EXTRACTION / Solvent Extraction Principles 569

HM Customs and Excise (1979) Laboratory Alcohol Tables. of the density of physiological fluids. Biomedizinische
RD C80/267/04. London: HMSO. Technik 22: 231–234.
HM Customs and Excise (1981) Tariff and Overseas Trade Noordzij PC and Roszbach R (eds.) (1987) Alcohol, Drugs
Classification. London: HMSO. and Traffic Safety T86. Amsterdam: Elsevier.
Leopold H, Jelinek R, and Tilz GP (1977) The application of OIML (1988) International Recommendations Relating to
the mechanical oscillator technique for the determination Evidential Breath Analysers. Reporting Secretariat
OIML (SP 30–SR 13), France.

EXPERT SYSTEMS
See CHEMOMETRICS AND STATISTICS: Expert Systems

EXPLOSIVES
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EXTRACTION

Contents
Solvent Extraction Principles
Solvent Extraction: Multistage Countercurrent Distribution
Microwave-Assisted Solvent Extraction
Pressurized Fluid Extraction
Supercritical Fluid Extraction
Solid-Phase Extraction
Solid-Phase Microextraction

and others. Depending upon the extraction system

Solvent Extraction Principles considered, different ligands may be used, normally
dissolved in organic diluents. Due to environmental
A M Sastre, Universitat Politectica de Catalunya, problems connected with the use of organic solvents,
Barcelona, Spain novel systems with more environment-friendly sol-
J Szymanowski, Poznan University of Technology, vents have been proposed for various new precon-
Poznan, Poland centration methods.
& 2005, Elsevier Ltd. All Rights Reserved. Various phenomena should be considered in solvent
extraction. The analytical purposes and determination
of complex stoichiometry are the classical problems.
Introduction The amphiphilic character of many extraction re-
agents must also be taken into consideration when
Solvent extraction is a classical analytical technique studying kinetics and extraction mechanism.
used to determine the contents of various inorganic
and organic species. Inorganic compounds are usu-
ally extracted after complexation with organic Types of Reagents and Extraction
ligands. The technique also enables preconcentration
Reactions
of solutes and their separation and finds practical
applications in various industries, including nuclear, Physical extraction is seldom used in practice; ex-
metal processing, petrochemistry, pharmaceutical, traction reagents are normally used. These can be
570 EXTRACTION / Solvent Extraction Principles

divided into acidic, basic, and solvating (neutral) Thus, solvent extraction can also be used as a re-
extractants. search method to determine certain physical–chemi-
Acidic extractants can be further subdivided into cal data.
simple organic acids, e.g., carboxylic acids, phos- Basic reagents are usually primary, secondary, and
phoric acids, phosphonic acids, phosphinic acids, tertiary amines or their ammonium salts with a dif-
thiophosphorus acids, and sulfonic acids, and che- ferent length and the structure of the alkyl group(s).
lating reagents, e.g., hydroxyoximes, 8-hydroxy- Amines require protonation before they can act as
(thio)quinolines, b-diketones, nitrosophenols, and extractants. For example,
pyridylazonaphthols. These reagents transfer metal
cations into the organic phase in the form of R3 No þ HClw ¼ R3 NHClo ½5

uncharged complexes, e.g., copper(II) with
hydroxyoximes (HL): They can only extract anions from acidic solutions,
by transferring bulky anions to the organic phase in
Cu2þ þ the form of ion-pairs. For example,
w þ 2HLo ¼ CuL2o þ 2Hw ½1

2R3 NHþ Cl 2 þ 2 

o þ ZnCl4w ¼ ðR3 NH Þ2 ZnCl4o þ 2Clw ½6

where subscripts ‘w’ and ‘o’ denote the aqueous and
organic phases, respectively.
An alternative mode of extraction involves an addi-
The distribution ratio ðD ¼ Co =Cw Þ is the function
tion reaction. For example,
of reagent concentration and equilibrium pH:
R3 NHþ Cl þ 2
o þ ZnCl2w ¼ ðR3 NH Þ2 ZnCl4o ½7

log D ¼ log Kex þ 2 log½HL
o þ 2pH ½2

The interpretation of extraction data must take into
An increased acidity of the aqueous phase shifts the account the formation of various chlorocomplexes
equilibrium of eqn [1] to the left. Due to this, acidic ZnCl2i  i, where i ¼ 1, 2, 3, 4, and a more complex
extractants cannot transfer large amounts of metal equation for log D is obtained. For example, for
cations, and the back-extraction is accomplished eqn [7]:
with mineral acids of appropriate concentration.
Extraction can be used to separate and pre- log D ¼ logðKex  b2 Þ þ 2 log½R3 NHCl
o þ 2 log½Cl
w
!
concentrate the analyte component(s), to recover X4
 i
valuable components from aqueous solutions (hydro-  log 1 þ bi  ½Cl
w ½8

i1
metallurgy, biotechnology), and also to determine the
stoichiometry of extracted complexes. In the latter
The stability constants of various metal anion
case, the relations log D versus pH and log D versus
complexes bi are given in the literature. Usually, re-
log HL are considered, and the composition of the
liable data can be obtained for typical analytical
complex can be determined from the slopes of the
diluted solutions, but such estimations are not
linear parts of these relationships.
reliable for concentrated solutions that contain var-
The extractant can form associated forms, usually
ious ions.
dimers, and the extracted complex can be solvated by
Quaternary ammonium salts react without
undissociated extractant molecules and can undergo
protonation and the extraction is not sensitive to
polymerization. Thus, the more complex eqn [3] can
the acidity of the aqueous phase.
be presented:
Solvating reagents such as neutral compounds
pMnþ þ (e.g., ethers, ketones, alcohols, and esters of car-
w þ 0:5ðnp þ mÞðHLÞ2o ¼ ðMLn Þp mHLo þ npHw ½3

boxylic acids, alkyl phosphates, phosphonates, phos-
phinates, phosphine oxides, and phosphine sulfides)
Values of n, m, and p can be determined from ex-
and also esters of pyridinecarboxylic acids and certain
traction data by slope analysis or by using computer
benzimidazole derivatives that have electron-with-
programs.
drawing substituents form solvates with extracted
The extraction constant Kex present in eqn [2] is
neutral species. For example, dialkylpyridine-3,5-
the function of several individual constants charac-
carboxylates extract Cu(II) at pH 3 from concen-
teristic of steps such as the partitioning of the ligand
trated chloride solutions:
(PHL), the dissociation of the ligand (Ka), the overall
complex stability constant (bCuL2), and the parti- CuCl2w þ 2So ¼ CuCl2 2So ½9

tioning of complex (PCuL2):
Solvating reagents can also extract charged species
Kex ¼ bCuL2 K2a PCuL2 P2
HL ½4
together with counterion(s). For example, tributyl
 EXTRACTION / Solvent Extraction Principles 571

phosphate or trialkylphosphine oxides extract solutions. For example, for copper(II) extraction:
zinc(II) from hydrochloric acid solutions: extraction step:
CuCl2w þ 2So þ2HLo ¼ CuCl2 2So þ 2HLo ½13

2Hþ 2
w þ ZnCl4w þ 2So ¼ H2 ZnCl4 2So ½10

scrubbing of chlorides with water:
Instead of protons, metal cations can also be trans-

ferred to the organic phase. CuCl2 2So þ2HLo ¼CuL2o þ 2So þ 2Hþ
w þ 2Clw ½14

As in the case of ion-pair extraction with basic
reagents, the formation of various chlorocomplexes back-extraction:
must be taken into consideration.
CuL2o þ 2So þ 2Hþ 2þ
w ¼ 2HLo þ 2So þ Cuw ½15

Solvating reagents can also extract bulky anions,
e.g., CrO24  , MoO24  , and anionic chlorocom-
Extractants are often used with modifiers (e.g., hy-
plexes, by means of the hydration mechanism. For
drophobic alcohols, alkylphenols, sterically hindered
example,
esters of carboxylic acids, and tributyl phosphate).
þ Modifiers are used for two different reasons: first, to
ZnCl2þ
4w þ 8H2 Ow þ 2Hw þ 6TBPo
increase the solubility of extractants and their com-
¼ ½ðH3 Oþ ÞðH2 OÞ3 ðTBPÞ3
2 ZnCl2
4o ½11
plexes and to avoid the formation of the third phase,
and second, to modify the extraction properties, i.e.,
The preprotonation of solvating reagents, such as the extraction and stripping abilities. The first option
alcohols, and the extraction of anionic species are is usually exploited in systems that contain various
also possible: amines. The second option is associated with hydro-
xyoximes and the formation of tailored blends,
þ þ
MCl2 2
4w þ 2ROH2o ¼ ðROH2 Þ2 MCl4o ½12
which optimize the extraction-stripping properties
and adjust them to the aqueous feed, i.e., to the
The parallel transfer of extracted species by means of acidity and concentration of copper(II). Modifiers
various mechanisms also occurs. that form hydrogen bonds with hydroxyoxime mole-
The solvating reagents are usually less selective cules decrease their extraction ability but facilitate
than acidic extractants and the transferred complex- back-extraction with acids. Weak hydroxyoxime or
es are not as well defined. A high concentration of b-diketone extractants (e.g., 2-hydroxy-5-alkylbenzo-
salts and/or the presence of complexing anions are phenone oxime) can also act as modifiers of strong
needed to obtain the efficient extraction of metal hydroxyoxime extractants (e.g., salicylaldoxime and
species. The drawbacks are coextraction of acids and its alkyl derivatives).
water. The back-extraction is usually carried out
with water.
Certain reagents can be considered bifunctional,
i.e., 8-hydroxyquinoline and its derivatives and Extractants as Amphiphilic
alkylpyridine carboxylates. The former, depending
on the pH of the aqueous phase and the type of metal
Compounds
cation, can act as a chelating acidic extractant, for- Extractants that have a hydrophobic substituent(s)
ming chelates with copper(II) and zinc(II), or after and a hydrophilic fragment(s) (Figure 1) show an
protonation as a basic reagent, forming ion-pairs amphiphilic character, adsorb at water/organic sol-
with anionic zinc(II) chlorocomplexes. Alkylpyridine vent interfaces, and decrease the interfacial tension.
carboxylates act as solvating reagents that Their interfacial activity depends on the type of hy-
extract copper(II) from chloride solutions at pH 3, drophilic and hydrophobic groups, the number and
but after protonation they extract palladium(II) structure of the alkyl group, and the type of solvent.
efficiently from HCl solutions. The use of bifunctional Thus, they behave in a similar way to hydrophobic
extractants or the mixtures of basic and chelating surfactants in surface tension reduction and
extractants or solvating (S) and chelating (HL) aggregation. However, in typical extraction systems,
extractants enables the extraction of metal species chelating extractants show moderate interfacial
from chloride solutions as ion-pairs or solvates. activity and decrease the interfacial tension to only
Scrubbing with water causes a transfer of metal cat- 15–25 mN m  1. Strong acidic extractants and pro-
ion into chelate from which the cation can be tonated alkylamines exhibit the highest interfacial
stripped with sulfuric acid. Thus, mixed extractants activity, while solvating reagents and neutral amines
enable a transfer of metals from chloride to sulfate are on the opposite side of the scale.
572 EXTRACTION / Solvent Extraction Principles

Organic
phase
C2H5
Interfacial
CH3 (CH2)3 CHCH2 O O surface layers
P Aqueous
CH3 (CH2)3 CHCH2 O (A) (B) phase
OH
C2H5 Figure 2 Interfacial zone with adsorbed extractant molecules
(A and B denote systems with aliphatic and aromatic hydrocar-
bons).

C8H17
14 48
C8H17 NH+ Cl−
O/W

Surface excess 107 (mol m–2)

C8H17 12

Interfacial tension (mN m–1)

44
10

8 O/W 40

6 T/W
R OH 36

4
C=N 32
Y OH 2
T/W
0 28
0 2 4 6
Concentration (mol l –1)
Hydrophobic parts Hydrophilic parts
Figure 3 Isotherms of interfacial tension and surface excess for
Figure 1 Extractants as amphiphilic substances. acidic chelating extractant at octane/water (O/W) and toluene/
water (T/W) interface.

All factors that lead to hydration, protonation, and

dissociation of the polar group decrease the hydro- extractant hydrophilic groups in the aqueous layers
phobicity of extractant molecules and polarize them. (Figure 2). The density of extractant population, or
The decrease in hydrophobicity makes the extractant the surface excess G, can be calculated from the
molecules less compatible with the nonpolar organic Gibbs isotherm alone or by the coupling of this iso-
phase, and enhances the attractive interaction be- therm with various equations that correlate the sur-
tween extractant head group(s) and water. Thus, the face tension with extractant concentration in the
forces that draw the extractant molecules from the organic phase, e.g., the Szyszkowski equation. The
bulk organic phase to the interfacial region increase density of population increases with the extractant
adsorption. On the other hand, phenomena such as concentration only for a limited range of low con-
solvation or aggregation of the extractant molecules centrations, assuming a constant value at the satu-
result in the formation of species that are less surface- rated interface (Figure 3). The interface already
active than monomeric extractants. The adsorption, becomes saturated at bulk extractant concentrations
however, needs an appropriate balance of forces ac- of 10  3–10  2 mol l  1, and even earlier in the pres-
ting on both sides of the interface, and excessively ence of solvating diluents.
strong interactions of the extractant head groups Modifiers also have some hydrophilic groups and
with water molecules favor the dissolution of adsorb at liquid–liquid interfaces. Thus, they compete
extractant in the aqueous phase and inhibit the with extractant molecules for access to the interface
adsorption at the hydrocarbon/water interface. and presence in the adsorption layer, thus decreasing
The density of population and orientation of the interfacial concentration of extractant molecules.
surfactants at the interface depends upon their struc- The same phenomenon occurs when different extract-
ture and concentration and the type of diluent. The ants are present in the extraction system.
effect of the latter is decisive. Molecules of aromatic Some extractants that have acidic groups, e.g.,
hydrocarbons that have p electrons compete with sulfonic, phosphonic, phosphinic, and also some ba-
extractant molecules for access to the hypothetical sic and solvating extractants in the systems contain-
interface, and solvating diluents disturb the adsorp- ing acidic aqueous phase, form reverse micelles
tion of extractant molecules and the penetration of (Figure 4). The formation of reverse micelles appears
 EXTRACTION / Solvent Extraction Principles 573

Microscopic 2 HL
interface ML2
Hydrocarbon
Water Bulk organic 2 HL Organic
pool reaction ML2 phase
2 HL
Interfacial ML2
Water reaction
2 H+ M2+
pool
2 H+ Bulk aqueous Aqueous
M2+
reaction phase
2 H+
Water M2+
pool
Figure 5 Extraction pathways for acidic extractant with different
Water Macroscopic location of complexing step.
interface
Figure 4 Reverse micelles in organic phase. (Adapted from
Depending on the relative rates of the chemical and
Nitsch W and Plucinski P (1990) Two-phase kinetics of the solu- diffusion steps, the reaction can proceed in the ki-
bilization in reverse micelles. Journal of Colloid and Interface netic, diffusion, or mixed regime, the entire process
Science 136: 338–351.) being controlled by the rate of the chemical step, a
diffusion process, or by both kinetics and diffusion.
to be a general phenomenon for acidic extractants Thus, under very good hydrodynamic conditions,
and occurs even at very low concentrations, e.g., e.g., upon vigorous agitation, the influence of the
10  5 and 10  3 mol l  1 for dinonylnaphthalene diffusion can be substantially eliminated and the ki-
sulfonic acid and di(2-ethylhexyl)phosphoric acid, netic results can be used to discuss the reaction
respectively. Even tributyl phosphate forms reverse mechanism. This conclusion is not always true, and
micelles in contact with solutions of HCl and HNO3. the use of typical surfactant micellar aqueous solu-
The presence of the water pool in the core of reverse tions with extractants dissolved (solubilized) in mi-
micelles causes nonspecific transfer of water-soluble cellar pseudophase (micelles) and inorganic species
components, thus decreasing the selectivity of ex- dissolved in aqueous pseudophase mimic the extrac-
traction and disturbing the interpretation of the tion systems effectively and the diffusion processes
equilibrium extraction data. However, the presence are totally eliminated.
of reverse micelles may increase the rate of extrac- The chemical step can occur in the bulk of the
tion. This phenomenon is exploited in the so-called aqueous phase or aqueous pseudophase, in the bulk of
micellar extraction, especially for the extraction of the organic phase or in the micelle and/or at the actual
biochemicals that need an aqueous environment to interface, or at the hypothetical interface of the micel-
keep them stable. les. Figure 5 shows the possible extraction pathways
Under certain conditions, in the presence of a cos- in typical extraction for metal recovery with an acidic
urfactant, e.g., butanol, and/or alkaline aqueous extractant. Metal ions, such as hydrophilic and
phase, reverse micelles swell, accepting a large charged species, are insoluble in typical organic phas-
amount of water, and transparent and stable micro- es. Thus, the version of complex formation in the
emulsions are formed. Microemulsion can also be organic phase can be disregarded as long as the for-
obtained when typical surfactants with cosurfactant mation of reverse micelles and W/O microemulsions is
are present in the organic phase. Such systems enable avoided. However, such an option is possible in the
the rapid extraction of germanium(IV) and gallium(III) extraction of organic compounds. The interfacial re-
with alkyl derivatives of 8-hydroxyquinoline, while action can be understood as the reaction in the real
classical extraction needs days of phase contact. interfacial zone of B2 nm thickness or as the reaction
in a thin boundary layer in the aqueous phase.
The location of the reaction step depends on ex-
tractant surface activity and hydrophobicity, metal
Kinetics and Mechanism of Extraction concentration, and hydrodynamics (agitation inten-
Extraction is performed by the diffusional flow of a sity). Low metal concentration and high hydrody-
metal across the interface between two liquid phases, namics, together with high surface activity and
accompanied by the chemical reaction of metal com- the low solubility of the extractant in the aqueous
plex formation. The diffusion of the species that phase (i.e., high hydrophobicity), favor the interfa-
participate in the chemical reaction is of great signi- cial reaction. However, the reaction place may also
ficance, as are the locations in which the chemical depend on experimental conditions, i.e., the method
reaction proceeds, and the rate of complexation. used for the studies. In general, case reaction
574 EXTRACTION / Solvent Extraction Principles

Organic Interface Aqueous

phase phase

+ −
HLo HLad HLaq = Haq + L aq

2+ 2+ + +
2 HLo = (HL)2,o +
HLad + Mint, aq = MLad + Haq
+ Maq + HLaq = MLaq + Haq
2+
Maq + Laq = MLaq
+ + + +
ML2,o MLad + HLint, aq = ML2,ad + Haq MLaq + HLaq = ML2,aq + Haq
+ −
MLaq + Laq = ML2,aq
Limiting step

[M2+]w [HL]oΓ
r = k .A . 2
[H+]w

Figure 6 Reaction scheme of metal complexing from acidic sulfate solutions with hydroxyoxime extractants. (Adapted from
Szymanowski J (1993) Hydroxyoximes and Copper Hydrometallurgy. Boca Raton: CRC Press.)

proceeds simultaneously both in the bulk of the interfacial resistance, but when the charge is opposite
aqueous phase and at the interface (Figure 6). The to that of the intermediate metal complex, they en-
contribution of the interfacial reaction increases in a hance the transfer due to electrostatic attraction.
homologous series of extractants, e.g., with an in-
crease in the alkyl group length.
In systems with reverse micelles/microemulsion, New Methods of Extraction and
the transfer of extracted species occurs both through
the macroscopic interface between dispersed and
Solute Preconcentration
continuous phases and through the large microscopic Sample pretreatment is still currently the weakest
interface between water pools and extractant hydro- link, the time-determining step in the whole analyti-
philic groups in the cores of the micelles. The transfer cal procedure and the primary source of errors. The
of water with hydrophilic species is possible due to increasing need for the determination of numerous
reverse micelles forming at the interface and sucking analytes at lower and lower levels and in increasingly
the aqueous phase. complex matrixes makes sample pretreatment, espe-
Although adsorbed molecules of extractants are cially trace enrichment, an indispensable step in
well oriented at the interface, the interfacial reactions many analytical procedures.
occur more slowly, as recalculated for the same Trace enrichment can be performed by liquid–liquid
volume, than reactions in the aqueous phase. The extraction (LLE) or solid-phase extraction (SPE).
extraction of palladium(II) from HCl solutions with Although SPE is a relatively more recent and popular
dialkyl sulfides is a classic example of a very slow technique, LLE is still one of the most versatile tech-
process. Modifying the extractant structure by ad- niques for enrichment because of its advantages: it is
ding a hydrophilic hydroxyl group and/or a phase simple to perform, requires simple and inexpensive
transfer catalyst, e.g., trialkylamine or quaternary equipment, has a high capacity for interfering com-
ammonium salt, increases the rate of extraction. The pounds, has a high potential for chemical tuning, and
addition of sulfonic and phosphoric acids to hydro- separates by incorporating different specific reagents.
xyoximes may enhance the rate of copper extraction The main drawbacks of LLE are the high consump-
due to the formation of reverse micelles and the tion of solvents, the difficulty of automation, and the
development of the microscopic interface. The a-acyloin formation of emulsion.
oximes that form an intermediate complex ‘that has Many efforts have been made to overcome these
a five-member ring’ with copper(II) increase the rate inherent drawbacks. There is also a tendency to
of extraction of aromatic hydroxyoximes. The addi- develop analytical procedures for sample preparation
tion of surfactants may cause both retardation and that reduce or completely eliminate the use of
acceleration of extraction. If the interfacial tension is organic solvents and decrease the number of opera-
decreased, surfactants cause an increase in the inter- tions. New processes are now being developed that
facial surface area in dispersed systems. When they employ aqueous-based systems. These use water ef-
adsorb at the interface, they cause an additional fectively and with a marked reduction in the risk to
 EXTRACTION / Solvent Extraction Principles 575

human health and the environment. The following proteins) can be first solubilized in micelles and then
new extraction processes can be considered: transferred to the SRP. Ions must first be neutralized
*
with hydrophilic complexing reagents. The CPE
cloud point extraction (CPE),
*
technique is used for the extraction and preconcen-
micellar enhanced ultrafiltration (MEUF),
*
tration of metal ions after the formation of sparingly
extraction in aqueous biphasic systems (ABS),
*
water-soluble complexes as an initial step for their
homogenous liquid–liquid extraction (HLLE),
*
determination by various instrumental methods as
extraction to ionic liquids (IL),
*
well as for the separation and purification of various
supercritical fluid extraction (SFE),
*
biochemicals, especially proteins.
continuous flow liquid–liquid extraction (CPLLE),
*
Coacervation, the clouding of solutions that con-
supported liquid membrane (SLM) extraction,
tain typical anionic surfactants, can be induced by
and
*
the addition of an electrolyte or by acidification and
microporous membrane liquid–liquid extraction
can also be used for preconcentration. However, the
(MMLLE).
phenomenon cannot be reversed as easily as the CP.
When surfactants aggregate in aqueous solutions, Substances that are solubilized in surfactant micel-
they form micelles even at relatively low concentra- les can be separated by ultrafiltration through mem-
tions, i.e., above the critical micelle concentration. branes whose pores are smaller in diameter than the
An increase in temperature causes the dehydration of micelle size. For a membrane molecular weight cut-
nonionic surfactants that have a hydrophilic poly- off from 1 to 50 kDa, the rejections are B98%. The
oxyethylene chain, e.g., Triton X-114, dissolved in stream of water-containing monomeric molecules of
aqueous solutions, the aggregation of micelles, and surfactant (permeate) flows through the membrane.
therefore the clouding of the solution at the cloud The remaining solution (retentate) contains solutes
point (CP) and the separation of the surfactant-rich solubilized in micelles. The MEUF process is used for
phase (SRP), as in Figure 7. The process can be the separation of organic substances and various
reversed by cooling. The volume of SRP is 1–2 orders ions, the latter after their previous complexation.
lower than the remaining aqueous micellar phase and Aqueous biphasic systems that contain two or
depends on the surfactant concentration and the more hydrophilic polymers, especially polyoxyethylene
temperature of separation. The SRP volume increases glycol–dextran–water or polymer and salt, and main-
with an increase in the surfactant concentration but ly polyoxyethylene glycol–inorganic salt–water, are
decreases with an increase in temperature above the classical techniques for recovering and separating bio-
CP. An increase in temperature also causes a decrease chemicals such as proteins and nucleic acids. They
in water content in the SRP, which becomes more also appear (especially the polyoxyethylene glycol–
hydrophobic. The phase can be considered a water inorganic salt–water system) to have some utility for
solution in the surfactant that is micelle-like in struc- solvent replacement in the extraction of metal ions
ture. The CP of nonionic surfactants can be modified and small organic molecules. The benefits of ABS are
by the surfactant structure and the addition of elec- connected with the aqueous environment of both
trolytes. An increase in surfactant hydrophobicity separated phases, which are formed without the
and an addition of salting-out electrolyte, e.g., NaCl, involvement of any organic solvent.
decreases CP. Salting-in electrolytes, such as KSCN, In HLLE, a small volume (microliter range) of
have the opposite effect. The cooling of solutions that water-immiscible liquid is separated from 10 to
contain zwitterionic surfactants, e.g., R(CH3)2N þ - 100 ml of homogeneous aqueous solution contain-
(CH2)3SO3 , also causes the clouding and separation ing perfluorooctanoate ion. This phenomenon is in-
of the SRP. Species that have some hydrophobi- duced by a change in pH or by the addition of
city (e.g., organic compounds, biochemicals, and counter-cations, such as quaternary ammonium ions.

Aqueous
Temp. phase
+
increase

Analyte Micellar Surfactant-

solution aqueous rich phase
solution
Figure 7 Cloud point extraction.
576 EXTRACTION / Solvent Extraction Principles

The solute species in the sample solution is concen- SLM extraction

trated in the sedimented phase, and a 100–1000-fold Aqueous
increase in concentration is achieved. This method sample Waste
is used to concentrate vital compounds such as
Porous impregnated
hemoglobin, vitamin B12, and various metal ions. membrane
HLLE seems to be a simple and powerful precon- Analyte transfer
centration method for several instrumentation tech- Stagnant acceptor

niques, including capillary gas chromatography and

capillary electrophoresis. MMLLE
ILs, mainly quaternary ammonium salts with hy- Aqueous
drophobic anions, e.g., 1-n-octyl-3-methylimidazolium sample Waste
hexafluorophosphate and tetrafluoroborate, are Porous membrane
nonvolatile solvents that can be also applied in ex-
Organic solution
traction. The selection of anions decides the IL hy- Enriched organic
solution
drophobicity, the formation of a two-phase system
with water, the solubility of ILs in water and of water Figure 8 Supported liquid membrane and microporous mem-
brane liquid–liquid extraction. (Adapted from Jonsson JA and
in ILs, and the IL’s hydroscopic properties. Up to
Mathiasson L (1999) Liquid membrane extraction in analytical
now, the hydrophobic ILs that form separated phases sample preparation. Trends in Analytical Chemistry 18: 318–
with water contain potentially dangerous anions, 324.)
such as PF6 and BF4 , which may decompose and
produce fluoride ions. ILs are more viscous than
typical solvents and may interfere with the transfer of Low pH High pH Low pH High pH
ionic species. New applications for small-scale sepa- S
rations may emerge in the future. ArOH ArOH
SFE is a well-established process for the recovery ArOH ArOH·S
of different organics, mainly nonpolar substances ArO− ArO−
from various solid matrices. It allows the selective
extraction of different chemicals without an addi-
tional clean-up step and uses small sample amounts. Simple transport Facilitated transport
Supercritical carbon dioxide (SC-CO2) is a convenient Figure 9 Simple and facilitated transport with solvating carrier
solvent, due to its moderate constants (T c ¼ 311C, of an aromatic compound having a phenolic group.
Pc ¼ 7.3 MPa), nontoxicity, nonflammability, suffi-
cient solvation power, and availability in pure form.
SC-CO2 is also used to extract various organic com-
pounds from environmental aqueous samples. Quan- with the carrier, then transported via diffusion
titative removal requires the addition of low through the pores on the other side of the mem-
molecular organic modifiers such as alcohols to en- brane and transferred to the acceptor phase. The
hance the polarity of SC-CO2. aqueous phases have different acidities to keep ana-
Automation and online connection to analytical lytes in neutral and charged forms in the donor and
instruments requires extraction to be performed in a acceptor phases, respectively, in simple transport,
continuous way and simultaneous with the flows of e.g., of amines, phenols, or organic acids, or to form
phases. The most successful techniques are MPLLE and decompose the complex in facilitated transport
and SLM extraction (Figure 8). SLM enables extrac- with carriers (Figure 9). The latter must be used for
tion and back-extraction to be carried out in one extraction of ionic species that are not soluble in the
continuous process due to the separation of flowing membrane without prior complexation. The SLM
aqueous phases (the acceptor phase is stagnant in extraction is a dynamic process that is usually con-
analytical applications) by a hydrophobic mem- trolled by diffusion in the pores and that gives sepa-
brane, which is usually of polytetrafluoroethylene, rations that are different to those for LLE, which is
and the organic phase immobilized in the pores of the an equilibrium process. By incorporating specially
membrane. The organic phase, used in small designed carriers, a very high selectivity can be ob-
amounts in comparison with LLE, may contain so- tained with an enrichment level of over 100 in
phisticated extractants called carriers. Membranes environmental samples. Using hollow fibers, en-
are impregnated by soaking in the organic phase. The richments of up to a few thousands were reported.
analyte present in the donor phase (aqueous sample) SLM extraction is well suited to automated inter-
is dissolved in the membrane phase or complexed facing with liquid chromatography and capillary
 EXTRACTION / Solvent Extraction: Multistage Countercurrent Distribution 577

E Waste See also: Analytical Reagents: Specification; Purification.

B Sampling: Theory; Practice. Surfactants and Detergents.
F J
I

A C Further Reading
Sample
G Gopalan AS, Wai CM, and Jackobs HK (eds.) (2003) Su-
H 2O D
percritical Carbon Dioxide. Separations and Processes.
H
ACS Symposium Series 860. Washington: Oxford
University Press.
Figure 10 Enrichment and separation setup for SLM extrac- Huldestone JG, Willauer HD, Griffin ST, and Rogers RT
tion. A – peristaltic pump, B – membrane device with hollow fiber (1999) Aqueous polymeric solutions as environmentally
installed into fused silica capillary, C – inlet on the donor side,
benign solvent extraction. Industrial & Engineering
D – washing line used after enrichment, E – microinjection pump
to transport the acceptor into loop F, G – C18 packed capillary
Chemistry Research 38: 2523–2539.
column, H – detector window, I – splitter unit, J – high pressure Pramauro E and Pelizzeti E (1996) Comprehensive analyti-
pump. (Adapted from Thordarson E, Palmarsdottir S, Mathiasson cal chemistry. In: Weber SG (ed.) Surfactants in Analyti-
L, and Jonsson JA (1996) Sample preparation using a miniaturi- cal Chemistry. Applications of Organized Amphiphilic
zed supported liquid membrane device connected on-line to Media, vol. 31. Amsterdam: Elsevier.
packed capillary liquid chromatography. Analytical Chemistry 68: Prochaska K (2002) Interfacial activity of metal ion ex-
2559–2563.) tractants. Advances of Colloid and Interface Science 95:
51–72.
Rogers RD and Seddon KR (eds.) (2002) Ion Liquids In-
electrophoresis. A miniature SLM device (Figure 10) dustrial Applications to Green Chemistry. ACS Sympo-
consists of polypropylene hollow fiber with pores sium Series 818. Washington: Oxford University Press.
filled with an organic solvent, inserted and fastened Rydberg J, Cox M, Musikas C, and Choppin GR (2004)
in a cylindrical channel of the module. The sample is Solvent Extraction. Principles and Practices. New York:
Dekker.
pumped on the outside of the hollow fiber, and the
Sastre AM, Kumar A, and Singh RK (1998) Improved
analyte is selectively enriched and trapped in the fiber
techniques in liquid membrane separations: An overview.
lumen. The volume of the stagnant acceptor solution Separation and Purification Methods 27: 213–298.
can be as low as 1–2 ml, and is transferred through Szymanowski J (1993) Hydroxyoximes and Copper Hydro-
capillaries to chromatographic systems. Using devices metallurgy. Boca Raton: CRC Press.
with a flat membrane, the volume of the enriched Szymanowski J (2000) Kinetics and interfacial phenomena.
sample is 10–15 ml. Solvent Extraction and Ion Exchange 18: 703–727.
A new version of CPLLE can be performed as Takagai Y and Igarashi S (2002) Homogenous liquid–
cross- and countercurrent flows of aqueous and liquid extraction as a simple and powerful preconcen-
organic phases separated by the microporous mem- tration method for capillary gas chromatography and
brane (MMLLE) in the same devices used for SLM capillary electrophoresis. American Laboratory July: 29–30.
Thornton JD (ed.) (1992) Science and Practice of Liquid–
extraction (Figure 8). The organic phase wets the
Liquid Extraction. Oxford: Oxford Science Publications,
membrane better than an aqueous solution and en- Clarendon Press.
ters the membrane pores. A leakage of the organic Zaslavsky BV (1994) Aqueous Two Phase Partitioning:
phase can be prevented by applying a suitably higher Physical Chemistry and Bioanalytical Applications. New
pressure on the aqueous side. York: Dekker.

Solvent Extraction: Multistage Countercurrent Distribution

C F Poole, Wayne State University, Detroit, MI, USA continuous or discontinuous depending on how the
& 2005, Elsevier Ltd. All Rights Reserved. liquid phases are contacted. Discontinuous processes
are characterized by a number of separate equilibra-
tion steps followed by transfer of either or both liq-
uid phases for further contact with the fresh liquid
phase. This multistage partitioning process is re-
Introduction ferred to as a countercurrent distribution. Manual
Separations by partitioning between two immisci- countercurrent distribution separations require little
ble liquids can be made more effective by using a equipment beyond suitable vessels, such as test tubes
cascade process. Suitable processes can be viewed as or separating funnels, and use either decantation or