MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 515
Muhammad WT, Tabb DL, Fox KF, and Fox A (2003)
Automated discrimination of polymerase chain reaction
products with closely related sequences by software-
based detection of characteristic peaks in product ion
spectra. Rapid Communications in Mass Spectrometry
16: 1–8.
Muddiman DC, Null AP, and Hannis JC (1999) Precise
mass measurement of a double stranded 500 base-pair
(309 kDa) polymerase chain reaction product by negative
ion electrospray ionization Fourier transform ion cyclo-
tron resonance mass spectrometry. Rapid Communica-
tions in Mass Spectrometry 13: 1201–1204.
Naito Y, Ishikawa K, Koga Y, et al. (1995) Molecular mass
measurement of polymerase chain reaction products am-
plified from human blood DNA by electrospray ioniza-
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
Dialysis and Reverse Osmosis
U Spohn, Martin-Luther Universitat Halle-Wittenberg,
Halle, Germany
& 2005, Elsevier Ltd. All Rights Reserved.
Introduction
Dialysis is a separation process with many applica-
tions in clinical, biochemical, and environmental
tion mass spectrometry. Rapid Communications in Mass
Spectrometry 9: 1484–1486.
Oefner PJ and Huber CG (2002) A decade of high-reso-
lution liquid chromatography of nucleic acids on sty-
rene–divinylbenzene co-polymers. Journal of
Chromatography B 782: 27–55.
Walters JJ, Fox KF, and Fox A (2002) Mass spectrometry
and tandem mass spectrometry, alone or after liquid
chromatography, for analysis of polymerase chain reac-
tion products in the detection of genomic variants. Jour-
nal of Chromatography B 782: 57–66.
Yiang Y and Hofstadler SA (2003) A highly efficient and
automated method of purifying and desalting PCR prod-
ucts by electrospray ionization mass spectrometry. Ana-
lytical Biochemistry 316: 50–57.
analysis. Donor and acceptor solutions are separated
by a membrane, which is permeable to one or more
solutes. When the solutions have different solute
activities, a diffusional transport from the higher to
the lower activity a (a ¼ cf , where c is the concen-
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
or eliminating small ones.
Different solvent activities generate an osmotic
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-
I
C pled with other equilibria. Without coupled reac-
II
D dM
A
Figure 1 Dialysis between quiescent (I) and stirred or flowing
solutions (II) solutions. C, concentration; D, donor solution; A,
acceptor solution; M, membrane; dM, thickness of the membrane;
dA and dD , thicknesses of the boundary layers.
of the lower solvent activity. This process is termed
osmosis. Reverse osmosis is the process during which
an outer pressure is applied to force the solvent
through a membrane, which rejects the solute.
Reverse osmosis is used almost exclusively to desalt
and purify water. In the ideal case, the separation
membrane is only permeable to water.
Thermodynamics
The difference between the chemical activities of the
solute i is the precaution for its diffusional transport
through the separation membrane. The free enthalpy
DG of diffusion can be calculated from the difference
between the chemical potentials mi;A and mi;D of the
solute i in the acceptor (A) and donor solution (D),
respectively (eqn [1]). moi;D and moi;A are the standard
chemical potentials,
DG ¼ mi;D
mi;A ¼ moi;D
moi;A þ RT lnðai;D =ai;A Þ
The equilibrium constant Ki depends on the activity
coefficients fi;A and fi;D , the concentrations ci;A and
ci;D , and the absolute temperature T according to eqn
[2]. R is the molar gas constant. Ki is given as
 o 
ai;A fi;A  ci;A mi;D
moi;A
Ki ¼ ¼ ¼ exp
ai;D fi;D  ci;D RT
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
compositions and/or the dialysis equilibrium is cou-
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-
X spectively. VA and VD are the volumes of the
corresponding solutions. Without trapping reaction
in the acceptor solution, during which the received
analyte is converted into a substance that cannot
permeate the membrane, the enrichment E approach-
es 0.5 for VA ¼ VD. If the activity coefficients are
equal (i.e., fi;A ¼ fi;D ) in the equilibrium state, E will
be 0.5. Also the chemical activities of the solvent S
are equal at dialysis equilibrium. Because
mS;D ¼ mS;A ½6
and
moS;D ¼ moS;A ½7
The thermodynamic equilibrium constant KS is given
as
ax;S;A
KS ¼ exp½ðVmS;D pD
VmS;A pA Þ=RT ¼ ½8
ax;S;D
where VmS;D and VmS;A are the partial molar volumes
of the solvent, which are equal to the VmS for dilute
solutions. pD and pA refer to the corresponding
osmotic pressures. ax;S;A and ax;S;D are the activities
of the solvent with respect to its mole fraction xS
in the acceptor and donor solutions, respectively. It
follows that
½1
KS ¼ exp½ðpD
pA ÞVmS =RT ½9
The resulting pressure difference p ¼ pD
pA can
be calculated according to eqn [10]:
p ¼
ðRT=VmS Þln ax;S;A for ax;S;D ¼ 1 ½10
This pressure difference causes a solvent flow
½2
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

pD
D
ci,DM
ci,D
JL
J ii
pA
D
Ci,A

C dM dS
Figure 4 Reverse osmosis with concentration polarization on
the asymmetric separation membrane. Ji , mass flux of the solute
i; pD , outer pressure from the donor side; pA , outer pressure from
the acceptor side; pA and pD , osmotic pressure in the acceptor
and donor chamber, respectively; dM and dS , thickness of the
membrane layer and the membrane supporting layer, re-
spectively; dC , thickness of the polarization layer; ci;DM , ci;A ,
ci;D , concentration of the solute i in the acceptor solution, in the
donor solution, and at the separation membrane, respectively.
calculated according to eqn [29]:
ci;D VD;o
E¼ ¼ ½29
ci;Do VD;o
VA
where VD;o is the initial volume of the donor
solution.
Geometric Aspects
The geometric shape and volume both of the donor
and the acceptor chambers as well as of the separa-
tion membrane have an essential influence on the
duration of the separation. To minimize the separa-
tion time, the thickness of the donor solution layer
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
factor for dialysis with enhanced selectivity, e.g., gas
dialysis, the volume ratio between the donor solution
and the acceptor solution has to be maximized. The
miniaturization of the membrane exchange area up
to the micro- or the ultramicroscale enables repro-
ducible sampling from quiescent or slowly flowing
solutions to be performed. This is an essential aspect
for in vivo sampling with microdialytic probes.
Figure 5 shows frequently used hollow-fiber and
flat-membrane setups.
The Separation Membrane
The dialytic transport of solute i through thin mem-
branes can be described by eqn [30]:
dni
Ji ¼ ¼ kM Aðci;MD
ci;MA Þ
dt
MEMBRANE TECHNIQUES / Dialysis and Reverse Osmosis 519
where ci;MD and ci;MA are the solute concentrations in
the membrane at the interfaces between donor and
acceptor solutions, respectively. The separation
membrane is chosen with respect to its selectivity
and mass transfer kinetics. The membrane material
determines the transport mechanism. Table 1 gives
an overview about membrane materials, their mod-
ifications, and the dominant transport mechanism. In
most cases the selectivity is based on the sieve effect
of the membrane pores. The dialysis across gas-filled
membranes, ion-exchange membranes, or supported
liquid membranes (SLMs), the pores of which are
filled with organic solvents or solvent mixtures with
and without additives, enables the enrichment of the
analyte to be detected. The selectivity of SLM tech-
niques is enhanced by the addition of selectively re-
acting ligands to the liquid membrane phase. When
charged ions are complexed and transported through
such membranes electroneutrality must be main-
tained. In some cases ion pairs with selected coun-
terions are transported through the liquid membrane
phase. When a binding ligand is dissolved in this
phase and the counterion cannot transverse the
membrane, the analyte ion transport is coupled with
back-diffusion of an ion from the acceptor solution.
A similar situation occurs in ion-exchange mem-
branes, which are used to enrich ions by Donnan
dialysis.
Using microporous membranes with a hydropho-
bic inner surface, the selectivity of gas dialysis
against other volatiles results predominately from
the ratio of the partial pressure of the analyte pi to
the total pressure. In homogeneous membranes, the
different solubilities of the gases in the membrane
material are the main selecting factor.
Applications
Dialysis through Microporous Membranes
In analytical chemistry this kind of dialysis is applied
for purifying, diluting, and conditioning the sample
solutions. The dialysis module can be placed prior to
or in the sample insertion unit, between the sample
insertion unit and the reaction/separation zone and
also into the detector zone. Figure 5A shows a typical
flow dialysis cell, which can be inserted in many on-
line configurations with liquid chromatography and
flow injection analysis (FIA), as shown in Figure 6.
Two meander channels (depth: d ¼ 0.1–0.5 mm,
width: b ¼ 1–2 mm) are separated by a membrane.
The main advantages are: easy exchange of the
membrane and the use of very different membrane
materials. In a second version of dialysis cell (Figure
½30
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

Ion-exchange membranes
Hydrophobic and microporous
As before but filled with organic solvent
phase with and without reactants
Homogeneous membranes
(kM ¼ Dme/xdM)
Retarded diffusion through micropores
Gas diffusion and flow
Diffusion through Micropores
Solvation and diffusion
Ion exchange, Donnan exclusion
Volatility
Solubility and chemical reaction
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.
Higher mass transfer efficiencies are achieved with
respect to the membrane area. There is a growing
interest in dialysis immersion probes working either
with a small membrane window or a hollow-fiber
membrane (Figures 5C and 5D). Immersion dialysis
probes with integrated sensors, e.g., biosensors open
up a way to adapt the sample solution to the sensor
with respect to the determination range and the
conditions of detection. The sensor can be calibrated
in situ by pumping standard solutions through the
immersion probe.
Figure 6 shows typical online dialysis configura-
tions. A continuously working dialysis cell can be
coupled directly to the valve IV (Figure 6A) injecting
the prepurified and conditioned sample solution into
a nonsegmented carrier flow stream, e.g., of liquid
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
or from precipitates and microparticles. Blocking of
the separation column is prevented and its life time is
prolonged. To improve the sensitivity, the transferred
amount of the analyte can be increased by the loop-
dialysis setup shown in Figure 6B. The analyte is
accumulated in the acceptor loop followed by injec-
tion into the detector channel D. To reduce the con-
tact time of sample solution with the separation
membrane, the setup shown in Figure 6C is used. The
probability of membrane fouling and clogging is de-
creased considerably. A dialysis cell (Figure 6D) with
integrated detector can be used to increase the sen-
sitivity and to shorten the analysis time.
A very promising and even more expanding field of
application was opened up more than 15 years ago
by the microdialysis technique, which is the most
widely used dialysis technique in bioanalytical and
clinical chemistry. The main advantages are: in situ
sampling, in situ calibration, and avoiding the influ-
ence of complex samples matrices on to the indicator
reaction. Table 2 summarizes the application areas.
Miniaturized dialysis probes with tip diameters
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
weight substances from the interstitial fluid. The
analyte is separated across small membrane win-
dows, e.g., of microporous cellulose acetate and po-
lysulfone membranes with cutoffs between 1000 and
60 000 Da into a slowly flowing acceptor stream. The
microdialysis probes are coupled online to micro-
column LC systems, to capillary FIA setups and to
capillary electrophoresis devices. Figures 7A and 7B
show a simple microdialysis probe and a probe with
integrated amperometric detection, respectively. In
the latter version, an enzyme solution can be used to
catalyze a reaction generating a substance, e.g.,
H2O2 or an oxidized redox mediator, which can be
detected selectively and sensitively. Much shorter re-
sponse times are achieved in comparison to the on-
line coupling to external analytical setups. According
to Hamberger et al. (1991) the solute concentration
cout at the outlet of microdialysis probes can be cal-
culated with eqn [31] with the sample concentration
c, the membrane area A, the volumetric flow rate v
and the overall mass transfer coefficient k, which
depends on the mass transport resistances in the
sample tissue, the membrane, and the dialysate.
cout ¼ cð1
exp½
kA=vÞ
Selective Dialysis across Solid and Liquid
Membranes
The analyte transport through such membranes is
based on a solvation/diffusion mechanism in a lipo-
philic phase. The liquid membranes have to be sup-
ported by a microporous and hydrophobic layer. The
flow separation cells shown in Figure 5 can be used
to apply these membranes for separation procedures
that can be coupled online to flow analytical, liquid,
and gas chromatographic setups.
In comparison to homogeneous membranes, e.g.,
of silicon rubber, the SLMs have the advantages of
faster membrane diffusion, and easier and wider
modification of the liquid phase, which determines
the transport mechanism and the selectivity. Further
advantages are the low amount of organic solvent
and of extractants, low operating costs, easy auto-
mation, and high enrichment factors. Dialysis across
SLMs has a wide and continuously growing field of
application in environmental analysis. Table 3 sum-
marizes some applications. Three modes of separa-
tion are used:
1. An electrical neutral substance diffuses from the
donor solution through the liquid membrane
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
substance by pH shift or chemical reaction, which
diffuses through the membrane and is trapped as a
substance that is insoluble in the membrane.
3. Co-ion-mediated transport on the basis of a car-
rier substance, which is dissolved in the liquid-
membrane phase. The carrier molecule takes up
the analyte molecules or ions, whereby a hydro-
phobic complex or an ion-pair is formed.
Gas Dialysis
Gas dialysis is based on the diffusion of a volatile
solute from the donor solution through a gas-filled
membrane or a membrane in which the volatile sub-
stance is soluble, into an acceptor solution.
By trapping a volatile analyte as a nonvolatile form
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
into volatiles. The configurations shown in Figures
5A–5D are used and adapted. Table 4 summarizes
the applications of the gas dialysis technique. Several
nonvolatile species, e.g., acetates can be separated
after acidification. Gas dialysis membranes can
separate aqueous solutions with very different pH
values and ionic strengths, which enables extreme
samples also to be adapted to primarily unsuitable
detection procedures. Microporous polytetrafluoro-
ethylene or polypropylene membranes are used in
most cases. However, it should be noted that, for
example, surfactants and many water-soluble organic
compounds adsorb on the membrane surface, which
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
permeable to hydrogen sulfide, hydrogen cyanide,
carbon dioxide, and many organic volatiles and
they also have higher selectivity against other hydro-
philic gases, e.g., NH3 and SO2 in comparison to
microporous membranes with a hydrophobic inner
surface.
Reverse Osmosis
Despite its advantages, reverse osmosis is seldom
used in analytical procedures. However, diluted sam-
ple solutions can be concentrated. Not only high
molecular weight substances, but also low molecular
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-
mosis is the separation of low molecular weight
substances from aqueous solutions to purify water
or to concentrate the substances that are to be
determined. The water is propelled by a relatively
high pressure gradient through a membrane, which is
permeable to water but rejects dissolved molecules
and ions. Bundles of hollow-fiber membranes are
used in most technical applications, e.g., to desalt
seawater.
Highly diluted sample solutions can be concen-
trated to analyte concentrations, which can be
determined by the available determination method.
The analyte can theoretically be concentrated up
to the precipitation level. Then an additional filter
layer is used, which is exchanged and directly
analysed, e.g., by X-ray fluorescence spectrometry.
For example, transition metals could be analysed
in drinking water up to the micrograms per liter
level.
See also: Membrane Techniques: Ultrafiltration; Liquid
Membranes; Pervaporation.
Further Reading
Jönsson JA, Lövquist P Audunsson, and Nilvé G (1993)
Mass transfer kinetics for analytical enrichment and
sample preparation using supported liquid membranes in
a flow system with stagnant acceptor liquid. Analytica
Chimica Acta 277: 9–24.
Jönsson JA (2002) Liquid membrane techniques. In: Pawl-
yszyn J (ed.) Comprehensive Analytical Chemistry, vol.
XXXVII, pp. Amsterdam: Elsevier Science.
Robinson T and Justice JB (1991) Microdialysis in the Ne-
urosciences. New York: Elsevier Science.
Torto N, Laurell Th, Gorton L, and Marko-Varga G (1999)
Analytica Chimica Acta 379: 281–305.
Ungerstedt U (1986) Microdialysis – a new bioanalytical
sampling technique. Current Separations 7: 43–46.
Valcarcel M and Luque de Castro MD (1991) Nonchro-
matographic Continuous Separation Techniques. Camb-
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