 Vw
∴D=
𝐶𝑤
= W1 = Vo
× W1
𝑉𝑤

∴ D Vo .W1 = (a− W1) Vw

D Vo .W1 = aVw − W1Vw

D Vo .W1 + W1Vw = aVw

(D Vo + Vw) W1 = aVw

aVw
W1 = [ ]
(D Vo + Vw)

Vw
W1 = [ ]a
(D Vo + Vw)

By this formula we one can calculate the amount

Vw
W1 = [ ]a
(D Vo + Vw) of solute left Unextracted after first extraction.

If extraction is repeated with ‘Vw’ cm3 of aqueous solution using same Vo cm3 of
organic solvent then solute to be extracted will be W1 and left unextracted after second
extraction is W2.
Vw
∴ W2 = [ ] × W1
(D Vo + Vw)

Substituting value of W1,

Vw Vw
∴ W2 = [ ] × [(D Vo ]a
(D Vo + Vw) + Vw)

Vw 2
∴ W2 = [ ] a
(D Vo + Vw)

∴ After ‘n’ extraction with Vo cm3, amount of solute remaining unextracted is given
by,

Vw 𝑛
Wn = [ ] a
(D Vo + Vw)

By this formula one can calculate the amount

Vw 𝑛
Wn = [ ] a of solute left Unextracted after’n’ extractions.
(D Vo + Vw)

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 ❖ Multistep Extractions:
It is observed that increase in number of extractions: Efficiency of extractions
increases.
In general, it is more beneficial to use small volumes of extractions. for more number
of extraction than total volume for a single extraction.
Ex.
If take volume of organic layer Vo cm3 = 10 cm3. And perform single extraction
taking whole amount the amount of solute left extracted is smaller than the amount
of solute left extracted after two consecutive extraction with same volume of organic
layer in two repetition i.e.( Vo cm3 = 10 cm3 ; two times with 05 cm3 of Vo cm3).

Case 1.

If solute ‘a’ = 0.1 gram, D=20, Vw= 100 cm3, Vo= 10 cm3 then,

Vw 100 100
W1 = [ ]a = [ ]0.1 = [ ]0.1
(D Vo + Vw) (20× 10 + 100) (200 + 100)

W1= 0.033 gram

Case 2.

Number of extractions n = 2

Two extractions with volume Vo cm3 = 10 cm3 instead; two times with 05 cm3 of Vo
cm3).
Vo= 05 cm3, n=2 then,

Vw 𝑛 100 2
Wn = [ ] a=[ ] × 0.1 = 0.25 × 0.01 = 0.025 gram.
(D Vo + Vw) (20×5 + 100)

W2= 0.025 gram.

Although same amount of organic solvent is used, it is beneficial to perform large

number of extractions with small volume of solvent. So multiple extractions, extract more
solute than single extraction.

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 Numericals on solvent extraction:

1. 200 cm3 of organic solution containing 0.28 g of certain solute. The solute is
extracted three times with 25 cm3 of ether . Find amount of solute remaining in
aqueous solution. If distribution ratio is 17.6
Given=
Number of extractions n = 3
Solute a = 0.28 g
Volume of aqueous solution Vw= 200 cm3
Volume of organic solution Vo = 25 cm3
Distribution ratio D = 17.6

Vw 𝑛
∴ Wn = [ ] a
(D Vo + Vw)

200 3
W3= [ ] × 0.28
(17.6×20 + 200)

W3= 8.545 × 10−3 g.

∴ Amount of solute remained after three extraction = 8.545 × 10−3 g.

2. A 100 cm3 of aqueous solution containing 0.1 g of iodine is equilibrated with 75

cm3 of carbon tetrachloride. The distribution ratio between carbon tetra chloride
and water at room temperature is 85 in favour of CCl4. Calculate the weight of
iodine remaining unextracted in aqueous layer after:
(i) Two extractions with 75 cm3 of CCl4.
(ii) Three extractions with 25 cm3 of CCl4.

Given:

D= 85, Vw= 100 cm3, a=0.1 g, when n=2 and Vo= 75cm3

Vw 𝑛
Wn = [ ] a
(D Vo + Vw)

100 2
∴ W2= [ ] × 0.1
(85×75 + 100)

= 2.385 × 10−5 g.

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 D= 85, Vw= 100 cm3, a=0.1 g, when n=3 and Vo= 25cm3

Vw 𝑛
Wn = [ ] a
(D Vo + Vw)

100 3
∴ W3= [ ] × 0.1
(85×25 + 100)

= 9.078 × 10−6 g.

❖ Percentage Extraction (E):

It’s important to calculate total percentage extraction after single step or after
multistep extractions. Percentage formula is denoted by E.
We the formula to calculate amount of solute left unextracted as follow.

Vw
W1 = [ ]a
(D Vo + Vw)

The amount extracted is (a-w1) grams.

Vw
∴ (a-w1) = a − [(D Vo + Vw)]a

The fraction of original amount that has been extracted as

Vw
a −[ ]a
etracted solute (a−w1) (D Vo + Vw)
X= = =
total solute taken 𝑎 𝑎
Vw
X = 1− [ ]
(D Vo + Vw)

Vw
X = 1− [ ]
(D Vo + Vw)

D Vo + Vw−Vw
X=
D Vo + Vw

D Vo
X= ( Divide numerator & denominator by Vo )
D Vo + Vw

D
X=
D + 𝑉𝑤
𝑉𝑜

X is the fraction of extraction. Multiplying by 100 gives % extraction.

100D
∴ Percentage extraction= E= 100X = 𝑉𝑤
D + 𝑉𝑜

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 100D This formula is applicable to calculate % extraction after single extraction
E=
D + 𝑉𝑤
𝑉𝑜

For ‘n’ extraction the fraction x of initial amount is extracted given by,

Vw 𝑛
X = 1− [(D Vo + Vw)] a

Vw 𝑛
∴ Percentage extraction =E= 100X= 100 {1 − [(D Vo + Vw)] }

Vw 𝑛
∴ % extraction after n extractions=E= 100 {1 − [(D Vo + Vw)] }

The above formula is applicable when % extractions to be calculated for multiple

extractions.

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Numerical based on percentage (%) extraction.

1. Lanthanum is extracted from its aqueous solution as its hydroxyl quinolate by

chloroform. A 100 cm3 of aqueous solution containing 0.04 moles are extracted
with 20 cm3 of chloroform. Calculate (i) amount of lanthanum unextracted (ii) the
percentage extraction. When D = 370.

Given:
Volume of aqueous layer Vw = 100 cm3
Volume of organic layer Vo = 20 cm3
Initial amount of solute taken (a) = 0.04 mole
Distribution coefficient (D) = 370

Vw 100 100
W1 = [ ]a = [ ]0.04 = [ ]0.04
(D Vo + Vw) (370×20 + 100) (7400 + 100)

W1 = 5.333 × 10−4. Mole

The amount of lanthanum unextracted = 5.333 × 10−4. Mole

Then,

100D 100×370 37000

% Extraction (E) after first extraction = = 100 =
D + 𝑉𝑤
𝑉𝑜
370 + 20 370+5

37000
E=
375
= 98.66

∴ Pecentage extraction (% E) = 98.66

2. A 200 cm3 of an aqueous solution containing 0.05 moles of a certain solute

extracted twice with 25 cm3 of ether. Calculate (i) the amount of solute remaining
unextracted (ii) the percentage extraction. (Given D= 12.0)

Given:
Volume of aqueous layer Vw = 200 cm3
Volume of organic layer Vo = 25 cm3
Initial amount of solute taken (a) = 0.05 moles
Distribution coefficient (D) = 12
Number of extractions (n) = 2

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 By using formula of multiple extractions we can calculate the solute remained
after two extractions.

Vw 𝑛
Wn = [ ] a
(D Vo + Vw)

200 2
W2= [ ] × 0.05 = 0.008 moles
(12×25 + 200)

∴ W2 = 8 × 10−3. Moles

The Percentage extractions after Two extractions (E),

Vw 𝑛 200 2
% E = 100 {1 − [ ] } = 100 {1 − [ ] }
(D Vo + Vw) (12×25 + 200)

2 2
% E = 100× [1 − (5) ]

21
% E = 100× [25]

% E = 84

Solute remained after First Extraction can Solute remained after ‘n’ Extraction can
be calculated by this formula, be calculated by this formula,

Vw Vw 𝑛
W1 = [ ]a Wn = [ ] a
(D Vo + Vw) (D Vo + Vw)

% Extraction (E) after First Extraction: % Extraction (E) after ‘n’ Extraction:
100D 𝑛
E= Vw
D + 𝑉𝑤 % E = 100 {1 − [(D Vo + Vw)] }
𝑉𝑜

Above formulae are very important to calculate amount of solute left extracted
and the % percentage of extraction.

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Continuous Extractions:

If Distribution ratio is low, quantitative extraction of given solute would require multiple
extractions, which would be difficult. In such case continuous extraction is used. The
principle of the method consists in distilling the extraction solvent from a reservoir and
condensing it and passing it continuously through the solution being extracted.

The apparatus used in this method is depends upon whether the extracting solvent is heavier
or lighter the phase being extracted.

Condenser Condenser

Organic layer lighter

Funnel
Solute+ Aqueous
layer

Organic layer heavier

Heated solvent

Solvent heavier than water:

In this technique, the organic solvent is passed through aqueous phase containing solute to be
extracted in the form of droplets. The extraction goes on continuously. The solvent with
solute overflows through the tube into reservoir. The solvent distilled from reservoir are
condensed and allowed to drip through aqueous phase and doing so they carry a certain
amount of solute. As time passes the solvent gets enriched with solute which gets collected in
the reservoir or separated out.

Solvent is lighter than water: If solvent is lighter than water then bubble type funnel has to
be used. The liquid being lighter than aqueous layer rises through solutions as a part of solute
and overflows into hot reservoir. The vapour from reservoir pass into extracting vessel/tube
gets condensed and drops into funnel. As the process continues, solvent becomes richer in
solute.

❖ Important facts:

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 -An organic solvent used for extraction must be immiscible with aqueous solution.
-organic solvent used for extraction must be good for solute to be extracted.
-K/D (Partition coefficient or Distribution ratio) values must be in favour of solvent.
-Solute must easily recoverable with from the solvent. i.e the extracted solute must
not chemically interact with solvent.
-After shaking with an aqueous layer, the organic liquid must quickly settle out as a
separate layer. Hence the specific gravity must be substantially greater or
considerably, lesser than one.

❖ Complexing Agent in solvent extraction:

Chelation or Inorganic salts affect on solvent extraction. The process of chelation
improves solubility of a complex organic phase. As we know organic substances are
soluble in organic solvents while inorganic salts are soluble in water due to
hydration.
Inorganic salts in solution mainly of ions. The metal ions are soluble in water due to
association of water molecule with ion charged metal. Bulkier the complex more
hydrophobic its nature and better is the extraction by organic solvent.
Take an example of Aluminium. If we has to take out aluminium from water (as we
know aluminium exist in water as Al(OH)3 .and present in Al3+ ion. so if we add
hydroxyl quinolate by addition of hydroxy quinoline as complexing agent the formed
chelate can be easily separate out by using benzene or chloroform.
Same way Fe, Ni, Vanadium, can be extracted.

n( HQ)+ (org) + (Mn+)(water) (MQn)org + n(H+)water

AlCl3

Al3+ Al(OH)3 Al3+ + 3 (OH-)

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