Membrane Techniques: Liquid Membranes☆

Spas D Kolev, The University of Melbourne, Melbourne, VIC, Australia

© 2018 Elsevier Inc. All rights reserved.

This is an update of S.D. Kolev, Membrane Techniques | Liquid Membranes, Editor(s): Paul Worsfold, Alan Townshend, Colin Poole, Encyclopedia of Analytical
Science (Second Edition), Elsevier, 2005, Pages 531–538, ISBN 9780123693976.

Introduction 1
Membranes and Related Processes Used in Analytical Separation 2
Single-Phase Membranes 2
Dual-Phase Membranes 2
Gas-Diffusion Membranes 2
Membranes for Dialysis and Membrane-Assisted Liquid–Liquid Extraction 3
Liquid Membranes 3
Classification 3
Supported Liquid Membranes (SLMS) 3
Polymer Inclusion Membranes (PIMs) 5
Emulsion Liquid Membranes (ELMs) 5
Bulk Liquid Membranes (BLMs) 5
Liquid Membrane Separation 5
Mechanism 5
Passive Mass Transfer 6
Facilitated Mass Transfer 6
Analytical Applications of Liquid Membranes 7
Liquid Membrane Separation Units 8
Flat Sheet Membrane Separation Units 8
Tubular Membrane Separation Units 8
Further Reading 10

Introduction

The analysis of complex samples frequently necessitates pretreatment of the sample to separate the analyte from the sample matrix.
In some cases, analyte separation also results in preconcentration. Conventional analytical separation involves physicochemical
processes, such as precipitation, adsorption, ion exchange, and extraction.
Extraction, in its various forms, is one of the most frequently used separation processes in the analytical practice. In this process
the analyte is transferred from the sample, usually an aqueous solution, to another immiscible phase, which is usually a condensed
phase. If the condensed phase is a liquid the extraction technique is called liquid–liquid or solvent extraction. In the case of a solid
condensed phase, the corresponding extraction technique can be either solid-phase extraction (SPE) or solid-phase microextraction
(SPME).
In liquid–liquid extraction (LLE), the analyte is partitioned between two immiscible liquid phases, which are usually an aqueous
sample and an organic extracting solution. The possibility of dissolving organic compounds in this solution capable of chemically
interacting with the analyte (e.g., forming a complex or an ion pair) can improve substantially the selectivity and efficiency of the
extraction process on the one hand and widen the range of analytes (e.g., from ionic inorganic species to nonpolar organic
compounds), which can be separated by LLE, on the other. The main disadvantages of LLE are associated with the use of relatively
large volumes of organic diluents, which are often expensive, volatile, flammable, and toxic and may form stable emulsions with the
aqueous phase. Often the low sample to extracting solution volume ratio does not allow high enrichment factors. These drawbacks
of LLE can be overcome to a considerable extent by SPE, SPME, and solvent microextraction (SME), known also as liquid-phase
microextraction. When the analytical procedure involves further separation and detection in the aqueous phase (e.g., reversed-phase
high-performance liquid chromatography) following the LLE step, an additional back-extraction step from the organic phase into a
new aqueous phase must be introduced, which complicates the separation process.
In SPE, a solid sorbent material (e.g., resin or alkyl bonded silica) packed into a cartridge or imbedded into a polytetrafluor-
oethylene (PTFE) or glass fiber disk, replaces the organic extracting solution used in LLE. Separation in SPME is based on absorption
or adsorption of the analyte into the coating of a fused silica fiber, which may be a thin nonvolatile liquid film
(e.g., polydimethylsiloxane) or a porous solid (e.g., C18-bonded silica). The relatively small number of suitable sorbents reduces
the applicability of both SPE and SPME to the separation of mainly organic analytes of low polarity and limits the selectivity of these

☆
Change History: November 2018. Spas D Kolev updated the text, tables, and further readings to this entire article.

Encyclopedia of Analytical Science, 3rd Edition https://doi.org/10.1016/B978-0-12-409547-2.14301-X 1

2 Membrane Techniques: Liquid Membranes

techniques compared to that offered by LLE. Analytes are usually thermally desorbed in SPME while analyte adsorption in SPE is
followed by elution with a relatively small amount of an organic solvent.
In SME, a single microdroplet of the organic phase (e.g., n-octane, toluene), which may contain an internal standard, is usually
suspended in the sample solution on the tip of a microsyringe needle. After a predetermined extraction time the droplet is retracted
back into the microsyringe to be injected later into a gas chromatograph. Repeated suspending and retracting of the organic
microdroplet in the microsyringe can induce convective mass transfer within both the microdroplet and the sample solution
adjacent to it, resulting in high enrichment factors. Alternatively, the concentration of the extracted analyte can be determined
spectrophotometrically directly in the microdroplet if it forms a colored compound. SME has been successfully applied to
headspace analysis. Similarly to LLE, SME offers higher selectivity compared to SPE and SPME, but it is not readily adaptable to
analytical separations where back-extraction is required.
Membrane separation involving liquid membranes is an attractive alternative to the extraction techniques outlined above. Like
SPE and SPME, separation based on liquid membranes requires small amounts of organic solvents, if any, while at the same time it
offers the high selectivity, flexibility, and enrichment factors of LLE and SME. Liquid membranes are suitable for online analytical
separation, since the extraction and back-extraction steps take place simultaneously on the corresponding sides of the membrane,
unlike their sequential arrangement when other extraction techniques are used.

Membranes and Related Processes Used in Analytical Separation

In most membrane separation processes, the membrane separates two miscible or immiscible fluid phases, each one of which can
be either static or mobile. Most frequently the two fluids are liquids, one of which is the liquid sample (often referred to as the feed,
source or donor solution) while the other liquid is usually referred to as the receiver, strip, or acceptor solution. The membrane
prevents mixing and, very often, even direct contact between the two solutions. The latter function of the separation membrane is
particularly important when the feed and receiver solutions are miscible fluids or when analyte preconcentration is also required.
The membranes used in analytical separation processes are usually single- or dual-phase membranes.

Single-Phase Membranes
Depending on its aggregate state a single-phase (SP) membrane can be solid or liquid. Typical examples of solid SP separation
membranes are nonporous polymer membranes made of silicone rubber. These membranes have been used successfully in
membrane introduction mass spectrometry or gas chromatography where a receiver gaseous phase is used. Mechanical stability
and relatively long lifetime compared to other types of separation membranes are among the main advantages of nonporous
polymer membranes. However, these membranes are hydrophobic in nature and thus their use is limited to the separation of
mainly nonpolar analytes. Another drawback of nonporous polymer membranes is their low permeability, resulting in slow mass
transfer between the feed and receiver solutions.
Emulsion and bulk liquid membranes, which will be outlined later in this article, are typical liquid single-phase membranes.

Dual-Phase Membranes
The dual-phase (DP) membranes used in analytical separation usually consist of a polymer, or in some cases a ceramic solid-phase
support impregnated with a fluid (i.e., gaseous or liquid phase). If the fluid is air the DP membranes are known as a gas-diffusion
membranes. DP membranes incorporating a liquid phase can be considered in a broader sense as liquid membranes. The liquid
phase in a liquid DP membrane can be identical to the feed and/or receiver solution (e.g., dialysis membranes, ion-exchange
membranes, membrane-assisted LLE (MALLE)) or it can form a third immiscible liquid phase in the membrane separation system
(e.g., supported and polymer inclusion membranes). Membranes incorporating a liquid phase immiscible with the feed and
receiver phases, which are usually aqueous solutions, are often referred to as liquid membranes. This narrower definition of liquid
membranes, currently accepted in the literature, will be used in subsequent discussions. The membranes covered by this definition,
which can be either SP or DP membranes, will be outlined in more detail separately.

Gas-Diffusion Membranes
Hydrophobic porous polymer membranes with air filling the membrane pores have been used successfully in the online separation
of volatile and semivolatile analytes between two miscible liquid streams in flow analysis systems, that is, most frequently in flow
injection analysis (FIA) systems and in some cases in sequential injection analysis (SIA) systems. The corresponding membrane-
based separation technique is frequently referred to as gas-diffusion separation. The mass transfer of an analyte across a gas-
diffusion membrane is controlled by the membrane pore size and the solubility of the analyte in the feed and receiver solutions. The
latter can be manipulated by appropriately modifying the chemical composition of the two solutions. In this way it is possible to
enhance both the evaporation of the analyte from the feed solution into the membrane pores and its subsequent absorption into
the receiver solution.
 Membrane Techniques: Liquid Membranes 3

Membranes for Dialysis and Membrane-Assisted Liquid–Liquid Extraction

Depending on the hydrophobicity of a porous polymer membrane and the solutions in contact with it, the membrane pores can be
filled with the feed solution, the receiver solution, or a mixture of both solutions. If both solutions are miscible (e.g., aqueous
solutions) the separation of the analyte is based on dialysis, while if they are immiscible the separation process is often referred to as
MALLE.
Dialysis describes a separation process usually involving two aqueous phases (i.e., feed and receiver solutions) divided by a
hydrophilic (e.g., cellulose acetate) porous membrane. The membrane pores are filled with water and solutes from both the feed
and the receiver solutions. Typically, dialysis is utilized for the determination of low molecular mass analytes in samples containing
macromolecular species like proteins (e.g., chloride in milk). The average pore size determines the molecular mass range within
which chemical species can cross the membrane. The driving force in dialysis is the analyte concentration gradient across the
membrane (i.e., passive dialysis). If an external electric field is applied electrodialysis takes place. Both dialysis and electrodialysis
have been frequently used as online separation techniques in flow analysis systems. When the analytes are charged chemical species,
they can be separated from the sample matrix and preconcentrated in a receiver solution by means of Donnan dialysis. In this
process, an appropriately selected ion-exchange membrane (e.g., Nafion) separates the sample from a receiver solution of a smaller
volume and higher ionic strength. Ions of appropriate charge from the receiver solution are transported into the sample solution as a
result of the existing concentration gradient while coions from the sample solution including the analyte ions diffuse in the opposite
direction in order to maintain electroneutrality. Electrodialysis and Donnan dialysis, unlike passive dialysis, allow preconcentration
of the analyte as well.
In MALLE a hydrophobic or hydrophilic porous polymer membrane separates two immiscible solutions, usually an organic
receiver solution and an aqueous feed (sample) solution. If the membrane is hydrophobic, its pores are filled with the organic
receiver solution and the actual analyte partitioning between the two immiscible solutions takes place at the membrane/feed
solution interface. The analyte then diffuses across the membrane into the bulk of the organic receiver solution. Unlike LLE, MALLE
does not require mechanical mixing of the two immiscible solutions followed by phase separation, as a result of which the
extraction process can be miniaturized and conducted online. However, similarly to LLE, analyte separation and preconcentration in
MALLE is governed by the corresponding equilibrium constant of the extraction process (i.e., extraction constant). MALLE has been
implemented in flow analysis as an attractive alternative to the technically more complex segmented LLE approach, involving phase
segmentation, extraction, and phase separation prior to analyte detection in the organic solution. Another analytical application of
MALLE, based on SME, is the so-called extracting syringe or hollow fiber protected liquid-phase microextraction where a hollow
fiber connected to the stainless steel needle of a microsyringe is filled with a suitable organic extracting solution and exposed to a
flowing or mechanically stirred aqueous sample. After extraction, the organic extracting solution in the fiber is retracted back into
the syringe and subsequently injected into a gas chromatograph.

Liquid Membranes

By definition the membrane liquid phase of a liquid membrane must be immiscible with the aqueous solutions in contact with it.
This allows the chemical composition of all three liquid phases (including the membrane liquid phase) in a system where the liquid
membrane separates aqueous feed and receiver solutions to be altered independently of one another. For this reason liquid
membranes offer a higher degree of control over the membrane separation process compared to other types of separation
membranes.

Classification

The liquid membranes most often employed in analytical and industrial separation are: supported liquid membranes, polymer
liquid membranes, emulsion liquid membranes, and bulk liquid membranes.

Supported Liquid Membranes (SLMS)

SLMs are the most frequently used type of liquid membranes in analytical separation. An SLM can be constructed by impregnating
the pores of a microporous hydrophobic membrane (e.g., PTFE; poly(vinylidene fluoride) (PVDF); polypropylene) with a
membrane liquid phase, consisting of an extractant, often referred to as carrier and similar to those used in LLE (e.g., Cyanex
301/302/272, Aliquat 336, Alamine 336, di(2-ethylhexyl)phosphoric acid (D2EHPA)), dissolved in a suitable diluent
(e.g., kerosene, xylene, toluene, hexane, cyclohexane) (Fig. 1A). The porous solid membrane phase acts as a support for the
membrane liquid phase retained in the membrane pores by capillary forces.
The main disadvantage of SLMs is the slow leaching of the membrane liquid phase into the receiver and feed aqueous solutions,
thus reducing their lifetime. Attempts have been made to slow down the loss of the membrane liquid phase by converting it to a
polymer gel. The corresponding SLMs are known as gelled SLMs.
4 Membrane Techniques: Liquid Membranes

Fig. 1 Schematic of: (A) SLM separating mechanically stirred aqueous feed and receiver solutions; (B) ELM; and (C) BLM.

The liquid membrane in a solvent microextraction/back-extraction (SME/BE) technique, where the organic solution separating
the feed and receiver aqueous solutions is located within a PTFE ring (i.d. 6.4 mm), can be viewed as an SLM with a single
macropore. Very high enrichment factors can be achieved if the aqueous receiver solution is suspended as a microdroplet from the
tip of a microsyringe needle in the organic membrane. SME/BE allows the use of fresh liquid membrane for each extraction, thus
eliminating memory effects and long-term stability problems.
 Membrane Techniques: Liquid Membranes 5

Polymer Inclusion Membranes (PIMs)

PIMs are a relatively new type of self-supporting liquid membranes, which resemble SLMs. They consist of a base polymer (e.g.,
poly(vinyl chloride) (PVC), cellulose triacetate (CTA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)) and mem-
brane liquid phase which is immobilized between the entangled polymer chains. The membrane liquid phase is composed of an
extractant, similar to those used in SLMs, which often acts as a plasticizer. In some cases, the incorporation of additional organic
liquids such as plasticizers or modifiers (e.g., dioctylphthalate; n-decanol, 2-nitrophenyloctylether (2-NPOE)) is required to achieve
adequate homogeneity, flexibility and mechanical stability of the membrane or increase the solubility of the extracted species in the
membrane liquid phase.
A typical PIM is homogeneous and transparent and has sufficient flexibility and mechanical strength to be self-supporting and to
withstand mechanical stress such as bending without tearing or visually deforming.
PIMs are usually cast from a homogeneous solution of the membrane components outlined above in a suitable solvent
(e.g., tetrahydrofuran for PVC- and PVDF-HFP-based PIMs and dichloromethane for CTA-based PIMs) by the slow evaporation
of the solvent. By increasing the concentration of the extractant both the permeability of a PIM and the amount of the analyte
extracted will increase while at the same time its mechanical stability will deteriorate. For example, the optimal concentration range
for Aliquat 336 chloride in a PVC-based PIMs is between 40% and 50%.
The structure of PIMs is currently being elucidated. Surface analysis results have suggested the presence of networks of
nanometer-sized channels filled with the membrane liquid phase. The small size of these channels explains the facts that PIMs
appear homogeneous at macroscopic level, and that the rate of loss of the membrane liquid phase is small compared to that of
SLMs. The latter fact is responsible for the longer lifetime of PIMs than SLMs which makes them of considerable interest to industrial
and analytical separation.

Emulsion Liquid Membranes (ELMs)

A typical ELM consists of emulsion globules (extracting emulsion) of the receiver solution and the organic membrane liquid phase.
The emulsion globules are stabilized by a surfactant (e.g., sorbitan monooleate) and are dispersed in the feed aqueous solution (Fig.
1B). The resulting double emulsion is characterized by a large interfacial surface area between the emulsion globules and the feed
solution on the one hand, and within the emulsion globules, between the receiver aqueous solution, and the organic membrane
liquid phase on the other. This configuration allows fast mass transfer between the feed and receiver solutions. The membrane
liquid phase in ELMs is similar in composition to that of SLMs. By appropriate selection of the composition of the extracting
emulsion (i.e., electrolyte composition of the receiver phase, concentration of emulsifier, adsorption of solid particles on the
interface of the emulsion globules, formation of nanodispersion droplets by using microemulsifiers) high stability to coalescence
and sedimentation can be achieved. These properties of ELMs are crucial in avoiding mixing between the feed and receiver solutions
during the separation process.
After equilibrium in the system has been attained, the aqueous feed solution is separated from the emulsion globules, which are
further demulsified (e.g., by adding n-butanol) to form an organic liquid membrane layer and an aqueous receiver layer. After the
separation of these two liquid layers the aqueous receiver solution is analyzed.
ELMs allow high enrichment factors due to the large ratio of the feed solution volume to the receiver solution volume. The
presence of emulsifiers and the relatively larger volume of the membrane liquid phase in ELMs compared to that in SLMs allow the
organic diluents and extractants (carriers) in ELMs to be less hydrophobic than those normally used in SLMs. This extends the range
of membrane liquid phases that can be used in ELMs.
The currently existing difficulties in handling ELMs, associated mainly with the formation and breakdown of the emulsion itself,
have prevented the widespread use of this type of liquid membranes in the analytical practice despite the advantages outlined
above.

Bulk Liquid Membranes (BLMs)

A BLM consists of a layer of membrane liquid phase (i.e., an extracting solution) in contact with both the aqueous feed and receiver
solutions, located in separate compartments. Depending on its density, the membrane liquid phase can be located either above or
below the two aqueous solutions (Fig. 1C). Mechanical stirring of the feed and receiver solutions, and in some cases of the
membrane liquid phase, is required to enhance the mass transfer processes in the BLM three-phase system. BLMs are not suitable for
routine analyte separation because of the complex manual operations involved in conducting this analytical procedure. The main
analytical interest in this type of liquid membranes is based on the fact that they use small quantities of carrier and diluent
compared to traditional LLE, and therefore are suitable for screening carrier properties.

Liquid Membrane Separation

Mechanism
Membrane separation involves the following membrane-based processes: (1) transfer of the analyte from the feed solution to the
membrane liquid phase at the membrane/feed solution interface as a result of partitioning or extraction reaction, producing often a
6 Membrane Techniques: Liquid Membranes

lipophilic complex or ion pair; (2) membrane transport of the analyte complex or ion-pair by Fickian diffusion, driven by the
corresponding concentration gradient, across the membrane; and (3) transfer of the analyte from the membrane liquid phase to the
aqueous receiver solution at the membrane/receiver solution interface as a result of a suitable stripping (back-extraction) reaction.
The membrane concentration gradient can be maintained at its maximum by minimizing the analyte concentration in the receiver
solution at the corresponding membrane/solution interface. This result can be achieved by (1) converting the analyte entering the
receiver solution into another chemical species, usually using a suitable protolytic or complexation reaction; (2) inducing
convective mass transfer (e.g., mechanical stirring or flow); or (3) combining approaches (1) and (2). Approach (2) can also be
used to enhance the mass transfer of the analyte from the bulk of the feed solution to the membrane/feed solution interface.
Depending on the chemical composition of the membrane liquid phase, the mass transfer of the analyte from the feed solution
to the receiver solution can be either passive or facilitated.

Passive Mass Transfer

In the case of passive mass transfer, the membrane liquid phase consists of an organic solvent or a mixture of organic solvents. The
transfer of the analyte across both membrane/solution interfaces is governed by its partition coefficient. Fig. 2A illustrates
schematically the passive transport of an organic acid across a liquid membrane involving suitable protolytic reactions in both
the feed and receiver solutions. If the volume of the receiver solution is smaller than the volume of the feed solution the analyte of
interest can be concentrated as well. The mechanism of passive liquid membrane separation is analogous to that involved in
separation based on the use of solid single-phase and gas-diffusion membranes. However, unlike these membranes, liquid
membranes exhibit a higher degree of flexibility due to the ease with which the membrane liquid phase composition can be
modified to meet the specific requirements of the analyte of interest (e.g., polarity).
Organic solvents used in liquid membranes for both passive and facilitated mass transfer can be either nonpolar aliphatic or
aromatic hydrocarbons such as toluene and kerosene, or polar organic compounds such as dihexylether. The polarity of the
membrane liquid phase can be modified readily by the addition of small amounts of hydrophobic polar organic solvents
(e.g., trioctyl phosphine oxide, dodecanol). Liquid membranes are generally more permeable than solid single-phase membranes
thus allowing faster separation. They are also suitable for the separation of both volatile and nonvolatile analytes.

Facilitated Mass Transfer

Similarly to LLE, the selectivity and efficiency of the liquid membrane separation process can be considerably improved if a suitable
extractant with a high selectivity for the analyte of interest is used. This extractant (carrier) facilitates the mass transfer of the analyte
between the feed and receiver solutions. The membrane liquid phase in this case usually consists of a suitable extractant or an

Fig. 2 Schematic representation of: (A) passive membrane mass transfer; and (B) facilitated membrane mass transfer (A
is the analyte anion and Xþ is a cationic
carrier).
 Membrane Techniques: Liquid Membranes 7

extractant dissolved in an organic solvent (diluent). The extractant facilitates the transport of the analyte from the feed solution to
the membrane liquid phase by chemically interacting with it. This interaction, as mentioned above, leads to the selective extraction
of the analyte into the membrane liquid phase as a lipophilic complex or ion pair. The analyte is released into the receiver solution
at the membrane/receiver solution interface as a result of another chemical reaction, and the freed extractant (carrier) diffuses back
to the membrane/feed solution interface where it can extract another analyte species. A typical liquid membrane anionic extractant
(carrier) is the positively charged quaternary alkylammonium cation of Aliquat 336 (tricaprylylmethylammonium cation).
Frequently used cationic extractants (carriers) of mainly metal cations are the negatively charged lipophilic conjugated bases of
organic acids (e.g., DEHPA). Both cationic and anionic extractants (carriers) form neutral ion pairs with the oppositely charged ionic
analyte. Metal complexes of macrocyclic ligands with hydrophobic functional groups such as sodium 1,10-didecyl-1,10-
diaza-18-crown-6 complex (Na-22DD) have been also used successfully as extractants (carriers) in the membrane separation and
preconcentration of metal ions. Ligand substitution reactions take place at both membrane/solution interfaces in these cases. Fig. 2B
shows schematically a typical mechanism of facilitated liquid membrane separation process involving an anionic extractant
(carrier) (Xþ).

Analytical Applications of Liquid Membranes

The analytical interest in BLMs and ELMs is based mainly on their use as a convenient research tool in screening carriers and
determining the optimal composition of SLMs. Though there are numerous environmental (Table 1) and clinical (Table 2)
applications of SLMs, these liquid membranes have been used relatively rarely in food and beverage analyses (e.g., biogenic amines
in wine, vanilla in chocolate and sugar, nicotine in Swedish snuff, and caffeine in coffee).
Despite the fact that PIMs can still be considered as a relatively new class of liquid membranes, they have already shown
promising results in numerous applications involving on-line (as part of flow analysis methods) and off-line separation and
preconcentration of analytes of environmental interest which include:

• Metallic species: Zn(II), Cu(II), V(V), Cr(VI), and As(V).

• Nonmetallic inorganic species: NHþ
2



4 , SCN , HPO4 , HCOO , ClO4 .
• Organic species: oxytetracycline, glyphosate, aminomethylphosphonic acid, chlorinated phenoxyacetic acids, basic drugs
(amphetamine, methamphetamine and 3,4-methylenedioxy-N-methylamphetamine), cationic herbicides (paraquat and
diquat), and anionic herbicides (2-(4-chlorophenoxy) acetic acid and 2-(2,4-dichlorophenoxy) acetic acid).

PIMs have been used successfully in chemical sensing for the development of optodes for a variety of analytes (e.g., Hg(II), Cu(II),
Al(III), Eu(III), Tb(III), Pb(II), I2, TcO



4 , CN , and NO3 ). Recently a microfluidic paper-based analytical device for Cu(II)
incorporating a PIM as its sensing element has been reported.
Both SLMs and PIMs have been used as the semipermeable barrier in passive samplers for the determination of the time-
weighted average concentration of various pollutants (e.g., Zn(II), NHþ
4 , and sulfamethoxazole) in aquatic systems.
Several SLM and PIM applications have involved electric filed-driven extraction.

Table 1 Analytes determined in environmental samples after SLM separation

Amino acids Tryptophan, phenylalanine, tyrosine

Aniline and its Aniline, chloroanlines, methylanilines, chloromethylanilines
derivatives
Aromatic compounds Nitrophenols, chlorinated phenols, phenolic acids (benzoic, p-hydroxybenzoic, vanillic, caffeic, p-coumaric, ferulic, salicylic, and
phenazine-1-carboxylic), alkylphenols (4-tert-butylphenol, 2,4-di-tert-butylphenol, 4-n-nonylphenol, and 4-n-octylphenol), aromatic
anionic surfactants (alkylbenzenesulfonates), PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, 4H-
cyclopenta[def]phenanthrene, fluoranthene, and pyrene), hydroxyaromatic compounds (2,7-dihydroxynaphthalene, 4,49-
dihydroxybiphenyl, 2-hydroxynaphthalene, 1-hydroxynaphthalene, p-phenylphenol, and o-phenylphenol), parabens (4-hydroxybenzoic
acid, methylparaben, ethylparaben, and propylparaben), phthalate esters (dimethyl phthalate, diethyl phthalate and butyl benzyl ester),
pyridine derivatives (pyridine, 3-methyl pyridine, 2,4-dimethyl pyridine, and quinoline)
Carboxylic acids Monocarboxylic acids (formic, acetic, propionic, butyric, iso-butyric, valeric, and iso-valeric), dicarboxylic acids (glutaric, dimethylglutaric,
and adipic), haloacetic acids (monochloroacetic, dichloroacetic, monobromoacetic, bromochloroacetic, dibromoacetic, trichloroacetic,
bromodichloroacetic, chlorodibromoacetic, and tribromoacetic), aromatic acetic acids (phenylacetic and p-hydroxy phenylacetic)
Metal ions Cu(II), Pb(II), Cd(II), Zn(II), Ni(II), Al(III), Cr(III), Cr(VI)
Pesticides Phenoxy acids (2,4-dichlorophenoxy acetic, MCPA and 2,4,5-trichlorophenoxy acetic) and similar acid herbicides (benzaton, dicamba,
dichlorprop, and mecoprop), sulfonurea herbicides (chlorsulforon, metsulforon methyl, tribenuron methyl, and thifensulfuron methyl),
triazine herbicides (methoxy-s-triazines, chloro-s-triazines and alkylthio-s-triazines); phenylurea herbicides (fenuron, monolinuron and
diuron), metabolites of the fungicide thiophanate-methyl (carbenazim and 2-aminobenzimidazole)
Drugs Diclofenac, fenoprofen, flurbiprofen, gemfibrozil, ibuprofen, indometacin, ketoprofen, probenecid, naproxen, hexobarbital, and warfarin
8 Membrane Techniques: Liquid Membranes

Table 2 Analytes determined in biological fluids (e.g., blood plasma, breast milk, and urine) after SLM separation

Biologically active Aliphatic and aromatic amines (methyl-, ethyl-, propyl-, and octyl-amines, piperidine, 1-ethylpiperidine, N-methylmorpholine,
compounds cyclohexylamine, N,N-dimethylcyclohexylamine, pyrrole, pyrrolidine, pyridine, and aniline); phenols (phenol, p-cresol,
4-chlorophenol, 2-secbutyl-4,6-dinitrophenol, 4,6-o-dinitrocresol, 2,4-dinitrophenol, and 3-methyl-4-nitrophenol); diphenyl
phosphate ester, alkaloids (morphine, codeine, noscapine, thebaine, papaverine, and cocaine)
Drugs Amperozide, amphetamine, methamphetamine, ketamine, bambuterol, antidepressants (paroxetine, fluvoxamine, mianserin, and
citalopram), anabolic steroids (glucuronides), hormonal drugs (megestrol acetate and levonorgestrel), amitriptyline, promethazine,
methadone, nortriptyline, haloperidol, loperamide, pethidine, ibuprofen, naproxen, ketoprofen, propofol, ropivacaine, tramadol,
ephedrine, cathinone
Metal ions Pb(II), Mn(II)

Liquid Membrane Separation Units

Depending on the geometry of the solid polymer support, SLMs and PIMs can be produced in the form of flat sheets or hollow tubes
(hollow fibers).

Flat Sheet Membrane Separation Units

Flat sheet membrane units incorporating SLMs and PIMs have been used for both offline and online analytical separation.
Offline separation can be conducted in a system consisting of two mechanically stirred feed and receiver solutions separated by a
flat sheet liquid membrane (Fig. 1A). Similar extraction systems have also been used in determining the permeability of SLMs and
PIMs and in studying the extraction mechanism and kinetics involved in membrane separation processes.
A typical flow-through membrane unit allowing online separation usually consists of two halves made of a chemically inert
polymer material (e.g., PTFE, PVDF), each furnished with a shallow groove. The two halves are separated by a flat liquid membrane.
The groove connected to the feed solution stream (often referred to in flow analysis to as the donor stream) is called the donor
chamber (channel), while the other groove is called the acceptor chamber (channel) (Fig. 3A). The receiver solution (referred to as
acceptor solution) flows through the acceptor chamber (channel). The grooves can be linear, meander shaped, or arranged as an
Archimedes’ spiral (Fig. 3B). Typically the groove width and depth can vary in the range from 1 to 3 mm and from 0.1 to 0.5 mm,
respectively. Though the two grooves must face each other, they can differ in depth. In most cases, however, they have identical
dimensions.
The donor and acceptor solutions usually flow concurrently through the membrane separation unit (continuous mode). Higher
efficiency can be achieved by decreasing the acceptor solution flow rate with respect to the donor solution flow rate, or by stopping
the acceptor solution for a predetermined period of time to trap the analyte in the stagnant acceptor solution located in the
acceptor chamber (stopped-flow mode). The acceptor solution can be flown through a suitable flow-through detector for
measuring the analyte concentration or it can be analyzed offline. In many sample clean-up applications the acceptor solution
is introduced into a high-performance liquid chromatograph or a gas chromatograph for further separation and subsequent
detection.

Tubular Membrane Separation Units

A typical flow-through tubular membrane separation unit frequently consists of two concentric tubes (Fig. 3C) and usually operates
in a stopped-flow mode. The acceptor solution is located in the inner tube, which in most cases is a single porous hollow fiber
impregnated with a suitable organic solvent (e.g., 1-octanol, 6-undecanone) which may contain an extractant (carrier). The sample
(donor) solution flows through the outer tube made of a polymeric material (e.g., Kel-F) or glass. PIMs have not been used so far in
flow-through tubular separation units.
It is also possible to immerse the hollow fiber SLM or PIM with one end sealed and filled with a suitable acceptor solution into a
vial containing a sample solution, which may be mechanically stirred. Electric field-driven extraction has been implemented in such
configurations.
Hollow fiber SLMs and PIMs allow faster analyte separation and higher enrichment factors compared to flat sheet membranes
because of their high surface area to extracting solution volume ratio. Extracting solutions volumes of the order of several microliters
can be employed, which allows the coupling of hollow fiber SLM- or PIM-based separation to other low sample capacity separation
techniques (e.g., packed capillary liquid chromatography and capillary electrophoresis).
 Membrane Techniques: Liquid Membranes 9

Fig. 3 Schematic of: (A) flow-through membrane separation unit for flat sheet membranes; (B) top view of one of the unit’s halves with linear, meander, and
Archimedes’ spiral groove; and (C) tubular flow-through membrane separation unit.
10 Membrane Techniques: Liquid Membranes

Further Reading
Alexovic, M.; Horstkotte, B.; Solich, P.; Sabo, J. Automation of Static and Dynamic Non-Dispersive Liquid Phase Microextraction. Part 2: Approaches Based on Impregnated
Membranes and Porous Supports; Anal. Chim. Acta 2018, 907, 18–30.
Almeida, M. I. G. S.; Cattrall, R. W.; Kolev, S. D. Polymer Inclusion Membranes (PIMs) in Chemical Analysis—A Review; Anal. Chim. Acta 2017, 987, 1–14.
Almeida, M. I. G. S.; Cattrall, R. W.; Kolev, S. D. Recent Trends in Extraction and Transport of Metal Ions Using Polymer Inclusion Membranes (PIMs); J. Membr. Sci. 2012, 415-416,
9–23.
Araki, T.; Tsukube, H. Liquid Membranes: Chemical Applications, 1st ed.; CRC Press: Boca Raton, 1990.
Dean, J. R. Extraction Methods for Environmental Analysis, 1st ed.; Wiley: Chichester, 1998.
Jönsson, J.Å.; Mathiasson, L. Membrane-based Technique for Sample Enrichment; J. Chromatogr. A 2000, 902, 205–225.
Jönsson, J.Å.; Mathiasson, L. Membrane Extraction in Analytical Chemistry; J. Sep. Sci. 2001, 24, 495–507.
Kolev, S. D.; Almeida, M. I. G. S.; Cattrall, R. W. Polymer Inclusion Membranes; In Handbook of Membrane Separations, 2nd ed.; Pabby, A. K., Rizvi, S. S. H., Sastre, A. M., Eds.; CRC
Press: Boca Raton, 2013; pp 723–739.
López-López, J. A.; Mendiguchía, C.; Pinto, J. J.; Moreno, C. Liquid Membranes for Quantification and Speciation of Trace Metals in Natural Waters; TrAC, Trends Anal. Chem. 2010,
29, 645–653.
Luque de Castro, M. D.; Álvarez-Sánchez, B. Membrane-based Separation Techniques: Liquid-Liquid Extraction and Filtration; In Advances in Flow Injection Analysis and Related
Techniques, 1st ed.; Kolev, S. D., McKelvie, I. D., Eds.; Elsevier: Amsterdam, 2008; pp 235–264.
Marothu, V. K.; Gorrepati, M.; Vusa, R. Electromembrane Extraction—A Novel Extraction Technique for Pharmaceutical, Chemical, Clinical and Environmental Analysis; J. Chromatogr.
Sci. 2013, 51, 619–631.
Pedersen-Bjergaard, S.; Rasmussen, K. E. Liquid-Phase Microextraction with Porous Hollow Fibers, a Miniaturized and Highly Flexible Format for Liquid–Liquid Extraction;
J. Chromatogr. A 2008, 1184, 132–142.
Pedersen-Bjergaard, S.; Rasmussen, K. E.; Halvorsen, T. G. Liquid–Liquid Extraction Procedures for Sample Enrichment in Capillary Zone Electrophoresis; J. Chromatogr. A 2000,
902, 91–225.
Valcarcel, M.; Luque de Castro, M. D. Non-Chromatographic Continuous Separation Techniques, 1st ed.; The Royal Society of Chemistry: Cambridge, 1991.
Vrana, B.; Mills, G. A.; Allan, I. J.; Dominiak, E.; Svensson, K.; Knutsson, J.; Morrison, G.; Greenwood, R. Passive Sampling Techniques for Monitoring Pollutants in Water; TrAC, Trends
Anal. Chem. 2005, 24, 845–868.
Yamini, Y.; Seidi, S.; Rezazadeh, M. Electrical Field-Induced Extraction and Separation Techniques: Promising Trends in Analytical Chemistry—A Review; Anal. Chim. Acta 2014, 814,
1–22.