Liquids, on the other hand, lie somewhere between the extremes of gases and

solids. Liquids contain particles that are close together; liquids are essentially
incompressible and have definite volume. These properties are very similar to
those of solids. But liquids also take the shape of their containers; this is closer to
the model of a gas. Although liquids and solids show similar properties, they
differ tremendously from gases. No simple mathematical relationship, like the
ideal gas law, works well for liquids or solids. Instead, these models are directly
related to the forces of attraction between molecules (Hein, 2011 : 291)

A liquid–liquid extraction is one of the most important separation

techniques used in environmental, clinical, and industrial laboratories. Two
examples from environmental analysis serve to illustrate its importance. Public
drinking water supplies are routinely monitored for trihalomethanes (CHCl3,
CHBrCl2, CHBr2Cl, and CHBr3) because of their known or suspected
carcinogeneity. Before their analysis by gas chromatography, trihalomethanes are
separated from their aqueous matrix by a liquid–liquid extraction using
pentane.21 A liquid–liquid extraction is also used in screening orange juice for the
presence of organophosphorous pesticides. A sample of orange juice is mixed
with acetonitrite and filtered (Harvey, : 215).

Liquid-liquid extraction is a technique in which a solution (usually

aqueous) is brought into contact with a second solvent (usually organic),
essentially immiscible with the first, in order to bring about a transfer of one or
more solutes into the second solvent. The separations that can be performed are
simple, clean, rapid, and convenient. In the case of inorganic solutes we are
concerned largely with samples in aqueous solution so that it is necessary to
produce substances, such as neutral metal chelates and ion-association complexes,
which are capable of extraction into organic solvents. For organic solutes,
however, the extraction system may sometimes involve two immiscible organic
solvents rather than the aqueous-organic type of extraction (Jeffery, 1989: 161).

Liquid-liquid extractions have several limitations. With extractions from

aqueous solutions, the solvents that can be used must be immisicible with water
and must not form emulsions. A second difficulty is that liquid-liquid extractions
use relatively large volumes of solvent, which can cause a problem with waste
disposal. Also, most extractions are performed manually, which makes them
somewhat slow and tedious. Solid-phase extraction, or liquid-solid extraction, can
overcome several of these problems. Solid-phase extraction techniques use
membranes or small disposable syringe-barrel columns or cartridges. A
hydrophobic organic compound is coated or chemically bonded to powdered silica
to form the solid extracting phase (Holler, 2014: 856-857).

The purpose of an extraction technique is physically to separate

components of a mixture (solutes) by exploiting differences in their relative
solubilities in two immiscible liquids or between their affinities for a solid
sorbent. Substances reach an equilibrium distribution through intimate contact
between the two phases, which are then physically separated to enable the species
in either phase to be recovered for completion of the analysis. An equilibrium
distribution of the solutes between the two phases is established by dissolving the
sample in a suitable solvent, then shaking the solution with a second, immiscible,
solvent or by passing it through a sorbent bed or disk. Where the equilibrium
distributions of two solutes differ, a separation is possible (Kealey, 2002: 109).

In a simple liquid–liquid extraction the solute is partitioned between two

immiscible phases. In most cases one of the phases is aqueous, and the other
phase is an organic solvent such as diethyl ether or chloroform. Because the
phases are immiscible, they form two layers, with the denser phase on the bottom.
The solute is initially present in one phase, but after extraction it is present in both
phases. The efficiency of a liquid–liquid extraction is determined by the
equilibrium constant for the solute’s partitioning between the two phases.
Extraction efficiency is also influenced by any secondary reactions involving the
solute. Examples of secondary reactions include acid–base and complexation
equilibria (Harvey, 2000: 215).

It is well known that hydrated inorganic salts tend to be more soluble in

water than in organic solvents such as benzene, chloroform, etc., whereas organic
substances tend to be more soluble in organic solvents than in water unless they
incorporate a sufficient number of hydroxyl, sulphonic, or other hydrophilic
groupings. In solvent extraction analysis of metals we are concerned with methods
by which the water solubility of inorganic cations may be masked by interaction
with appropriate (largely organic) reagents; this will in effect remove some or all
of the water molecules associated with the metal ion to which the water solubility
is due (Jeffery, 1989: 163).

A typical cartridge system for solid-phase extractions is shown in Figure 31-4.

The sample is placed in the cartridge and pressure is applied by the syringe or from an
air or nitrogen line. Alternatively, a vacuum can be used to pull the sample through the
extractant. Organic molecules are then extracted from the sample and concentrated in
the solid phase. They can later be displaced from the solid phase by a solvent such as
methanol. By extracting the desired components from a large volume of water and then
flushing them out with a small volume of solvent, the components can be concentrated.
Preconcentration methods are often necessary for trace analytical method (Holler,
2014: 857).

The selection of extractants and diluents are two vital aspects of a successful
solvent extraction system. The influence of diluents on distribution of metal is correlated
with the physic-chemical properties of organic solvent such as solubility parameter,
dipole moment, dielectric constant, etc. The extraction of Zr(IV) from 3M H2SO4 using
0.01M cyanex 923 was studied in different organic diluents namely kerosene, benzene,
diethyl ether, xylene, carbon tetrachloride, chloroform (Swain, 2019).

Shaking time represent kinetic law effect on indirect extraction method. The
results value for shaking time giving higher extraction efficiency and help to reach best
equilibrium for formation ion pair association complex, any shaking time less than
optimum not suitable for extraction so that shaking time more than optimum value. The
results shows there was not any linear relation between dielectric constant of the
solvents and distribution ratio for extraction that is mean there was not any effect of
polarity of organic solvent on extraction efficiency as well as the results appears there is
un effect for organic solvent structure on extraction (Jawad, 2018).