MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 515

Muhammad WT, Tabb DL, Fox KF, and Fox A (2003) tion mass spectrometry. Rapid Communications in Mass
Automated discrimination of polymerase chain reaction Spectrometry 9: 1484–1486.
products with closely related sequences by software- Oefner PJ and Huber CG (2002) A decade of high-reso-
based detection of characteristic peaks in product ion lution liquid chromatography of nucleic acids on sty-
spectra. Rapid Communications in Mass Spectrometry rene–divinylbenzene co-polymers. Journal of
16: 1–8. Chromatography B 782: 27–55.
Muddiman DC, Null AP, and Hannis JC (1999) Precise Walters JJ, Fox KF, and Fox A (2002) Mass spectrometry
mass measurement of a double stranded 500 base-pair and tandem mass spectrometry, alone or after liquid
(309 kDa) polymerase chain reaction product by negative chromatography, for analysis of polymerase chain reac-
ion electrospray ionization Fourier transform ion cyclo- tion products in the detection of genomic variants. Jour-
tron resonance mass spectrometry. Rapid Communica- nal of Chromatography B 782: 57–66.
tions in Mass Spectrometry 13: 1201–1204. Yiang Y and Hofstadler SA (2003) A highly efficient and
Naito Y, Ishikawa K, Koga Y, et al. (1995) Molecular mass automated method of purifying and desalting PCR prod-
measurement of polymerase chain reaction products am- ucts by electrospray ionization mass spectrometry. Ana-
plified from human blood DNA by electrospray ioniza- lytical Biochemistry 316: 50–57.

MEAT AND MEAT PRODUCTS

See FOOD AND NUTRITIONAL ANALYSIS: Meat and Meat Products

MECA
See MOLECULAR EMISSION CAVITY ANALYSIS

MEMBRANE TECHNIQUES
Contents
Dialysis and Reverse Osmosis
Ultrafiltration
Liquid Membranes
Pervaporation

analysis. Donor and acceptor solutions are separated

Dialysis and Reverse Osmosis by a membrane, which is permeable to one or more
solutes. When the solutions have different solute
U Spohn, Martin-Luther Universitat Halle-Wittenberg, activities, a diffusional transport from the higher to
Halle, Germany the lower activity a (a ¼ cf , where c is the concen-
& 2005, Elsevier Ltd. All Rights Reserved.
tration and f the activity coefficient) through the
membrane takes place (Figure 1). The main driving
force for the diffusion of small molecules or ions is
their concentration gradient. In most cases, dialysis is
employed to retain large molecules while exchanging
Introduction or eliminating small ones.
Dialysis is a separation process with many applica- Different solvent activities generate an osmotic
tions in clinical, biochemical, and environmental pressure, which causes a solvent flow to the solution
516 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis

C D A The effective separation ratio Ki is calculated ac-

cording to eqn [3]
ci;A
Ki ¼ ½3
ci;D
At Ki ¼ 1 a stationary state, called the thermody-
namic equilibrium is reached and no directed diffu-
sion can take place. Ki differs from unity when the
activity coefficients of the solute i are different, e.g.,
if the donor and acceptor solutions have different
I
compositions and/or the dialysis equilibrium is cou-
C pled with other equilibria. Without coupled reac-
tions, the enrichment E and the purification P can be
calculated according to eqns [4] and [5],
ci;A ðci;Do
ci;D ÞVD
E¼ ¼ ½4
ci;Do ci;Do  VA

ci;Do
ci;D ðci;A
ci;Ao ÞVA

P¼ ¼ ½5
ci;Do ci;Do  VD
where ci;Do and ci;Ao are the initial solute concentra-
tions in the donor and in the acceptor solution, re-
II
D dM
A X spectively. VA and VD are the volumes of the
corresponding solutions. Without trapping reaction
Figure 1 Dialysis between quiescent (I) and stirred or flowing
in the acceptor solution, during which the received
solutions (II) solutions. C, concentration; D, donor solution; A,
acceptor solution; M, membrane; dM, thickness of the membrane; analyte is converted into a substance that cannot
dA and dD , thicknesses of the boundary layers. permeate the membrane, the enrichment E approach-
es 0.5 for VA ¼ VD. If the activity coefficients are
of the lower solvent activity. This process is termed equal (i.e., fi;A ¼ fi;D ) in the equilibrium state, E will
osmosis. Reverse osmosis is the process during which be 0.5. Also the chemical activities of the solvent S
an outer pressure is applied to force the solvent are equal at dialysis equilibrium. Because
through a membrane, which rejects the solute. mS;D ¼ mS;A ½6
Reverse osmosis is used almost exclusively to desalt
and purify water. In the ideal case, the separation and
membrane is only permeable to water. moS;D ¼ moS;A ½7

The thermodynamic equilibrium constant KS is given

Thermodynamics as
ax;S;A
The difference between the chemical activities of the KS ¼ exp½ðVmS;D pD
VmS;A pA Þ=RT ¼ ½8
ax;S;D
solute i is the precaution for its diffusional transport
through the separation membrane. The free enthalpy where VmS;D and VmS;A are the partial molar volumes
DG of diffusion can be calculated from the difference of the solvent, which are equal to the VmS for dilute
between the chemical potentials mi;A and mi;D of the solutions. pD and pA refer to the corresponding
solute i in the acceptor (A) and donor solution (D), osmotic pressures. ax;S;A and ax;S;D are the activities
respectively (eqn [1]). moi;D and moi;A are the standard of the solvent with respect to its mole fraction xS
chemical potentials, in the acceptor and donor solutions, respectively. It
follows that
DG ¼ mi;D
mi;A ¼ moi;D
moi;A þ RT lnðai;D =ai;A Þ ½1
KS ¼ exp½ðpD
pA ÞVmS =RT ½9
The equilibrium constant Ki depends on the activity
coefficients fi;A and fi;D , the concentrations ci;A and The resulting pressure difference p ¼ pD
pA can
ci;D , and the absolute temperature T according to eqn be calculated according to eqn [10]:
[2]. R is the molar gas constant. Ki is given as p ¼
ðRT=VmS Þln ax;S;A for ax;S;D ¼ 1 ½10
 o 
ai;A fi;A  ci;A mi;D
moi;A This pressure difference causes a solvent flow
Ki ¼ ¼ ¼ exp ½2
ai;D fi;D  ci;D RT through the separation membrane (Figure 2A) up
 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 517

p Faraday constant F:
A D A D A D
Ki ¼ expðzi FDf=RTÞ ½12

An additionally applied electric voltage U generates

 −p h an electromigration of the anions to the positively
charged anode and of the cations in the opposite
direction. This process is termed electrodialysis.

(A) M (B) M (C) M

Mass Transport
Figure 2 (A) Osmosis; (B) osmotic equilibrium; (C) reverse
osmosis. M, semipermeable membrane; p h , hydrostatic pres- Dialysis
sure; p, osmotis pressure; p, external pressure, D, aqueous salt
For quiescent donor and acceptor solutions, the
solution, A, water.
equilibration time ranges from minutes to several
hours and is dependent on the thickness and other
∆U geometrical parameters of the corresponding cham-
 bers, the membrane permeability, and the tempera-
ture. The equilibration is dominated by diffusion.
The equilibration can be accelerated by convective
mass transport according to Figure 1 by achieving
Anode (+) Cathode (−) thin diffusional boundary layers on the membrane.
The overall flux of the substance i with its molar
H2O H2O
amount ni from the donor to the acceptor solution
+
B B+ can be described according to eqn [13]:
A− A−  
+ − dni KAM
B X Ji ¼ ¼ kA bi;D ci;D
bi;A ci;A ½13
dt KDM

where bi;D and bi;A are the fractions of the substance i

D M A in the donor and in the acceptor solutions, re-
Figure 3 Donnan dialysis. M, semipermeable membrane; spectively, that can permeate through the separation
D, donor solution; A, acceptor solution, f, Donnan potential; U membrane. KDM and KAM are the distribution con-
applied voltage. stants between the donor solution and the membrane
and between the acceptor solution and the mem-
to the state at which the hydrostatic or another back- brane, respectively. In the classical case of dialysis of
pressure compensates for the osmotic pressure, e.g., low molecular substances through a membrane with
in batch-type arrangement shown in Figure 2B. If the symmetric and open pores eqn [14] holds
outer pressure p is higher than the osmotic pressure dni
difference p, the osmosis will be reversed (Figure 2C). Ji ¼ ¼ kAðci;D
ci;A Þ ½14
dt
An equilibrium desribed by eqn [11] will be reached:
  The general overall mass transfer coefficient k can be
VmS derived from eqn [15]
KS ¼ exp ðp
ph Þ ½11
RT
1 1 1 KAM
The rejected solute is enriched in the donor solution. ¼ þ þ ½15
k kD kM KDM kA KDM
To take into account the electric charge zi of the sol-
utes and of the separation membrane, the Donnan where kD , kM , and kA are the mass transfer coeffi-
effect has to be considered. The chemical potential mi cients of the permeating fractions of substance i for
is extended by the electric potential gradient, Df. the donor, the membrane, and the acceptor phases,
When a membrane separates two solutions of a dis- respectively. In many cases, the mass transfer across
sociating salt BA (BA"Bþ þ A
), one of which the phase boundary also needs to be considered, e.g.,
contains a rejected ion X
, an electric potential dif- for gas-filled microporous membranes. Equation [16]
ference Df ¼ fD
fA is built up between the solu- has an additional term on the right-hand side:
tions (Figure 3). The thermodynamic equilibrium
constant can be calculated in the absence of osmotic 1 1 KAM
a¼ þ ½16
pressure differences according to eqn [12] with the kpDM kpAM KDM
518 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis

where kpDM and kpAM are the phase transfer coeffi- the acceptor solutions, respectively:
cients from the donor solution into the membrane
ci;g;D pi;D
phase and from the membrane into the acceptor KDM ¼ D ½24
bi;D  ci;D bi;D RTci;D
phase, respectively.
From the general eqns [15] and [16], some cases of
practical interest can be deduced. ci;g;A pi;A
KAM ¼ D ½25
bi;A  ci;A bi;A RTci;A
Dialysis through hydrophilic and microporous mem-
branes As KDM ¼ KAM ¼ 1 and no phase transfer For low partial pressures pi;D and pi;A , KDM and KAM
occurs, eqn [15] simplifies to eqn [17] as follows: approximate the right-hand terms of eqns [24] and
[25]. ci;g;D and ci;g;A are the gas-phase concentrations
1 1 1 1 at the interface between the donor or the acceptor
¼ þ þ ½17
k kD kM kA solution and the membrane gas phase, respectively.
Because the nonvolatile forms of the analyte cannot
For large concentration gradients and very intensive permeate and KAM approximates zero at pH precal-
stirring or in flow-through dialysis cells at high culated by eqn [21]. Equation [15] simplifies to eqn
enough flow rates, the membrane diffusional trans- [26] as follows:
port becomes rate determining particularly for re-
latively thick membranes with small pores (eqn [18]) 1 1 1
¼ þ þa ½26
k kD kM KDM
k ¼ km ½18
For fast-flowing donor solutions with 1=kD -0 the
Dialysis of volatile and volatilizing substances mass transport is determined by the gas diffusion
through hydrophobic and microporous mem- through the membrane, the partial pressure of the
branes To separate a nonvolatile base AH þ , its analyte in the donor solution, and the phase-transfer
corresponding volatile base A, e.g., NH3 is produced resistances.
according to the following equilibrium: Reverse Osmosis
þ

AH þ OH #A þ H2 O ½19 The driving force of reverse osmosis is the difference
between the outer pressure ph and the osmotic pres-
The donor pH value is adjusted according to eqn [20] sure difference p. The mass transfer can be described
so that there is 99.9% degree of conversion into the according to the following equation:
volatile and the permeable base:
JS ¼ nS =t ¼ PAðph
fR pÞ ½27
Ka
bi;D ¼ 40:999 ½20
10
pH þ Ka where JS , P, and A are the mass flux of the solvent
through the separation membrane, the water perme-
where Ka is the acid-dissociation constant of AH þ . ability of the membrane, and the membrane area,
The acceptor pH value should be adjusted according respectively. The mass flux is influenced by the re-
to eqn [21] to trap the analyte in its nonvolatile form: flection factor fR, which is a measure of the solute
rejection by the membrane. The osmotic pressure
10
pH
1
bi;A ¼ 40:999 ½21 difference increases continuously during the enrich-
10
pHþ Ka
ment of the solutes in the donor solution up to
Analogous equations can be derived for volatile ac- ph ¼ fR p. The rejection ratio R is defined by eqn [28]:
ids, e.g., HCN. Since only the volatile part of the ci;A
analyte amount permeates the membrane, it follows R¼1
½28
ci;D;o
that
with ci;A as the solute concentration in the filtrate,
Ji ¼ kAci;D ½22 and ci;D;o as the initial concentration in the donor
solution. The rejected solutes accumulate on the
with membrane surface (Figure 4). This phenomenon is
1 1 1 KAM
called concentration polarization. On achieving the
¼ þ þ þa ½23 saturation level, the solute will start to precipitate
k kD KM KDM KA KDM
forming a secondary layer on the membrane, which
The distribution ratios KDM and KAM are inversely drastically reduces the mass flux through it. The
proportional to the concentrations bi;D  ci;D and analytical usefulness of the reverse osmosis is based
bi;A  ci;A of the volatile forms in the donor and in on the high enrichment factor E, which can be
 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 519

pD where ci;MD and ci;MA are the solute concentrations in

D the membrane at the interfaces between donor and
ci,DM acceptor solutions, respectively. The separation
ci,D
JL membrane is chosen with respect to its selectivity
and mass transfer kinetics. The membrane material
J ii
determines the transport mechanism. Table 1 gives
an overview about membrane materials, their mod-
pA ifications, and the dominant transport mechanism. In
D most cases the selectivity is based on the sieve effect
Ci,A of the membrane pores. The dialysis across gas-filled
membranes, ion-exchange membranes, or supported

C dM dS liquid membranes (SLMs), the pores of which are
filled with organic solvents or solvent mixtures with
Figure 4 Reverse osmosis with concentration polarization on and without additives, enables the enrichment of the
the asymmetric separation membrane. Ji , mass flux of the solute
i; pD , outer pressure from the donor side; pA , outer pressure from
analyte to be detected. The selectivity of SLM tech-
the acceptor side; pA and pD , osmotic pressure in the acceptor niques is enhanced by the addition of selectively re-
and donor chamber, respectively; dM and dS , thickness of the acting ligands to the liquid membrane phase. When
membrane layer and the membrane supporting layer, re- charged ions are complexed and transported through
spectively; dC , thickness of the polarization layer; ci;DM , ci;A , such membranes electroneutrality must be main-
ci;D , concentration of the solute i in the acceptor solution, in the
donor solution, and at the separation membrane, respectively.
tained. In some cases ion pairs with selected coun-
terions are transported through the liquid membrane
calculated according to eqn [29]: phase. When a binding ligand is dissolved in this
phase and the counterion cannot transverse the
ci;D VD;o membrane, the analyte ion transport is coupled with
E¼ ¼ ½29
ci;Do VD;o
VA back-diffusion of an ion from the acceptor solution.
A similar situation occurs in ion-exchange mem-
where VD;o is the initial volume of the donor branes, which are used to enrich ions by Donnan
solution. dialysis.
Using microporous membranes with a hydropho-
Geometric Aspects
bic inner surface, the selectivity of gas dialysis
The geometric shape and volume both of the donor against other volatiles results predominately from
and the acceptor chambers as well as of the separa- the ratio of the partial pressure of the analyte pi to
tion membrane have an essential influence on the the total pressure. In homogeneous membranes, the
duration of the separation. To minimize the separa- different solubilities of the gases in the membrane
tion time, the thickness of the donor solution layer material are the main selecting factor.
should be as thin as possible. The ratio of the mem-
brane exchange area to the donor solution volume
should be maximized. To maximize the enrichment Applications
factor for dialysis with enhanced selectivity, e.g., gas
Dialysis through Microporous Membranes
dialysis, the volume ratio between the donor solution
and the acceptor solution has to be maximized. The In analytical chemistry this kind of dialysis is applied
miniaturization of the membrane exchange area up for purifying, diluting, and conditioning the sample
to the micro- or the ultramicroscale enables repro- solutions. The dialysis module can be placed prior to
ducible sampling from quiescent or slowly flowing or in the sample insertion unit, between the sample
solutions to be performed. This is an essential aspect insertion unit and the reaction/separation zone and
for in vivo sampling with microdialytic probes. also into the detector zone. Figure 5A shows a typical
Figure 5 shows frequently used hollow-fiber and flow dialysis cell, which can be inserted in many on-
flat-membrane setups. line configurations with liquid chromatography and
flow injection analysis (FIA), as shown in Figure 6.
The Separation Membrane Two meander channels (depth: d ¼ 0.1–0.5 mm,
The dialytic transport of solute i through thin mem- width: b ¼ 1–2 mm) are separated by a membrane.
branes can be described by eqn [30]: The main advantages are: easy exchange of the
membrane and the use of very different membrane
dni materials. In a second version of dialysis cell (Figure
Ji ¼ ¼ kM Aðci;MD
ci;MA Þ ½30
dt 5B) a hollow-fiber membrane is concentrically placed
520 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis

Donor solution D

D
Membrane
Acceptor solution A
(A) (B)

A
Hollow-fiber membrane
Hollow-fiber membrane
D D

(C) (D)
Figure 5 Frequently applied dialysis setups. (A) Thin layer flow cell, (B) immersion membrane probe, (C) hollow-fiber membrane
module, and (D) immersing hollow-fiber membrane probe.

Table 1 Membrane transport and selectivity

Membrane material Transport mechanism Factors determining selectivity

Hydrophilic and electrically uncharged Diffusion trough micropores Sieve effect

(kM ¼ Dme/xdM)
Ion-exchange membranes Retarded diffusion through micropores Ion exchange, Donnan exclusion
Hydrophobic and microporous Gas diffusion and flow Volatility
As before but filled with organic solvent Diffusion through Micropores Solubility and chemical reaction
phase with and without reactants
Homogeneous membranes Solvation and diffusion Solubility in the membrane

Dm, molecular diffusion coefficient; e, membrane porosity; x, tortuosity of the pores; dM, thickness of the membrane.

inside a tube forming a thin-layer acceptor chamber. conditions of detection. The sensor can be calibrated
Higher mass transfer efficiencies are achieved with in situ by pumping standard solutions through the
respect to the membrane area. There is a growing immersion probe.
interest in dialysis immersion probes working either Figure 6 shows typical online dialysis configura-
with a small membrane window or a hollow-fiber tions. A continuously working dialysis cell can be
membrane (Figures 5C and 5D). Immersion dialysis coupled directly to the valve IV (Figure 6A) injecting
probes with integrated sensors, e.g., biosensors open the prepurified and conditioned sample solution into
up a way to adapt the sample solution to the sensor a nonsegmented carrier flow stream, e.g., of liquid
with respect to the determination range and the column chromatography. The analytes are separated
 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 521

P1 CC
D
DC
M

P2 IV
A
P4 LC-column MC
B
Flow-reactor
D
(A)

P3
D
DC
M

P2 IV LC-column MC
A
Flow-reactor
D
P3
Waste
(B)

S
P1 IV MC CC
D
DC
M

P2
A D
(C)

S
P1 IV MC CC
D

P2
A Detector

(D)
Figure 6 Continuous and pulsed dialysis in flow analytical setups. P1–P4, pumps; IV, injection valve; DC, thin layer dialysis cell;
M, separation membrane; S, sample solution; B, carrier solution; CC, compensation coil; MC, mixing coil.

from high molecular weight substances, e.g., proteins integrated detector can be used to increase the sen-
or from precipitates and microparticles. Blocking of sitivity and to shorten the analysis time.
the separation column is prevented and its life time is A very promising and even more expanding field of
prolonged. To improve the sensitivity, the transferred application was opened up more than 15 years ago
amount of the analyte can be increased by the loop- by the microdialysis technique, which is the most
dialysis setup shown in Figure 6B. The analyte is widely used dialysis technique in bioanalytical and
accumulated in the acceptor loop followed by injec- clinical chemistry. The main advantages are: in situ
tion into the detector channel D. To reduce the con- sampling, in situ calibration, and avoiding the influ-
tact time of sample solution with the separation ence of complex samples matrices on to the indicator
membrane, the setup shown in Figure 6C is used. The reaction. Table 2 summarizes the application areas.
probability of membrane fouling and clogging is de- Miniaturized dialysis probes with tip diameters
creased considerably. A dialysis cell (Figure 6D) with smaller than 1 mm are implanted into different
522 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis

Table 2 Application of microdialysis

Analyte

Neuroscience Glucose, L-lactate, L-glutamate and other amino acids, ascorbic acid, acetylcholine,
choline, NO
Clinical chemistry and Pharmacokinetics Glucose, L-lactate, drugs and their metabolites
Bioprocess analysis Glucose, L-lactate, D-lactate, ethanol, enzyme activities, peptides, proteins
Environmental analysis Aniline, 2-chloroaniline

RE

A RS
AE

Detector

DE

M M

(A) (B)
Figure 7 Microdialysis probes: (A) without detector; (B) with internal amperometric detector. DE, detector electrode; AE, auxiliary
electrode; RE, reference electrode; A, acceptor solution; RS, reagent solution.

tissues of living animals for sampling low molecular Selective Dialysis across Solid and Liquid
weight substances from the interstitial fluid. The Membranes
analyte is separated across small membrane win- The analyte transport through such membranes is
dows, e.g., of microporous cellulose acetate and po- based on a solvation/diffusion mechanism in a lipo-
lysulfone membranes with cutoffs between 1000 and philic phase. The liquid membranes have to be sup-
60 000 Da into a slowly flowing acceptor stream. The ported by a microporous and hydrophobic layer. The
microdialysis probes are coupled online to micro- flow separation cells shown in Figure 5 can be used
column LC systems, to capillary FIA setups and to to apply these membranes for separation procedures
capillary electrophoresis devices. Figures 7A and 7B that can be coupled online to flow analytical, liquid,
show a simple microdialysis probe and a probe with and gas chromatographic setups.
integrated amperometric detection, respectively. In In comparison to homogeneous membranes, e.g.,
the latter version, an enzyme solution can be used to of silicon rubber, the SLMs have the advantages of
catalyze a reaction generating a substance, e.g., faster membrane diffusion, and easier and wider
H2O2 or an oxidized redox mediator, which can be modification of the liquid phase, which determines
detected selectively and sensitively. Much shorter re- the transport mechanism and the selectivity. Further
sponse times are achieved in comparison to the on- advantages are the low amount of organic solvent
line coupling to external analytical setups. According and of extractants, low operating costs, easy auto-
to Hamberger et al. (1991) the solute concentration mation, and high enrichment factors. Dialysis across
cout at the outlet of microdialysis probes can be cal- SLMs has a wide and continuously growing field of
culated with eqn [31] with the sample concentration application in environmental analysis. Table 3 sum-
c, the membrane area A, the volumetric flow rate v marizes some applications. Three modes of separa-
and the overall mass transfer coefficient k, which tion are used:
depends on the mass transport resistances in the
sample tissue, the membrane, and the dialysate. 1. An electrical neutral substance diffuses from the
donor solution through the liquid membrane
cout ¼ cð1
exp½
kA=vÞ ½31 phase into the acceptor solution.
 MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 523

Table 3 Applications of supported liquid membranes

Analytes Conversion with Membrane Trapping by Detection

Mode A
Alcohols n-Heptane, PTFE GC

Mode B
Amines OH
n-Decane, supported by microporous PTFE Hþ GC
Phenols Hþ n-Dodecane, PTFE OH
LC, GC
Carboxylates Hþ n-Nonane, PVDF OH
LC
Thiolates Hþ n-Dodecane, PVDF OH
phot
Atrazine, Simazine pHp7 Dihexyl ether, PTFE H2SO4 MEKC
Caffeinec Neutral Dihexyl ether/n-undecane in PTFE H2SO4 phot
Nicotinec Neutral n-Undecane in polypropylene H2SO4 phot

Mode C
Al(III), Cd(II), Cu(II) pH 4.0 Di(2-ethylhexyl)phosphate in kerosene, PTFE pH ¼ 0.3 AAS
Nd(III) Weakly acidic As in former lines 0.1 mol l
1 HNO3 phot
Cu(II)a PAR n-Pentane containing di-2-ethylhexylphosphoric Hþ
acid, PVDF
Pb(II)b Anions Phenylhexane, containing bis(1- EDTA AAS
hydroxylheptylcyclohexano)-18-crown-6, PTFE
Cr(VII) pH 3.0 Aliquat 336 in tri-n-butyl-phosphate/kerosen, PTFE NaNO3 AdSV
a
Jönsson JA and Mathiasson L (1999) Trends in Analytical Chemistry 18: 318–334 and references cited therein; Barnes DE and van
Staden JF (1992) Analytica Chimica Acta 261: 441–451.
b
Izatt RM, Bruening RL, Bruening ML et al. (1989) Analytical Chemistry 61: 1140–1148.
c
Luque-Perez E, Rios A, Valcarcel M, Danielsson L-G, and Ingman F (1999) Laboratory Automation 34: 131–142; Idem (1999)
Analytica Chimica Acta 387: 155–164.
AAS, atomic absorption spectrometry; AdSV, adsorptive stripping voltammetry; Amp, amperometric; GC, gas chromatography; LC,
liquid chromatography; MEKC, micellar electrokinetic chromatography; PAR, 4-(20 -pyridylazo)-resorcinol; phot, photometric; PTFE,
polytetrafluoroethylene; PVDF, polyvinylidenedifluoride.

2. The analyte is converted into a membrane soluble separate aqueous solutions with very different pH
substance by pH shift or chemical reaction, which values and ionic strengths, which enables extreme
diffuses through the membrane and is trapped as a samples also to be adapted to primarily unsuitable
substance that is insoluble in the membrane. detection procedures. Microporous polytetrafluoro-
3. Co-ion-mediated transport on the basis of a car- ethylene or polypropylene membranes are used in
rier substance, which is dissolved in the liquid- most cases. However, it should be noted that, for
membrane phase. The carrier molecule takes up example, surfactants and many water-soluble organic
the analyte molecules or ions, whereby a hydro- compounds adsorb on the membrane surface, which
phobic complex or an ion-pair is formed. then becomes increasingly hydrophilized. In some of
such situations, homogeneous membranes, e.g., sili-
con–rubber membranes can be advantageous. It
should be noted, that silicon–rubber membranes are
Gas Dialysis permeable to hydrogen sulfide, hydrogen cyanide,
Gas dialysis is based on the diffusion of a volatile carbon dioxide, and many organic volatiles and
solute from the donor solution through a gas-filled they also have higher selectivity against other hydro-
membrane or a membrane in which the volatile sub- philic gases, e.g., NH3 and SO2 in comparison to
stance is soluble, into an acceptor solution. microporous membranes with a hydrophobic inner
By trapping a volatile analyte as a nonvolatile form surface.
these substances can strongly be enriched. Gas dial-
ysis is used in FIA procedures and other flow-analyt-
ical methods to enhance their selectivity for volatile
substances or substances, which can be converted
Reverse Osmosis
into volatiles. The configurations shown in Figures Despite its advantages, reverse osmosis is seldom
5A–5D are used and adapted. Table 4 summarizes used in analytical procedures. However, diluted sam-
the applications of the gas dialysis technique. Several ple solutions can be concentrated. Not only high
nonvolatile species, e.g., acetates can be separated molecular weight substances, but also low molecular
after acidification. Gas dialysis membranes can weight substances, are rejected by ultrafiltration
524 MEMBRANE TECHNIQUES / Ultrafiltration

Table 4 Applications of gas dialysis

Analyte Conversion to Trapping as or by Detection

Without conversion phot, cheml, cond,

pot, amp
Cl2, Br2, I2, ClO2, O3, H2O2, A color or chemiluminiscence reaction or reduction
NO, NO2 Oxidation cheml, pot
N2H4 Oxidation phot, cheml
Ethanol, methanol, Oxidation, enzymatic conversion phot, amp, fluor,
acetaldehyde, formaldehyde, cheml
acetic acid
Propylene oxide Hydrolysis, enzymatic conversion, oxidation fluor
Conversion by acid–base
reactions
CN
HCN CN
, Ag(CN)2
, 1-cyanoisoindole amp, pot, fluor
SCN
HSCN SCN
, color-forming reaction phot, pot
CO2, HCO3
, CO23
CO2 HCO3
phot, pot
NH3, NH4þ , RNH2 NH3, RNH2 NH4þ , RNH3þ , derivative of isoindole pot, pot, cond
HS
, H2S H2S HS
, S2
, color-forming reaction phot, pot, fluor
HSO
3 , SO3
2
SO2 HSO3
, color-forming reaction pot, coul, phot,
fluor, cheml
F
HF F
phot, pot
Conversion by redox reactions
Cl
, Br
, I
Cl2, Br2, I2 Reduction to Cl
, Br
, I
phot, pot, amp
OCl
, ClO2
, ClO3
,
BrO3

Phot, photometry; cheml, chemiluminescence; cond, conductivity; pot, potentiometry; amp, amperometry; fluor, fluorimetric detection.

membranes. The typical application of reverse os- See also: Membrane Techniques: Ultrafiltration; Liquid
mosis is the separation of low molecular weight Membranes; Pervaporation.
substances from aqueous solutions to purify water
or to concentrate the substances that are to be Further Reading
determined. The water is propelled by a relatively Jönsson JA, Lövquist P Audunsson, and Nilvé G (1993)
high pressure gradient through a membrane, which is Mass transfer kinetics for analytical enrichment and
permeable to water but rejects dissolved molecules sample preparation using supported liquid membranes in
and ions. Bundles of hollow-fiber membranes are a flow system with stagnant acceptor liquid. Analytica
used in most technical applications, e.g., to desalt Chimica Acta 277: 9–24.
seawater. Jönsson JA (2002) Liquid membrane techniques. In: Pawl-
Highly diluted sample solutions can be concen- yszyn J (ed.) Comprehensive Analytical Chemistry, vol.
trated to analyte concentrations, which can be XXXVII, pp. Amsterdam: Elsevier Science.
determined by the available determination method. Robinson T and Justice JB (1991) Microdialysis in the Ne-
urosciences. New York: Elsevier Science.
The analyte can theoretically be concentrated up
Torto N, Laurell Th, Gorton L, and Marko-Varga G (1999)
to the precipitation level. Then an additional filter
Analytica Chimica Acta 379: 281–305.
layer is used, which is exchanged and directly Ungerstedt U (1986) Microdialysis – a new bioanalytical
analysed, e.g., by X-ray fluorescence spectrometry. sampling technique. Current Separations 7: 43–46.
For example, transition metals could be analysed Valcarcel M and Luque de Castro MD (1991) Nonchro-
in drinking water up to the micrograms per liter matographic Continuous Separation Techniques. Camb-
level. ridge: Royal Society of Chemistry.

Ultrafiltration
B Spivakov and V Shkinev, Russian Academy of Introduction
Sciences, Moscow, Russia
The use of ultrafiltration (UF), microfiltration (MF),
& 2005, Elsevier Ltd. All Rights Reserved. and other filtration techniques using semipermeable