In liquid–liquid extraction (also called solvent extraction or extraction), a liquid feed of two or more

components is contacted with a second liquid phase, called the solvent, which is immiscible or only
partly miscible with one or more feed components and completely or partially miscible with one or
more of the other feed components. Thus, the solvent partially dissolves certain species of the liquid
feed, effecting at least a partial separation of the feed components.

The solvent may be a pure compound or a mixture. If the feed is an aqueous solution, an organic solvent
is used; if the feed is organic, the solvent is often water. Important exceptions occur in metallurgy for
the separation of metals and in bioseparations for the extraction from aqueous solutions of proteins
that are denatured or degraded by organic solvents

Batchwise single stage extractions[edit]

This is commonly used on the small scale in chemical labs. It is normal to use a separating funnel.
Processes include DLLME and direct organic extraction.

Dispersive liquid–liquid microextraction (DLLME)[edit]

A process used to extract small amounts of organic compounds from water samples.[7] This process is
done by injecting small amounts of an appropriate extraction solvent (C2Cl4) and a disperser solvent
(acetone) into the aqueous solution. The resulting solution is then centrifuged to separate the organic
and aqueous layers. This process is useful in extraction organic compounds such as organochloride and
organophsophorus pesticides, as well as substituted benzene compounds from water samples.[7]

Direct organic extraction[edit]

By mixing partially organic soluble samples in organic solvent (toluene, benzene, xylene), the organic
soluble compounds will dissolve into the solvent and can be separated using a separatory funnel. This
process is valuable in the extraction of proteins and specifically phosphoprotein and phosphopeptide
phosphatases.[8]

Another example of this application is extracting anisole from a mixture of water and 5% acetic
acid using ether, then the anisole will enter the organic phase. The two phases would then be separated.
The acetic acid can then be scrubbed (removed) from the organic phase by shaking the organic extract
with sodium bicarbonate. The acetic acid reacts with the sodium bicarbonate to form sodium
acetate, carbon dioxide, and water.

Caffeine can also be extracted from coffee beans and tea leaves using a direct organic extraction. The
beans or leaves can be soaked in ethyl acetate which favorably dissolves the caffeine, leaving a majority
of the coffee or tea flavor remaining in the initial sample.[9]

Multistage countercurrent continuous processes[edit]

These are commonly used in industry for the processing of metals such as the lanthanides; because the
separation factors between the lanthanides are so small many extraction stages are needed.[10] In the
multistage processes, the aqueous raffinate from one extraction unit is fed to the next unit as the
aqueous feed, while the organic phase is moved in the opposite direction. Hence, in this way, even if the
separation between two metals in each stage is small, the overall system can have a higher
decontamination factor.

Multistage countercurrent arrays have been used for the separation of lanthanides. For the design of a
good process, the distribution ratio should be not too high (>100) or too low (<0.1) in the extraction
portion of the process. It is often the case that the process will have a section for scrubbing unwanted
metals from the organic phase, and finally a stripping section to obtain the metal back from the organic
phase.

Mixer–settlers[edit]

Battery of mixer-settlers counter currently interconnected. Each mixer-settler unit provides a single
stage of extraction. A mixer settler consists of a first stage that mixes the phases together followed by a
quiescent settling stage that allows the phases to separate by gravity.

In the multistage countercurrent process, multiple mixer settlers are installed with mixing and settling
chambers located at alternating ends for each stage (since the outlet of the settling sections feed the
inlets of the adjacent stage’s mixing sections). Mixer-settlers are used when a process requires longer
residence times and when the solutions are easily separated by gravity. They require a large facility
footprint, but do not require much headspace, and need limited remote maintenance capability for
occasional replacement of mixing motors. (Colven, 1956; Davidson, 1957)[11]
4 stage battery of mixer-settlers for counter-current extraction.

Centrifugal extractors[edit]

Centrifugal extractors mix and separate in one unit. Two liquids will be intensively mixed between the
spinning rotor and the stationary housing at speeds up to 6000 RPM. This develops great surfaces for an
ideal mass transfer from the aqueous phase into the organic phase. At 200–2000 g, both phases will be
separated again. Centrifugal extractors minimize the solvent in the process, optimize the product load in
the solvent and extract the aqueous phase completely. Counter current and cross current extractions
are easily established.[12]

Extraction without chemical change[edit]

Some solutes such as noble gases can be extracted from one phase to another without the need for a
chemical reaction (see absorption). This is the simplest type of solvent extraction. When a solvent is
extracted, two immiscible liquids are shaken together. The more polar solutes dissolve preferentially in
the more polar solvent, and the less polar solutes in the less polar solvent. Some solutes that do not at
first sight appear to undergo a reaction during the extraction process do not have distribution ratio that
is independent of concentration. A classic example is the extraction of carboxylic acids (HA) into
nonpolar media such as benzene. Here, it is often the case that the carboxylic acid will form a dimer in
the organic layer so the distribution ratio will change as a function of the acid concentration (measured
in either phase).

For this case, the extraction constant k is described by k = [[HAorganic]]2/[[HAaqueous]]

Solvation mechanism[edit]

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Using solvent extraction it is possible to extract uranium, plutonium, thorium and many rare earth
elements from acid solutions in a selective way by using the right choice of organic extracting solvent
and diluent. One solvent used for this purpose is the organophosphate tributyl phosphate (TBP).
The PUREX process that is commonly used in nuclear reprocessing uses a mixture of tri-n-butyl
phosphate and an inert hydrocarbon (kerosene), the uranium(VI) are extracted from strong nitric
acid and are back-extracted (stripped) using weak nitric acid. An organic soluble
uranium complex [UO2(TBP)2(NO3)2] is formed, then the organic layer bearing the uranium is brought
into contact with a dilute nitric acid solution; the equilibrium is shifted away from the organic soluble
uranium complex and towards the free TBP and uranyl nitrate in dilute nitric acid. The plutonium(IV)
forms a similar complex to the uranium(VI), but it is possible to strip the plutonium in more than one
way; a reducing agent that converts the plutonium to the trivalent oxidation state can be added. This
oxidation state does not form a stable complex with TBP and nitrate unless the nitrate concentration is
very high (circa 10 mol/L nitrate is required in the aqueous phase). Another method is to simply use
dilute nitric acid as a stripping agent for the plutonium. This PUREX chemistry is a classic example of
a solvation extraction.

Here in this case DU = k TBP2[[NO3]]2

Ion exchange mechanism[edit]

Another extraction mechanism is known as the ion exchange mechanism. Here, when an ion is
transferred from the aqueous phase to the organic phase, another ion is transferred in the other
direction to maintain the charge balance. This additional ion is often a hydrogen ion; for ion exchange
mechanisms, the distribution ratio is often a function of pH. An example of an ion exchange extraction
would be the extraction of americium by a combination of terpyridine and a carboxylic acid in tert-
butyl benzene. In this case

DAm = k terpyridine1carboxylic acid3H+−3

Another example is the extraction of zinc, cadmium, or lead by a dialkyl phosphinic acid (R2PO2H) into a
nonpolar diluent such as an alkane. A non-polar diluent favours the formation of uncharged non-
polar metal complexes.

Some extraction systems are able to extract metals by both the solvation and ion exchange mechanisms;
an example of such a system is the americium (and lanthanide) extraction from nitric acid by a
combination of 6,6'-bis-(5,6-dipentyl-1,2,4-triazin-3-yl)-2,2'-bipyridine and 2-bromohexanoic acid in tert-
butyl benzene. At both high- and low-nitric acid concentrations, the metal distribution ratio is higher
than it is for an intermediate nitric acid concentration.

Ion pair extraction[edit]

It is possible by careful choice of counterion to extract a metal. For instance, if the nitrate concentration
is high, it is possible to extract americium as an anionic nitrate complex if the mixture contains
a lipophilic quaternary ammonium salt.

An example that is more likely to be encountered by the 'average' chemist is the use of a phase transfer
catalyst. This is a charged species that transfers another ion to the organic phase. The ion reacts and
then forms another ion, which is then transferred back to the aqueous phase.

For instance, the 31.1 kJ mol−1 is required to transfer an acetate anion into nitrobenzene,[13] while the
energy required to transfer a chloride anion from an aqueous phase to nitrobenzene is 43.8 kJ
mol−1.[14] Hence, if the aqueous phase in a reaction is a solution of sodium acetate while the organic
phase is a nitrobenzene solution of benzyl chloride, then, when a phase transfer catalyst, the acetate
anions can be transferred from the aqueous layer where they react with the benzyl chloride to form
benzyl acetate and a chloride anion. The chloride anion is then transferred to the aqueous phase. The
transfer energies of the anions contribute to that given out by the reaction.
A 43.8 to 31.1 kJ mol−1 = 12.7 kJ mol−1 of additional energy is given out by the reaction when compared
with energy if the reaction had been done in nitrobenzene using one equivalent weight of
a tetraalkylammonium acetate.[15]