Solvent Extraction

INTRODUCTION
In chemistry, liquid-liquid extraction, also known as solvent extraction and partitioning, is used to
separate compounds based on their relative solubilities in two different immiscible liquids, usually water
(or water-based solution) and an organic solvent which is immiscible with water. It is an extraction of a
substance from one liquid phase into another liquid phase. The success of this method depends upon the
difference in solubility of a compound in various solvents and becomes a very useful tool if you choose a
suitable extraction solvent.
Solvent Extraction (SX) is a useful method to separate a substance selectively from a mixture, or to
remove unwanted impurities from a solution.
Solvent Extraction while not commonly used for quantitative analysis, it is a very common method for
sample preparation and concentration. In addition, concepts covered are directly applicable to
chromatography.
Liquid-liquid extraction is a basic technique in chemical laboratories, where it is performed using
a separatory funnel. This type of process is commonly performed after a chemical reaction as part of
the work-up.
In other words, this is the separation of a substance from a mixture by preferentially dissolving that
substance in a suitable solvent. By this process, a soluble compound is usually separated from an
insoluble compound.
Liquid-liquid extraction is possible in non-aqueous systems: In a system consisting of a molten metal in
contact with molten salt, metals can be extracted from one phase to the other.
Solvent extraction is used in nuclear reprocessing, ore processing, the production of fine organic
compounds, the processing of perfumes and other industries.
GENERAL CONCEPTS
Solvent extraction (SX) is the traditional term of liquid-liquid distribution that involves the distribution of
a solute between two immiscible liquid phases in contact with each other. The principle is illustrated in
Figure 2.1.
The vessel (a separatory funnel) contains two layers of liquids, that one is usually water (Saq) while the
other, an organic solvent (Sorg).
The organic phase often settles as the upper layer when it has a lower density than water, but the opposite
situation also occurs. A solute A, which initially is dissolved in one of the two liquids, eventually
distributes between the two phases. When this distribution reaches equilibrium, the solute has one
concentration [A]aq in the aqueous phase and another concentration [A]org in the organic phase.

Figure 2.1. A schematic representation of solvent extraction (liquid-liquid distribution). A solute A is
distributed between the upper layer, an organic phase (Sorg), and the lower layer, an aqueous phase (Saq).
In other words, when a solution (solute A in solvent 1) is shaken with a solvent (solvent 2) with which is
immiscible, the solute will distribute itself between the two liquid phases. When the two phases have
separated again into two distinct solvent layers, an equilibrium situation will have been achieved such that
the ratio of the concentrations of the solute in each layer will define a constant. This constant is called the
DISTRIBUTION RATIO (D) or PARTITION COEFFICIENT (K, P) and is a measure of how well-
extracted a species is.
Distribution ratio
In solvent extraction, the distribution ratio of the solute A is expressed as:
2
1
] [
] [
,
C
C
A
A
D K
aq
org

where K or D is defined as "the total analytical concentration of the substance in the organic
phase to its total analytical concentration in the aqueous phase, usually measured at
equilibrium", irrespective of whether the organic phase is the lighter or heavier one.

C1 and C2 are the concentration at equilibrium of solute A in solvent 1 (organic) and in solvent 2
(water) respectively. The solute distributes itself between the two solvents so that its chemical
activity is the same in each phase.

If a second solute, B, is present, the distribution ratios for the various solutes are indicated by DA , DB ,
and so on. If DB is different from DA , A and B can be separated from each other by (single or multistage)
solvent extraction. D is also called the distribution coefficient or the extraction coefficient.
Depending on the system, the distribution ratio can be a function of temperature, the concentration of
chemical species in the system, and a large number of other parameters.
In summary, partition (K, P) or distribution coefficient (D) is the ratio of concentrations of a compound in
the two phases of a mixture of two immiscible solvents at equilibrium. Hence these coefficients are a
measure of differential solubility of the compound between these two solvents. The phrase "Partition
Coefficient" is now considered obsolete by IUPAC, and the appropriate alternative ("partition constant",
"partition ratio" or "distribution ratio") should be used as appropriate.
Separation factors
The SEPARATION FACTOR (SF) is one distribution ratio divided by another, it is a measure of the
ability of the system to separate two solutes.
For instance if the distribution ratio for nickel (DNi) is 10 and the distribution ratio for silver (DAg) is 200,
then the silver/nickel separation factor (SFAg/Ni) is equal to DAg/DNi = SFAg/Ni = 20.
Solvent Extraction Videos
http://www.youtube.com/watch?v=vcwfhDhLiQU
http://www.youtube.com/watch?v=cMrWdx1KdU8
http://en.wikipedia.org/wiki/File:Separation02.ogg

TYPES OF EXTRACTION
Transfer of a solute from one solvent to another. To extract a solute from a solution, it is always better to
use several small portions. Extractions form an important part of the purification procedure of many
compounds formed from reactions. Extractions are grouped in three (3) categories:

1. Extraction of an organic material with water. This is designed to remove such highly polar
materials as in organic salts, strong acids or bases, and such low molecular weigh polar substances
as alcohols, carboxylic acids and amines. Water extractions are also used immediately following
extractions with either acid or base to ensure that all traces of acid or base have been removed.

2. Extraction of an organic material with a dilute acid, usually five or ten percent HCl . These
extractions are intended to remove basic impurities as amines. These bases are converted to their
corresponding cationic salts by the acid used in the extraction.

2
RNH + HCl

Cl RNH
3
(water soluble salt)
A water extraction may be used immediately following the acid extraction to ensure that all traces
of the acid have been removed from the organic material

3. Extraction of an organic material with a dilute base usually five percent sodium bicarbonate
(dilute sodium hydroxide may also be used). This type of extraction is used to convert acids into
their corresponding anionic salts. In the preparation of an ester, a sodium bicarbonate extraction
might be used to remove any excess carboxylic acid which might be present.

RCOOH +
3
NaHCO

Na RCOO + O H
2
+
2
CO
The anionic salts, being highly polar, would be expected to be soluble in the aqueous phase. As a
result these acidic impurities are extracted from the organic material into the basic solution. A
water extraction may be used immediately following the basic extraction to ensure that all traces
of the base have been removed.

Example: An organic MTBE solution is extracted with aqueous sodium bicarbonate solution. This
base removes benzoic acid as benzoate but leaves non-acidic benzil (yellow) behind in the upper
organic phase. {http://en.wikipedia.org/wiki/File:Separation02.ogg}

The separatory funnel is the piece of apparatus used in the extraction procedure. After an organic solvent
has been shaken with an aqueous solution, it will be wet. A drying agent may be used to remove water
from the organic layer. A drying agent is an anhydrous inorganic salt which acquires water of hydration
when exposed to the moist air or wet solution, e.g. anhydrous Na2SO4, CaCl2, MgSO4
APPLICATION
Solvent extraction is used in nuclear reprocessing, ore processing, the production of fine organic
compounds, the processing of perfumes and other industries.
In an industrial application, this process is done continuously by pumping an organic and aqueous stream
into a mixer. This mixes the organic component with the aqueous component and allows ion transfer
between them. The mixing continues until equilibrium is reached. Once the ion transfer is complete
(equilibrium is reached), the mixture flows into a vessel, where the organic and aqueous are allowed to
separate, similar to the way oil and water would separate after mixing them. Fresh material is
continuously fed into the mixer, and a two continuous streams is removed from the settler (one organic,
and one aqueous).

CALCULATIONS
Question:
1. Consider an aqueous solution which contains 8 g of solute A in 1 dm
3
of water. Given the
partition coefficient for solute A between water and ether is 66. Calculate the mass of
solute A extracted in
(i) A single 100 cm
3
portion of ether and
(ii) Two successive 50 cm
3
portion of ether

2. (a) Define the term partition coefficient
(b) List two conditions under which the partition coefficient remains constant
(c) Benzene is immiscible with water. When 50 cm
3
of an aqueous solution
containing 0.5 g of an organic solute X is shaken with 5 cm
3
of benzene, 0.2 g of
solute X is extracted in the benzene. Calculate a value for the partition coefficient
of X between benzene and water
(d) If aqueous layer from (c) above is shaken with another 5 cm
3
of benzene, what
mass of solute X will be extracted in the benzene when equilibrium is reached?

Solution: