Separation by Liquid-Liquid Extraction

 Liquid - Liquid Extraction - separation process that takes advantage of

the relative solubilities of solutes in two immiscible solvents.

 The solute dissolves more readily and becomes more concentrated in

the solvent in which it has a higher solubility.

 A partial separation occurs when a number of solutes have different

relative solubilities in the two solvents used.

 This technique is extremely useful for very rapid and clean separation of
both organic and inorganic substances.

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How to separate the solute in two immiscible liquid?

 Separated on the basis of relative solubility

 The distribution coefficient, KD, is an equilibrium constant

that determines the distribution of a solute between two
immiscible solvents.

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How it works?

 Two immiscible solvents flow in opposite directions.

 The lighter solvent flows upward while the heavier solvent flows downward.

 The substance to be separated is in contact with both solvents and is

dissolved in each stream according to a ratio determined by the distribution
coefficient.

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 The separating agent for extraction is the addition of a third
component.

liquid-liquid extraction
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 EXAMPLES
EXAMPLES

 Suppose the compound  has a distribution coefficient KD = 2 between

solvent1 and solvent2

KD = [  ] solv2 = 2
[  ] solv1

 A more efficient extraction is achieved with several small volumes of

solvent than with a single large one

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 If there are 30 particles of compound , these are distributed between
equal volumes of solvent1 and solvent2

 If there are 300 particles of compound , the same distribution ratio is

observed in solvents 1 and 2

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 See ? No matter how much solute there is, the distribution coefficient, KD
remains constant, equal to 2
 When you double the volume of solvent2 (i.e. 200 ml of solvent2 and 100
ml of solvent1), the 300 particles of compound distribute as shown

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Why this method is chosen ?

 Separation by distillation is ineffective or difficult.

 Boiling points of mixtures are close.

 Flexibility in operation conditions choice is desired.

 Two or more components are present.

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The distribution coefficient, KD

 KD is approximately equal to the ratio of the solubility of a in two solvents.

KD =

Where;

[s]1 = concentration of solvent 1 ( normally organic solvent)

[s]2 = concentration of solvent 2 (aqueous solvent, e.g water)
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 If the KD is large, the solute will tend toward quantitative distribution
in solvent 1.

 Examples of component A distribution between organic solvent-

water solvent from a mixture of component A, B, and C in aqueous
solvent .
i. KD = = 2
Examples of organic solvents:
ii. KD = = 9 (hexane, tetrachloromethane,
n-butane)
iii. KD = = 12

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Exercise 1:

50 ml of aqueous solution containing 5.0 mmol of benzoic acid. After added and
shaken with 20 mL of CH2 Cl2, only 0.88 mmol of benzoic acid remained in
aqueous layer? What is the Kd benzoic extracted?

KD = = 11.7

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Exercise 2

Based on the data in table below, calculate Kd of unknown extraction:

KD = = 1.6

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 Distribution ratio

 Refer to the substances which are partially ionized in the aqueous

layer.

 D is defined as the ratio of the concentrations of all the species of the

solute in each phase.

D=

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 Consider, for example, the extraction of benzoic acid from an aqueous
solution:

 Benzoic acid (HBz) is a weak acid in water, therefore the distribution

ratio, D, is given by;

D=

e = ether solvent, a = aqueous solvent

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 Part of the benzoic acid in the aqueous layer will exist as Bz-

HBz H+ (aq) + Bz- (aq)

C aq = [HBz]aq + [Bz-]aq

C org = [HBz]org

D=
 Therefore;
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 We can readily derive the relationship between D and KD from the
equilibria involved. The acidity constant, Ka for the ionization of the acid in
the aqueous phase is given by:

HBz H+ (aq) + Bz- (aq)

Ka =

Hence;

[Bz-]a =

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KD =
KD [HBz]a= [HBz]e

D=

D=

D=

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 This equation predicts that when [H+]aq >> Ka, D is nearly equal to KD.

 If KD is large, the benzoic acid will be extracted into the ether layer.

 If [H+]aq << Ka, then D reduces to KD [H+]aq / Ka , which will be small, and
the benzoic acid will remain in the aqueous layer.

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 Extraction Percentage, %E

 The fraction of solute extracted depend on the volume ratio of the two solvents.

 If the larger organic volume is used, more solute dissolve in this layer.

 The fraction of solute extracted is equal to the milimoles of solute in the organic
layer divided by the total number milimoles of solute.

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 Where the percent extracted is given by following formula;

%E = x 100

= x 100

Where;

VO and Va = Volumes of the organic and aqueous phases

SO and Sa = Solutes of organic and aqueous phases

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 Percent extracted is related to the distribution ratio by:

%E=

 If Vo = Va , then ;

%E=

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Exercise 1:

Twenty millilitres of an aqueous solution of 0.10 M butyric acid is shaken with 10 mL

ether. After the layers are separated, it is determined by titration that 0.5 mmol
butyric acid remains in the aqueous layer. What is the distribution ratio, and what is
the percent extracted?
mmol of butyric acid;

na = (0.10 M) (20 mL)

= 2.0 mmol

After separated, 0.5 mmol remain in aqueous;

Therefore, na = 0.5 mmol

no = 2.0 mmol – 0.5 mmol

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= 1.5 mmol extracted
Therefore in ether;

Co = 1.5 mmol / 10 mL
= 0.15 M

Ca = 0.5 mmol / 20 mL
= 0.025 M

D = Co / Ca
= 0.15 M / 0.025 M
= 6.0
Since 1.5 mmol was extracted;

% E = = 75%
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Exercise 2:

Ninety six percent of a metal chelate is extracted when equal volumes of

aqueous and organic phases are used. What will be the percent extracted if
the volume of the organic phase is double.

%E= Therefore, % of solute extracted (when double

organic solvent is used) is:

96% = %E = = 98%

D = 24

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Percent after several times extraction

%E = [1 – ()n ] 100

The percentage of un-extracted solute also can be calculated by using formula below:

Wn = Wo()n

Wo = initial weight of solute in aqueous solution

Wn = weight of unextracted solute in aqueous solution

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Example:

1. 50 ml of organic solvent extracts 96% of Y solute from 100 ml

aqueous solvent;

i) Calculate distribution ratio (D) of Y solute in the extraction system above.

ii) How many percent of Y solute extracted after 3 times extraction?

2. 100 ml of aqueous solution contains 1.0 g of X solute. If D equal to 10, calculate total amount
of X solute remain in the aqueous phase solution after:

i) One time extraction with 90 ml of organic solvent

ii) One time extraction with 30 ml of organic solvent
iii) Three times consecutive extraction with 30 ml of organic solvent.

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3. Ninety-six percent of a solute is removed from 100 ml of an aqueous solution by
extraction with two portions of 50 ml of an organic solvent. What is the distribution ratio of
the solute?

4. Arsenic (III) is 70% extracted from 7M HCl into an equal volume of toluene. What
percentage will remain unextracted after three times extractions with toluene?

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1. (i) %E = 1 – ()n x 100

n = 1, %E= 96%, Va = 100 ml and Vo = 50 ml

%E1 = 1 – ()1 x 100

96 % = 100D/[D + 100/50]

96/100 = D/(D+2)

D = 48

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1. (ii)
n = 3, D= 98
% E = [ 1 – ( )n x 100
% E = [ 1 – ( )3 x 100
= 100 – 0.0064
= 99.99% extraction

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