Desalination 241 (2009) 315 330

Studies on the role of site-binding and competitive adsorption

in determining the charge of nanofiltration membranes

Luigi Bruni, Serena Bandini*

Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali,
Alma Mater Studiorum * University of Bologna, Via U. Terracini, 28, I-40131, Bologna, Italy
Tel. +39 051 2090231; Fax +39 051 2090247; email: serena.bandini@mail.ing.unibo.it; serena.bandini@unibo.it
Received 10 September 2007; revised 19 December 2007; accepted 26 December 2007

Abstract
The “adsorptionamphoteric” model is used to investigate the role of the main phenomena determining the
mechanism of the membrane charge formation in nanofiltration membranes. The prevailing mechanisms considered
are: acid/base dissociation of the hydrophilic groups of the membrane, counter-ion site-binding on dissociated
hydrophilic sites and competitive adsorption of ions on the hydrophobic groups of the membrane. The total
membrane charge is given by the contribution of a proper charge, which is screened by the dissolved ions giving
rise to site-binding phenomena, and by the contribution of an adsorption charge located on the hydrophobic sites.
Aqueous solutions containing single symmetric (1:1, 2:2) as well as non-symmetric (1:2, 2:1) electrolytes are
studied, by a simulation of the performances of a polyamide Desal-type membrane, taken as a reference, as a
function of pH and salt concentration. The role of counter-ion site-binding on the total membrane charge is
investigated in comparison with competitive adsorption. A sensitivity analysis is performed in which the overall
effect of competitive adsorption is studied.
With symmetric salts, the membrane charge is determined by the competitive adsorption on hydrophobic sites.
With non-symmetric salts, on the contrary, the behaviour of the total volume membrane charge as a function of salt
concentration is given by the relative effects of counter-ion site-binding vs. competitive adsorption.
Keywords: Site-binding; Competitive adsorption; Nanofiltration; Electrolytes; Membrane charge; Polyamide
membranes

*Corresponding author.

Presented at the Third Membrane Science and Technology Conference of Visegrad Countries (PERMEA), Siofok,
Hungary, 2–6 September 2007.

0011-9164/09/$– See front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2007.12.055
316 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330
1. Introduction
Filtration characteristics of nanofiltration
(NF) membranes with electrolyte solutions are
greatly affected by the electrochemical proper-
ties of the membrane surfaces which depend on
membrane material as well as on operative
conditions such as feed pH, type and concentra-
tion of ionic species.
It is experimentally recognized that the role
of electrolyte is remarkable in determining the
separation performances of polymeric mem-
branes as well as of inorganic membranes.
Different trends have been observed for the
rejection of symmetric and non-symmetric salts,
as a function of feed ionic strength. In the former
case, rejection generally decreases as the con-
centration increases at constant pH values [1
5].
In the latter case, on the contrary, different
reversed trends are obtained [1
3,6
10]: poly-
amide membranes rejection greatly increases as
the concentration increases; with Desal 5-DK
membranes in the case of CaCl2-water solutions,
a maximum rejection value was obtained as
the salt concentration increases, at constant
pH [9,10].
The typical characterization procedures by
electrokinetic measurements of streaming poten-
tial [11
17] put clearly in evidence that the
physical
chemical interactions of multivalent
ions with the membrane are stronger with respect
to what obtained with univalent electrolytes. In
the case of CaCl2
water solutions, calcium
binding on ionized sites of the membrane
appears so remarkable that zeta-potentials switch
from negative to positive values as the concen-
tration increases and the points of zero charge
are greatly affected by the salt concentration, as
it was obtained by Teixeira et al. [15] with
polyamide NFT50 membranes.
The behaviours observed with electrolyte

water solutions can be explained accounting the
relevant role of a superficial membrane charge
which is typically related to the membrane
material and it is strictly dependent on pH, as
well as on the type and on the concentration of
electrolytes. Generally speaking, most of NF
membranes show amphoteric behaviour: value
and sign of the membrane charge are the macro-
scopic result of ionic adsorption on the pore walls
which are endowed with a sort of a fixed charge
proper of the functional groups existing on the
membrane [14,17
25].
The question of modelling the mechanism of
membrane charge formation is well-known for
many years and it must be kept separated from
the question of modelling partitioning and
transport mechanisms within the membrane
pore. In various partitioning
transport models,
the volume membrane charge could be assumed
(and it really was) as an adjustable parameter to
be calculated exclusively by fitting rejection data
through the equations of the same models
[3,4,6,7,9
11,26
31]. Bowen et al. [26,27] con-
sidered the negative membrane charge as an
increasing empirical function with the feed
electrolyte concentration, according to a Freun-
dlich-type isotherm, which was independent of
the electrolyte type and did not contain any pH
effect. In Ref. [7], authors demonstrated that this
very simple interesting model was very good in
the case of single salts as well as in the case of
some multicomponent mixtures, for some kinds
of membranes, whereas it failed in the case of
CaCl2
water solutions with Desal DK mem-
branes, as an example, for which a negative
membrane charge was obtained as a decreasing
function with the salt concentration. That result
is absolutely independent of the assumptions
performed to describe ionic partitioning at the
feed/membrane interface: either considering
Donnan equilibrium as the prevailing mechan-
ism [3,32] or accounting also dielectric exclusion
effects [7], the same opposite behaviours can be
obtained for the membrane charge as a function
of the salt concentration in the case of NaCl and
CaCl2 (or MgCl2) water solutions, respectively.
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330
Understanding the correct mechanism of
membrane charge formation is indeed the key
point to solve. Some authors proposed to solve
the problem through the calculation of the
surface membrane charge as a function of the
feed ionic strength and pH through the elabora-
tion of zeta-potential data, according to simple
fittings [11,14,33] or to semi-empirical models
[14]. Other authors [17
21,34] developed
physical
chemical models to describe the
mechanism of charge formation, with reference
to simple specific cases. The crucial problem of
all those models can be identified in the fact that
they collect and classify as generic adsorption all
the types of chemical
physical interactions
between the membrane materials and the dis-
solved ions. However, the behaviour observed
with calcium ions cannot be explained without
accounting the competitive adsorption phenom-
ena separately from the screening effects of the
membrane proper charge. To this purpose,
Bandini et al. [22
24] developed the
“adsorption
amphoteric model” (ADS-AMF)
to describe the mechanism of charge formation
in polyamide membranes. The model introduces
a site-representation of the membrane as the sum
of hydrophobic as well as of hydrophilic groups
which can support charges derived from various
chemical and physical mechanisms, such as acid/
base dissociation, counter-ion site-binding and
competitive adsorption. The most innovative
aspects of the model are essentially related to
its structure. Basing on the assumption of three
prevailing phenomena, the model is able to
describe in a simple manner very different
membrane charge behaviours with salt concen-
tration and pH existing for various electrolyte
types; it is also able to predict amphoteric
behaviours which sometimes are observed
depending on pH as well as on the electrolyte
concentration. In addition, the model allows
investigating the contribution of each mechan-
ism involved as a function of the operative
317
conditions, so that the controlling mechanism
determining the membrane charge can be put in
evidence. Finally, the model can be used to get
an analytical relationship for the membrane
charge as a function of salt concentration and
pH, which can be used to interpret charge data
obtained from very different measurement tech-
niques (both from direct measurements such as
streaming potential data and from indirect
measurements such as the elaboration of rejec-
tion data by transport models). Alternatively, the
relationship can be inserted in a transport model
in which the membrane charge can be consid-
ered either as a function of the local salt
concentration inside the pore or as an uniform
charge in the volume depending on the salt
concentration and pH in the feed bulk.
The ability of the ADS-AMF model has been
tested by the authors on Desal-5 DK membranes
with NaCl as well as with CaCl2
water solutions
[24,25], starting from volume membrane charge
data obtained from the elaboration of experi-
mental rejections by the Donnan Steric Pore
Model and Dielectric Exclusion [4,9,10], in
which all the partitioning effects related to the
membrane charge are assumed as located at the
feed/membrane interface.
In this paper, after a synthetic description of
the basic equations, the model is used as a
predictive tool to investigate the effect of
counter-ion site-binding in comparison with
competitive adsorption, at various operative
conditions. In addition, a sensitivity analysis is
performed in which the role of competitive
adsorption is investigated. The paper is the
natural continuation of the investigation pre-
sented in [25] and it represents a synthesis of the
studies performed. Aqueous solutions containing
single symmetric (1:1, 2:2) and non-symmetric
(1:2, 2:1) electrolytes are considered; a poly-
amide Desal-type membrane is taken as a
reference membrane, by assuming as character-
istic parameters of the polymeric material quite
318 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330

similar values to those calculated for Desal-5 DK modelled as the sum of two different groups of
membranes. Main purpose of this paper is to sites: the group of hydrophilic functional sites
show that various different behaviours may exist (R1H) and the group of hydrophobic functional
of the function membrane charge versus the salt sites (RH).
concentration and pH and that the ADS-AMF When an NF membrane is immersed in an
model allows discussing the relative role of the aqueous electrolyte solution at a well defined pH
phenomena in determining the corresponding value, it can assume a surface charge owing to a
overall macroscopic effect. simultaneous acid/base dissociation of the hydro-
philic functional groups. The simultaneous pre-
2. Theory sence of positively and negatively charged
groups on the membrane surface gives rise to
The ADS-AMF model has been developed in electrostatic interaction phenomena between the
a rough version in [22,23] and it has been widely surface and the dissolved ions. This phenomenon
revised in Ref. [24], in which the basic features is known as counter-ion site-binding and it can be
and equations are described in detail; key points classified as a sort of ionic adsorption on the
are reported hereafter for clarity sake. membrane surface mainly related to electrostatic
A schematic representation of the ADS-AMF interactions. In addition, ionic adsorption can
model is reported in Fig. 1 with reference to occur on the membrane surface owing to non-
NaCl
water solutions. The active part of the electrostatic interactions; indeed some authors
polymer involved in the charge formation is widely recognize that preferential adsorption of
Diffuse layer anions is most likely on hydrophobic surfaces, in
view of their lower hydration radii [12,35]. We
ϕ0 ψ ϕfb
classify this latter type of interaction as compe-
RH
H+
titive adsorption between positive and negative
R1– Na
+

OH- Cl- ions occurring on the hydrophobic functional

Cl-
Membrane polymer

RH
H+ groups of the membrane [24].
R1H Na+
Cl- Cl-
Basically, in the ADS-AMF model the pre-
Liquid bulk

RH -
Cl
RH – H+ Na+
Na+
+
R1 Cl-
+
Na
+ +
H OH H Cl
-
- vailing mechanisms determining the membrane
R1H2 Cl- Na+
+
Cl- Na+
charge formation are accounted by:
RH Na Cl- H+
+ - Cl-
R1H2 Cl
H+ OH H+
-

R1H Na+ i acid/base dissociation of hydrophilic func-

RH Cl- Na+ Cl-
tional sites R1H;
R1H
X RH Na+ Cl- Na+ ii counter-ion site-binding on dissociated
RH
hydrophilic sites;
Adsorbed ions
iii competitive adsorption of anions and
RH = hydrophobic sites R1H = hydrophilic sites cations on hydrophobic functional sites RH.

Fig. 1. ADS-AMF model: site representation of a NF Acid/base dissociation gives rise to the proper
membrane and the electric double layer at a generic
charge of the membrane, which undergoes
interface between the membrane and the feed liquid
phase, with reference to NaCl
water solutions in the counter-ion screening owing to site-binding
acidic pH range. “Adsorption complexes” (RHCl, effects.
RHNa ) and “ion-pairs” (/R1 Hþ   þ
2 Cl , /R1 Na ) are
Competitive adsorption and counter-ion site-
marked. binding can occur simultaneously in the electric
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330 319

double layer (EDL) close to the membrane/liquid Since the reactions occur on the membrane
interface. From a general point of view, ions are surface, the corresponding chemical equilibrium
located very close to the membrane surface at relationships can be obtained straightforwardly
their corresponding planes; for simplicity, in the (Eq. (2), Table 1). The development of those
ADS-AMF model, the planes at which the ions equations was performed by a rigorous thermo-
are located as “adsorbed” ions are considered dynamic approach and it has been reported
coincident and c is the overall electric potential
value existing at the “adsorption” plane (Fig. 1). Table 1
In principle, the local membrane charge can be Basic equations of ADS-AMF model
assumed as the complementary part of the diffuse
layer charge in the EDL close to the membrane/ Acid/base dissociation
liquid interface, along the membrane pore as well
/R1 H þ Hþ ¼ R1 Hþ 2 (1.1)
as at the membrane/feed interface. In the follow- R1 H ¼ R þ
/
1 þH (1.2)
ing, we will assume as a simplification that the fb 800
/K c
B R1 H cHþ e ¼ ctot
R1 Hþ (2.1)
chemical and physical effects determining the
fb 80  2
tot
membrane charge are due to the interactions /K c
A R1 H = c Hþ e 0 ¼ c R (2.2)
1

mainly located at the feed/membrane interface.

Counter-ion site-binding
That hypothesis is also supported by all the
streaming potential measurements performed by /R1 þM
zþ
¼ ðR 1M Þ
zþ
(1.3)
þ
now, which put in evidence that an EDL occurs /R H
1 2 þX
z
¼ ðR1 Hþ 2X Þ
z
(1.4)
close to the feed/membrane interface which is cðR Mzþ Þ 00
/
1
fb
¼ kþSB ezþ 8 (2.3)
responsible for the formation of a surface mem- cR cMzþ
1
brane charge. The simplification is substantially cðR1 Hþ X z Þ 0
/
2
¼ kSB ez 8 (2.4)
coherent with the assumption of some transport cR1 Hþ cfb
X z
2
models, such as the Donnan Steric Pore Model
and Dielectric Exclusion [7] or modifications of Competitive adsorption
that [6,36], which consider the volume charge
/RH þ Mzþ ¼ RHMzþ (1.5)
uniform in the membrane and mainly related to
/RH þ X  ¼ RHX 
z z
(1.6)
the equivalent concentration existing in the feed cRHMzþ 0
/ ¼ kþADS ezþ c (2.5)
bulk. Of course, in the general case, the mem- cRH cfb
Mþ z

brane charge could be considered as a function of cRHX z 0

/ ¼ kADS ez c (2.6)
the local concentration inside the pore; however, cRH cfbz
X 

owing to the small dimensions of pore radii, in which

 
superposition of the EDL can occur and the DG0ADS
kADS ¼ exp 
/ cRS;
location of the adsorption planes might be very 
RT
.
DG0SB
difficult to determine. /k
SB ¼ exp  RT cRS
With reference to an aqueous solution con-
F F
taining a single strong electrolyte (generally c0 ¼ ðc  8fb Þ; /800 ¼ ð8  8fb Þ;
RT 0
/
RT
indicated as M
þ X
 ¼
þ M zþ þ
 X z ), making
/

0 F
SB  F
SB 
use of the pseudo-chemical reaction approach /8 ¼ 8  8fb ; /800 ¼ 8  8fb ;
[24], the phenomena involved in the membrane RT  RT þ
SB 1
charge formation can be described by the /8
 ¼ cþ 8
jz j 0
reactions set reported in Table 1 as Eq. (1).
 320 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330

extensively in [24]; the main features of those accounting for the screening effect of the proper
equations are related to the fact that (i) all the charge by the dissolved ions. RHMzþ and RHX z
/ /

concentration values on the surface can be indicate physical
chemical complexes taking into
related to the corresponding feed bulk values account the interaction between the membrane
by a Boltzmann-type distribution, (ii) all the surface and the adsorbed ions which are located
parameters assume a physical meaning (as it at a plane close to the membrane (Fig. 1). R 1 /

is reported in the Notation). and R1 Hþ

Assuming the total concentration of the
chargeable hydrophilic (X1MAX) and hydropho-
bic (XMAX) sites as constant values, the follow-
ing relationships can be obtained, in which the
concentration of each site is accounted:
/
2 represent the unbound dissociated
sites; R1H and RH are the undissociated hydro-
philic sites and the uncharged hydrophobic sites,
respectively.
Finally, under the hypothesis that each ionic
species can bind only on one available site,
the net negative total volume charge (X) can /

X1MAX ¼ cR1 H þ ctot

R1
þ ctot
R1 Hþ be obtained as the algebraic combination of
2

¼ cR1 H þ cR1 þ cR1 Hþ2 þ cðR Mzþ Þ each site supporting a charge according to
1
Eq. (5):
þ cðR1 Hþ X z Þ ð3Þ
2
X ¼ ðXFIX þ XADS Þ
XMAX ¼ cRH þ cRHMzþ þ cRHX z ð4Þ h

¼ cR1  cR1 Hþ2  zþ  1 cðR Mzþ Þ
1
/ ctot
R1 H þ
and ctot
/
R
1
represent the total concentrations i
2
of the dissociated hydrophilic sites and can be ðz þ 1ÞcðR1 Hþ X z Þ
2
obtained from Eqs. (2.1) and (2.2) in Table 1,
respectively; their relative value determine the þ z cRHX z  zþ cRHMzþ  ð5Þ
value and the sign of the proper charge.
/ ðR zþ
/
þ z
1 M Þ and ðR1 H2 X Þ indicate the bound Eq. (2) * Table 1, in association with
cation and anion, located close to the membrane Eqs. (3)
(5), can be finally solved to obtain a
(Fig. 1); they are a sort of physical
chemical general relationship describing the total volume
complex, often called “ion-pairs” [37,38], which membrane charge as reported in Eq. (6) which
represent the counter-ion site-binding phenomenon synthetically represents the ADS-AMF model in

X1MAX
X ¼ ðXFIX þ XADS Þ ¼
fb 8 0
 0
1 þ KA = cHþ e 0 þ KB cfb Hþ
e80
"
0 
KA = cfb
Hþ
e80
zþ 800 fb

 1  ðz þ  1Þk þSB e c M zþ
1 þ kþSB ezþ 8 cfb
00
M zþ
#


0
KB cfb
Hþ
e80 z 80 fb
 1 þ ðz þ 1ÞkSB e cX z
1 þ kSB ez 80 cfb
X z

0
zþ c0 fb

XMAX z kADS ez c cfb X z  zþ kþADS e cM zþ
þ 0
zþ c0 cfb
ð6Þ
1 þ kADS ez c cfb X z þ kþADS e M zþ
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330
the case of a water solution containing a single
electrolyte [24,25].
XFIX and XADS represent the contribution to the
total charge of the hydrophilic and hydrophobic
groups, respectively; XFIX contains information
about the screening of the proper charge by the
dissolved ions caused by site-binding phenomena.
The proper charge is represented in Eq. (6) by the
X value corresponding to the situation at infinitely
diluted solutions.
From the general point of view, some com-
ments are in order.
A Langmuir-type equation is obtained to
describe the contribution of competitive adsorp-
tion (XADS); in that term, the prevalence of
/ titration experiments, as an example Ref. [39].
cation adsorption over anion adsorption can
determine a reversal in the charge sign. It is
self-evident that a Langmuir-type isotherm
adsorption is obtained in the case in which c0 / values for some parameters characteristics of the
is a function of pH only. On the contrary, in the
case in which the electric potential is a remark-
able function of salt concentration, it could be
easily rearranged also into a Freundlich equation.
The contribution of counter-ions site-binding
can lead to a XFIX which is different in value and
sign with respect to the corresponding value of
the proper charge. In the case of univalent
symmetric salts, as the salt concentration
increases, site-binding screens the proper charge
and the XFIX contribution vanishes to zero. On
the contrary, in the case of multivalent ions, site-
binding effects of counter-ions can cause a sign
reversal with respect to the value existing for the
proper charge, whereas site-binding effects of
co-ions always lead to an increase of the
absolute value of the proper charge.
Finally, we can observe that the structure of the
model is relatively simple and it allows describing
each phenomenon individually: the role of each
mechanism in determining the membrane charge
can be investigated case by case.
Eq. (6) contains several parameters, with a
well-defined physical meaning [24,25]: the
321
parameters related to the characteristics of the
polymeric material (X1MAX, XMAX, KA, KB); the
parameters accounting of the characteristics of
the ionic species in relation with the membrane
material (kADS and kSB); the parameters related
/ /
to the surface phenomena in the electric double
layer which depend on the operative conditions
(c0 ; 800 ;80 ; 800), we consider the pH dependence
/
as prevailing. The problem of their determination
through suitable measurements is anything but
trivial and it is still open; in this paper, all the
parameters are considered as adjustable para-
meters, although some of them might be deter-
mined by independent measurements, such as
However, since the parameters appear in Eq. (6)
as factors of their products, we can perform the
fitting procedure by assuming firstly reasonable
membrane and then by calculating all the others.
The fitting procedure has been widely discussed
in Ref. [24]; the choice has been made in which
some values for X1MAX and KA are assumed and
all the others are calculated accordingly; when it
is possible, we suggest using the whole products
as adjustable parameters. The results obtained in
Ref. [24] and in this paper are certainly valid
only on a relative scale, however they allow us
to investigate with a good precision which are
the phenomena determining the mechanism of
charge formation and to understand whether any
of them prevails as the controlling one.
3. Model application and results
The ADS-AMF model is applied to the case of
polyamide Desal DK membranes (here abbre-
viated as DK02), manufactured by Osmonics (flat
TFC membranes, polyamide selective layer
supported on a polysulfone layer). For those
membranes, a detailed characterization of the
separation properties has been performed in
the case of NaCl
water solutions [4] as well
322 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330

as in the case of CaCl2
water solutions [9], to
understand the role of pH and salt concentration in
the feed. In the same papers, authors reported the
volumetric membrane charge values correspond-
ing to each operative condition, which had been
calculated through the elaboration of rejection
data by the Donnan Steric Pore and Dielectric
Exclusion model (DSPM&DE) [7]. In this paper,
such membrane values are used as the data points
for the development of the model and they are
improperly indicated as “experimental” values.
Although some of those results have already been
presented in Ref. [24], they are necessary to
support the study here developed.
A twofold use of the ADS-AMF model is
made. Firstly, a test on the predictive ability of
the model is presented by using data obtained for
Desal-DK membranes with NaCl and CaCl2

water solutions, and the corresponding adjusta-
ble parameters are reported. Secondly, the model
is used as a predictive tool to investigate the role
of each phenomenon accounted in the mechan-
ism of charge formation for different operative
conditions and for different electrolytes. In the
latter case, the model parameters to draw the
corresponding membrane charge as a function of
salt concentration and pH are chosen taking as a
reference the values calculated in the NaCl and
CaCl2 cases. In other words, a Desal-type
polyamide membrane is assumed as a reference
membrane: the same values obtained for DK02
membranes are kept for the hydrophilic para-
meters characteristic of the polymeric material
(X1MAX, KA, KB); the values of site-binding and
competitive adsorption parameters are chosen as
reasonable values basing on the information got
from the “experimental” cases.
In Fig. 2, the case of NaCl
water solutions is
considered for which volumetric membrane
charges are reported as a function of pH and
salt concentration in the feed.
In Fig. 2(a) a comparison between “experi-
mental” data and theoretical values calculated by
a fitting through Eq. (6) is shown; the correspond-
ing adjustable parameters are reported in Table 2.
In this case, the general equation can be simplified
into a relationship accounting only the hydrophilic
parameters (X1MAXKA) and (X1MAXKB),

NaCl–water, 25°C, DK02

(a) (b)
70
pH = 6.5 5
30 pH = 5.8
pH = 5.8
pH = 6.2 3
50
–X (mol m–3)

1
–X (mol m–3)

–X (mol m–3)

pH = 5.8 -1
–1
pH = 3.0
20 30 pH = 3.0
–3
pH = 5.8
–5
10 0 1 2 3 4 5 6
cS (mol m–3)
10 pH = 5
–10
pH = 4.5 pH = 3.0
0 –30
0 10 20 30 40 50 60 0 20 40 60 80 100 120 140
cs (mol m–3) cs (mol m–3)

pH = 6.5 pH = 6 pH = 5.6 pH = 5 –X –XADS –XFIX

pH = 6.2 pH = 5.8 pH = 5.3 pH = 4.5

Fig. 2. (a) Comparison between “experimental” membrane charges (symbols from Ref. [4], rp /0.59 nm, d /23.7 mm) and
theoretical membrane charges (lines) calculated by a fitting through Eq. (7) (parameters from Table 2). (b) The effect of
counter-ion site-binding (/XFIX) in comparison with the competitive adsorption (/XADS) on the total membrane charge
(/X) at various pH and salt concentrations in the feed side. Calculations are performed by Eq. (7), parameters from Table 3.
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330 323

Table 2
Adjustable parameters of ADS-AMF model for NaCl (Fig. 2(a)) and CaCl2
water solutions (Fig. 3(a))

X1MAX (mol/m3) / 10,000; KB/KA (m3/mol)2 /250; X1MAXKA (mol/m3)2 /10; IEP/4.2 (/800 ¼ 0)

pH 800 RT
/
F
NaCl CaCl2
(mV)
0 00 0 00
kSB eþ8 kþSB e8 X

MAX/ c0  /kSB e
þ8
kþSB e28 X

MAX/ c0 0
/ / / / /
c0
(m3/mol) (m3/mol) kADS e  kþADS e 3
(m /mol) (m3/mol) kADS e  kþADS e2c

4.5 /17.7 1.73 1.74 0.18

5.0 /47.0 1.71 1.76 0.31 ~104 4.1/103 0.300
5.6 /82.3 1.70 1.77 0.38



5.8 /93.9 1.68 1.79 0.46 ~104 3.4/103 0.301
6.0 /105.8 1.71 1.75 0.50



6.2 /117.5 1.73 1.74 0.51



6.5 /134.6 1.73 1.74 0.63 ~104 4.1/103 0.353

IEP, isoelectric point of the membrane. The fitting procedure is reported in [24].

0
the site-binding parameters (kSB eþ8 ), / site-binding seems to be remarkable only at very
800
(kþSB e ) and the adsorption parameter
/ low salt concentrations and it determines the
0 0
(XMAX ðkADS ec kþADS ec Þ), as reported in
/ / decreasing behaviour of the membrane charge
Eq. (7). in that concentration range; at higher salt con-
centrations, on the contrary, the competitive
 X ¼ ðXFIX þ XADS Þ
" 0 0
# adsorption on hydrophobic sites becomes the
X1MAX KA =ðcfb
Hþ
e80 Þ X1MAX KB ðcfb
Hþ
e80 Þ dominant effect and an increasing behaviour of
ffi  the net negative membrane charge is obtained.
1 þ kþSB e800 cfb
NaCl 1 þ kSB e80 cfb
NaCl
 0 0
 Remarkably, competition between counter-ion
þ XMAX kADS ec  kþADS ec cfb NaCl site-binding and competitive adsorption is the
F
80 ¼ 800 ¼ ½ðc þ 80 Þ  8fb  ð7Þ Table 3
RT Parameters of ADS-AMF model used for NaCl (Fig. 2(b))
and CaCl2
water solutions (Fig. 3(b)) X1MAX (mol/m3)
Apparently, the model agrees well with the / 10,000; KB/KA (m3/mol)2 /250; X1MAXKA (mol/
experimental trend. The influence of pH is remark- m3)2 /10; IEP/4.2 (/800 ¼ 0)
able only on the adsorption parameter which
decreases as pH decreases; on the contrary, site- NaCl CaCl2
binding parameters are practically pH independent.
pH 5.8 3.0 5.8 3.0
Based on those results, the parameters
/XMAX
0.5 /0.2 0.3 /0.1
reported in Table 3 are estimated for the case / k
z c0
ADS e
of pH 3. The relative effect of counter-ion
/ /k
þADS e
zþ c0
Þ
0
site binding and of competitive adsorption /8 RT =F (mV) /94.0 70.0 /94.0 70.0
0
z 80
can be then investigated at pH 3 and 5.8, / /k
SB e 1.7 1.7 1/104 1/104
which correspond to positive and negative (m3/mol)
zþ 800
/k
þSB e 1.7 1.7 4/103 4/103
proper charge values, respectively. Results are 3
(m /mol)
reported in Fig. 2(b). At pH 5.8, the effect of
/
324 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330

CaCl2–water, 25οC, DK02

(a) (b)
45 350
40
35 250
30
20 pH = 5.8
10

–X (mol m–3)
25 0

–X (mol m–3)
–X (mol m–3)

150 –10
–20
15 –30
50 –40
–50
pH = 3.0

5 –60
0 50 100 150 200 250 300
–50 cS (mol m–3)
–5
pH = 5.8
–15 –150
pH = 3.0
–25 –250
0 50 100 150 200 250 300 0 50 100 150 200 250 300
cs (mol m–3) cs (mol m–3)

pH = 5 pH = 5.8 pH = 6.5 –X –XADS –XFIX

Fig. 3. (a) Comparison between “experimental” membrane charges (symbols from Ref. [9], rp /0.59 nm, d /23.7 mm) and
theoretical membrane charges (lines) calculated by a fitting through Eq. (8) (parameters from Table 2). (b) The effect of
counter-ion site-binding (/XFIX) in comparison with the competitive adsorption (/XADS) on the total membrane charge
(/X) at various pH and salt concentrations in the feed side. Calculations are performed by Eq. (8), parameters from Table 3.

cause of the presence of the minimum point in the sodium adsorption on hydrophobic sites and
function (X) vs. the salt concentration. The
/ depends only on the feed pH.
behaviour is obtained in a reversed manner at The same kind of investigation is performed in
pH3, at which it is evident the presence of a
/ the case of CaCl2
water solutions; the results are
maximum point. From a general point of view, as reported in Fig. 3. With reference to Fig. 3(a),
the salt concentration increases, the proper mem- we can observe that, also in this case, the general
brane charge due to the acid/base dissociation is relationship represented by Eq. (6) can be simpli-
completely screened by the bound ions and the net fied into Eq. (8), accounting only four adjustable
2800
membrane charge approaches the adsorption parameters,


(X1MAXcK A), (X1MAXK B), (kþ e )
0 
/
0
charge; in that concentration range the membrane and XMAX kADS e  kþADS e2c , since chlo-
/
0
charge equation becomes very simple and it ride site-binding (kSB eþ8 ) is negligible with/
00
requires only the adsorption parameters. In that respect to calcium site binding (kþSB e28 ). /

case, the membrane amphoteric behaviour is the The relevant adjustable parameters are reported
result of the competitive effect of chloride versus in Table 2; apparently, calcium adsorption on

" 0
#
X1MAX KA =ðcfb
Hþ
e80 Þ 00
fb 800
 X ¼ ðXFIX þ XADS Þ ffi ð1  kþSB e28 cfb
CaCl2 Þ  X1MAX KB ðcHþ e Þ
1 þ kþSB e2800 cfb
CaCl2

0 0  F

þ 2XMAX kADS ec  kþADS e2c cfb CaCl2 8 ¼

0
c þ 80 Þ  8fb ;
RT
F
1 

800 ¼ c þ 80  8fb ð8Þ

RT 2
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330 325

hydrophobicsites seems to be negligible with proper charge is obtained; as the concentration

respect to chloride adsorption. Also in this case increases, chloride adsorption on hydrophobic
site-binding parameters are less dependent on pH sites becomes the prevailing mechanism and a
conditions. sign reversal in the total membrane charge can
In additions, the model well reproduces the occur again. In this case, the amphoteric beha-
“experimental” trend (Fig. 3(a)), which seems to viour of the membrane remarkably depends on
be very different from what observed for the the salt concentration.
NaCl case. The explanation of the behaviour Basing on all the previous results, including
observed is reported in Fig. 3(b). At pH5.8, / what obtained for the NaCl case, we presume
the mechanism of charge formation is controlled that at pH3 calcium adsorption on hydropho-
/

by calcium site-binding on the dissociated bic sites might be considered as prevailing on

hydrophilic sites at the lower salt concentrations, chloride adsorption, and the parameters reported
whereas chloride adsorption on hydrophobic in Table 3 are estimated accordingly. As a
sites becomes the prevailing mechanism at the consequence, at pH3, the corresponding total /

higher concentrations. At low concentrations, membrane charge is predicted as a monotone

owing to the cation double valence, calcium function, since adsorption and site-binding
screening of the proper charge is relevant and a co-currently determine the membrane charge
sign reversal with respect to that existing for the (Fig. 3(b)).
Salt-water/polyamide membrane
(a) (b)
1:2 2:2
350 170
pH = 5.8
250
120
–X (mol m–3)

150
–X (mol m–3)

60
50 70 pH = 5.8
50 40
–X (mol m–3)

30 pH = 5.8
20
–50 10 20
0
–150 pH = 3.0 –10
–20
pH = 3.0

–30 –30
–250 0 50 100 150 200
–3
cs (mol m )
250 300
pH = 3.0
–350 –80
0 50 100 150 200 250 300 0 50 100 150 200 250 300
cs (mol m–3) cs (mol m–3)

–X –XADS –XFIX
(a) (b)

pH 5.8 3.0 5.8 3.0

XMAX (k–ADSe–z–ψ ′ –k+ADSe–z+ψ ′) (–) 0.2 –0.3 0.3 –0.1

ϕ0′ RT/F (mV) –94.0 70.0 –94.0 70.0

k–SBe–z–ϕ ′ (m3/mol) 4 × 10 –3 4 × 10 –3
3 × 10 –3 3 × 10 –3
k+SBe–z+ϕ ′′ (m3/mol) 1 × 10 –4 1 × 10 –4 3 × 10–3 3 × 10 –3

X1MAX (mol/m3) = 10000 KB/KA (m3/mol)2 = 250 X1MAXKA (mol/m3)2 = 10 IEP = 4.2 (ϕ0 ′= 0)

Fig. 4. ADS-AMF model (Eq. (6)). NF of aqueous solutions containing single binary electrolytes through a Desal-type
membrane. Simulation of the volume membrane charge at various pH and salt concentrations in the feed side.
326 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330
80
60
–XADS (mol m–3)
40
20
0 4
–20
–40
–60
XMAX = 5000 mol/m3
k–ADSe–z–ψ ′ (m3/mol)
k+ADSe–z+ψ ′ (m3/mol)
Fig. 5. ADS-AMF model (Eq. (6)). NF of NaCl
water solutions: the effect of anion vs. cation adsorption on
hydrophobic sites.
Following the same procedure, the model is also
used to simulate the membrane charge behaviour
for the cases of solutions containing (1:2) or (2:2)
electrolytes; the results are reported in Fig. 4, the
parameters have been estimated quite close to those
obtained in the previous cases. Apparently, in the
case of non-symmetric salts (1:2) (Na2SO4 for
instance), reported in Fig. 4(a), at pH3 the total
membrane charge can undergo a sign reversal as
the salt concentration increases. We get the same
reversed trend obtained in the case of CaCl2
solutions (Fig. 3(b)), which is a non-symmetric
(2:1) salt. In the case of divalent symmetric salts
(2:2) (CaSO4 for instance), reported in Fig. 4(b), a
behaviour is predicted very similar to what
obtained for the NaCl-case (Fig. 2(b)).
The investigation is completed accounting
also the effect of competitive adsorption. The
role of competitive effect of anion versus cation
adsorption on hydrophobic sites (XADS) is
reported in Fig. 5, for the representative case
of NaCl
water solutions. Also in this case,
reference is made to a Desal-type membrane
and the model parameters are estimated basing
NaCl–water/polyamide membrane
1
k+ADS .e–z+ψ ′
2
3
5
6
k–ADS .e–z–ψ ′ ′
0 25 50 75 100 125 150
cs (mol m–3)
1 2 3 4 5 6
1.5 × 10 –4 1.3 × 10 –4 1.2 × 10 –4 9.3 × 10 –5 7.5 × 10 –5 6.5 × 10 –5
5.0 × 10 –5 7.2 × 10 –5 8.0 × 10 –5 1.1 × 10 –4 1.2 × 10 –4 1.3 × 10 –4
on the results obtained for the real cases (see
Fig. 2 and Ref. [24]). The study is performed by
0 0
changing the ratio kADS ez c =kþADS ezþ c , in
/
order to simulate the effect of pH and of the
membrane material on adsorption parameters.
The overall effect of competitive adsorption on
the total membrane charge is reported in Fig. 6, in
/ which the specific cases of symmetric and non-
symmetric salts are considered. Calculations are
made assuming the same values of competitive
adsorption parameters as used for the NaCl case
(Fig. 5), which simply means that the adsorption
charge related to hydrophobic sites is mainly
related to the valence of the ionic species rather
than to the type of electrolytes. That assumption
can be certainly removed once experimental
results are available; however, a quite similar
behaviour had been already observed by Bowen
et al. [26] and by Tsuru et al. [28] in the case of
/ NaCl as well as of Na2SO4
water mixtures and it
had been used to predict the membrane charge
behaviour in the case of mixtures of the same
electrolytes, for a pH range at which the mem-
brane was negatively charged.
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330 327

(a) (b)
1:1 2:2
80 400
1 1
60 k+ADS .e–z+ψ ′ 300 k+ADS .e–z+ψ ′
40 2 2
200
–X (mol m–3)

–X (mol m–3)
20 3 100 3
0 0
–20 4 4
–100
–40 5 5
k–ADS .e–z–ψ ′
–200
6 k–ADS .e–z–ψ ′ 6
–60 –300
0 25 50 75 100 125 150 0 100 200 300 400
cs (mol m–3) cs (mol m–3)

(c) (d)
2:1 1:2
300 600
200 k+ADS .e–z+ψ ′ 500 k+ADS .e–z+ψ ′ 1
100
1 k–ADS .e–z–ψ ′
400 2
–X (mol m–3)

–X (mol m–3)
2
0
300
–100 3 3
4 200
–200 5 4
–300 6 100
5
–400 0
k–ADS .e–z–ψ ′ 6
–500 –100
0 100 200 300 400 0 100 200 300 400
cs (mol m–3) cs (mol m–3)

(a) (b) (c) (d)

k–SBe–z–ϕ ′ (m3/mol) 1.7 3 × 10 –3 1 × 10 –1 4 × 10 –3
k+SBe–z+ϕ′′ (m3/mol) 1.7 3 × 10 –3 4 × 10 –3 1 × 10 –4

X1MAX (mol/m3) = 10000 KB/KA (m3/mol)2 = 250 X1MAXKA (mol/m3)2 = 10 IEP = 4.2 (ϕ0′ = 0)

XMAX = 5000 mol/m3 1 2 3 4 5 6

k–ADSe–z–ψ ′ (m3/mol) 1.5 × 10 –4 1.3 × 10 –4 1.2 × 10 –4 9.3 × 10 –5 7.5 × 10 –5 6.5 × 10 –5
k+ADSe–z+ψ ′ (m3/mol) 5.0 × 10 –5 7.2 × 10 –5 8.0 × 10 –5 1.1 × 10 –4 1.2 × 10 –4 1.3 × 10 –4

Fig. 6. ADS-AMF model (Eq. (6)). NF of aqueous solutions containing single binary electrolytes through a Desal-type
membrane. Simulation of the volume membrane charge as a function of salt concentration in the feed side, at various
adsorption parameters. pH/5.8 (/800 RT =F ¼ 94 mV). (a), (b): Symmetric salts; (c), (d): non-symmetric salts.

Again the results reported in Figs. 5 and 6 the relative role of the adsorption on hydro-
put clearly in evidence the different behaviours phobic sites in comparison with site-binding
observed for symmetric and non-symmetric effects.
salts. In the case of symmetric salts the mem- The results reported in Figs. 5 and 6 can be
brane charge always presents a monotone beha- compared with those obtained in Figs. 2
4 and
viour, whereas in the case of non-symmetric the following general conclusions can
electrolytes the kind of function depends on be drawn.
328 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330
4. Conclusions
In this paper, the “adsorption
amphoteric”
model has been used to describe the fundamental
phenomena determining the mechanism of
charge formation in NF membranes and to
investigate the relative role of each of them.
The effect of counter-ion site-binding has
been investigated in comparison with the com-
petitive adsorption; in addition, a sensitivity
analysis has been performed in which the overall
effect of competitive adsorption has been studied
on the total membrane charge. Aqueous solu-
tions containing single symmetric (1:1, 2:2) as
well as non-symmetric (1:2, 2:1) electrolytes
have been considered, simulating the perfor-
mances of a polyamide Desal-type membrane,
taken as a reference, as a function of pH and salt
concentration.
In the cases in which symmetric salts are
processed, as the salt concentration increases, the
total membrane charge approaches the adsorp-
tion charge located on the hydrophobic sites.
Since the proper charge of the membrane is
screened by site-binding effects at the same
extent, the absolute value of the total membrane
charge is directly related to the feed ionic
strength. The amphoteric behaviour is always
the result of the competitive effect of anion
versus cation adsorption on hydrophobic sites
and it depends only on the feed pH.
In the case in which non-symmetric salts are
considered, we can observe that the behaviour
of the total volume membrane charge as a
function of the salt concentration is given by
the relation between the multivalent ion valence
and the proper charge sign. In the case in which
the divalent ion is the co-ion, the total mem-
brane charge shows a monotone behaviour with
the salt concentration; on the contrary, in the
case in which the divalent ion is the counter-ion,
the total membrane charge is obtained as a
unimodal function. In addition, the total mem-
brane charge can assume a monotone behaviour
or alternatively a unimodal behaviour, depend-
ing on the relative values used for the compe-
titive adsorption parameters. In the case in
which site-binding and competitive adsorption
are co-current in determining the membrane
charge, the total volume membrane charge is
directly related to the feed ionic strength; on the
other hand, in the case in which competitive
adsorption effects are opposite to site-binding
phenomena, a unimodal trend is obtained and
the amphoteric behaviour of the membrane may
depend on salt concentration.
Acknowledgements
Financial support by Italian Ministry of
Education University and Research (RFO ex
60%) is acknowledged.
Nomenclature
c mole concentration (mol m
3)
F Faraday constant (C mol
1)
DG0 standard Gibbs free energy (J mol1)
KA acid dissociation constant as defined
in Table 1 (mol m
3)
KB base dissociation constant as defined
in Table 1 (m3 mol
1)
/ kSB site-binding constants as defined in
Table 1 (m3 mol
1)
/ kADS adsorption constants as defined in
Table 1 (m3 mol
1)
/ rP membrane average pore radius (m)
R universal gas constant (J mol1 K1)
RH, R1H hydrophobic/hydrophilic functional
groups
/ RHMzþ ; adsorption complexes on hydropho-
/ RHX z bic groups
/ R1 ;
/ R H þ
1 2 de-protonated/protonated hydrophi-
lic sites
/ ðR 1 M zþ
Þ; site-binding “ion-pairs”
þ z
/ ðR1 H2 X Þ
XADS/XFIX charge contribution of hydrophobic/
hydrophilic sites (mol m
3)
 L. Bruni, S. Bandini / Desalination 241 (2009) 315
330 329

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 screening potential defined in [8] X. Wang, W. Wang and D. Wang, Experimental
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