Desalination 261 (2010) 99–103

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

The effect of feed pH on the performance of a reverse osmosis membrane

T. Hoang, G. Stevens, S. Kentish ⁎
Particulate Fluids Processing Centre, Department of Chemical and Biomolecular Engineering, University of Melbourne, Victoria 3010, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Membranes are predominantly characterized using single salts at one pH. In this paper, a more com-
Received 6 November 2009 prehensive characterization of a reverse osmosis membrane is provided. The zeta potential, flux and
Received in revised form 13 May 2010 rejection behaviour of a brackish water membrane is examined over a wide pH range. Performance in both
Accepted 14 May 2010
single salt solutions (sodium chloride, calcium chloride and sodium sulfate) and a binary solution of calcium
Available online 17 June 2010
and sodium chloride are considered. Results are consistent with the Donnan exclusion theory. That is, larger,
more highly charged ions are rejected more strongly than smaller or less strongly charged species. In
Keywords:
Membrane
particular, this behaviour can lead to hydronium ion rejections of up to −300% as this ion permeates
Reverse osmosis preferentially over other cations. Membrane flux is relatively constant with respect to pH although there is
Nanofiltration some evidence of an increase in flux in doubly charged salt solutions at high pH.
Donnan theory © 2010 Elsevier B.V. All rights reserved.

1. Introduction developed a general theory of multicomponent electrolyte separa-

The permeate flux and the salt rejection are the two parameters
usually used to evaluate the efficiency of membranes in desalination.
Both these factors are influenced by pH as well as the composition of
the feed water [1–7]. In contrast to microfiltration and ultrafiltration,
the separation mechanism of nanofiltration (NF) and reverse osmosis
(RO) membranes is based not only upon molecular size but also upon
ionic charge. Changes to the feed pH may alter the nature of the
membrane surface charge, which can subsequently affect the
membrane performance [8–11]. The relationship between feed pH
and the separation capability of NF membranes has been the focus for
many researchers over the past twenty years [5–18]. However, much
less work on RO membrane performance has been reported. Ozaki
et al. [19] concluded that the ES20 ultra low pressure RO membrane
had a high rejection capacity of heavy metals (Ni, Cu and Cr),
which was influenced by pH and the presence of divalent cations such
as Ca2+ and Mg2+. Wagner et al. [1] reported a fairly linear relation-
ship between sodium chloride salt rejection and feed pH for their RO
membranes due to the increasingly negative charge of the polyamide
membrane surface. The pH range investigated in this work was from
5 to 9 and the effect of pH under 5 on RO membrane performance is
less clear.
It was found by Lipp et al. [2] that the rejection of calcium by a
seawater membrane in single salt solutions was smaller than that of
sodium under similar conditions. This contradicted the Donnan
exclusion theory, which argues that the rejection of multivalent
ions should be higher than that of monovalent species. Hall et al. [3]
⁎ Corresponding author. Tel.: +61 3 8344 6682; fax: +61 3 8344 4153.
E-mail address: sandraek@unimelb.edu.au (S. Kentish).
tions based on the extended Nernst–Plank equation and Donnan
potentials. Agreeing with this theory, their experimental data showed
constant values of sodium and chloride rejection for SS10 cellulose
acetate membrane in sodium chloride solution as pH was lowered
until pH 4–4.5, then chloride rejection decreased and sodium rejec-
tion increased [4]. Similar results were found for calcium and chloride
rejection in a calcium chloride solution.
The aim of this paper is to clarify the effects of feed composition
and pH across a wide range on the performance of an RO membrane.
The change of permeate flux and both cation and anion rejection is
monitored and interpreted in terms of the membrane surface charge
and the Donnan theory of dielectric exclusion.
2. Experimental
The RO membrane used for this study was a brackish water AK
membrane from GE Osmonics. Salt solutions are prepared from AR
grade crystalline NaCl, CaCl2∙2H2O and Na2SO4 as supplied by Chem
Supply (South Australia). The pH was adjusted with AR grade HCl,
NaOH, Ca(OH)2 and H2SO4 corresponding to the co-ions present in the
feed solution. All solutions were prepared to a total ionic strength of
0.034 M, corresponding to 2 g/L of NaCl. Deionised water with
resistivity of 18.2 MΩ cm was used exclusively in all experiments.
A schematic diagram of the flat membrane crossflow rig set up for
the laboratory test is shown in Fig. 1. The rig consists of a Hydra-Cell
G10 pump connected with a 60 L feed tank and three parallel
Sterlitech CF042 membrane cells. The feed solution is pumped from
the feed tank passing through a spiral tube placed in a water bath for
temperature control to the membrane cells. The retentate is circulated
back to the feed tank through valves (which are used to adjust the
system pressure) and flowmeters. The permeate is collected by three

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.05.024
100 T. Hoang et al. / Desalination 261 (2010) 99–103
Fig. 1. Experimental apparatus. Pressure gauges denoted by P.
separate containers placed on an electronic balance (Pioneer Series,
Ohaus, Australia), which transfers the measured weight data to a
computer for monitoring the weight change versus time.
Membranes were washed and soaked in deionised water
overnight before use. They were then installed in the rig and com-
pacted at 1600 kPa for 2 h. Water at pH 6.5 ± 0.2 was run for 2 h
through the unit at the experimental pressure, then replaced by salt
water at the experimental pH. The entire permeate from each
membrane unit and a small amount of retentate were collected every
30 min and stored for analysis. Six sets of permeate and retentate
were collected for every experiment. After completion of the
experiment, fresh water was run to wash and clean the membranes.
Unless otherwise stated, the experimental pressure was 800 kPa and
the retentate flowrate was 12.5 L/min across each cell, giving a
crossflow velocity of 2 m/s and a Reynolds Number of 12,000.
Processing temperature was 30 ± 1 °C.
A Varian 720-ES ICP-Optical Emission Spectrophotometer was
used for determination of sodium, calcium and sulfur contents.
Chloride concentration was determined by potentiometry using a
Metrohm autotitrator Titrando Dosino with Ag–Pt electrodes and
0.02 N silver nitrate solution. pH and conductivity were measured
using an Orion 720A+ pH-meter and an Orion 3 star conductivity
meter. The apparent rejection (Rapp) was obtained from the following
equation:
 
Rapp = 1 − Cp = Cr × 100 ð1Þ
where Cp is the average value of the element concentration of three
permeate solutions collected and Cr is the retentate concentration at
the same period.
The normalized flux was calculated from:
J = Jsalt = Jwater ð2Þ
where Jsalt is the mass of permeate collected in 1 min during salt water
circulation and Jwater is the corresponding mass of permeate collected
during water circulation.
The streaming potential was measured with a commercial
electrokinetic analyser EKA from Anton Paar GmbH, Austria. Two
membranes were placed within the rectangular measuring cell, with a
PTFE spacer creating a channel between them. An Ag/AgCl electrode
was mounted at each end of the channel. In a typical experiment,
membrane samples were washed and soaked in deionised water
overnight before use. Each electrolyte solution was placed into the
feed container and the streaming potential measured as a function
of pressure (dU/dp); initially at the unadjusted pH. Acid was then
gradually added to reduce the solution pH and the streaming potential
was measured with each addition. The acid addition was carried
out very slowly around the isoelectric point (IEP) to ensure a good
estimation of this point. After the IEP was passed, the solution was
replaced with a fresh supply of the same electrolyte, the membranes
were washed thoroughly and repacked into the cell and the
measurement was continued with increasing pH using hydroxide
solution.
The relationship between the measurable streaming potential and
the zeta potential is given by the Helmholtz–Smoluchowski equa-
tion [20]:
dU η L
ζ = ð3Þ
dp ε:εo Q :R
where ζ is the zeta potential, dU/dp is the slope of a plot of streaming
potential versus pressure, η is solution viscosity, εo is the permittivity,
ε is the dielectric constant, L and Q are the length and the cross
sectional area of the capillary system, and R is the AC resistance of
the cell.
3. Results and discussion
3.1. Validation of testing protocols
Pre-compaction of the membranes was carried out at high
pressure before new membranes were used. The purpose of this
stage was to attain a stable permeate flux and improve reproducibility
of the results [21–24]. The period of pre-compaction described in the
literature has varied from 20 [21] or 24 [22,23] to 48 h [24]. Other
researchers only condition the membranes under normal operating
pressure without high pressure pre-compaction [2,3,19,25,26]. In
our case, pre-compaction was performed for 2 h before a 2 h run of
water at the standard operating pressure of 800 kPa and then 3 h of
 T. Hoang et al. / Desalination 261 (2010) 99–103
circulation of 0.034 M NaCl solution. Results showed that the most
stable permeate flux was achieved after pre-compaction at 1600 kPa.
The flux was a little higher after pre-compaction at 1200 kPa but
reduced to the same value over the period of the salt water run. Thus,
compaction at 1600 kPa was chosen for the remaining experiments.
To determine reproducibility, six pieces of the AK membrane
were tested in two runs using the 3-cell crossflow rig under the
standard processing conditions of 0.034 M NaCl, 2 m/s crossflow
velocity and 800 kPa transmembrane pressure drop. Results gave an
average salt water flux of 33.0 L m− 2 h− 1 with a standard deviation
of 0.6 L m− 2 h− 1 and an apparent rejection of 92.2% with a standard
deviation of 0.55%. These values are both lower than the manufac-
turer's specifications which indicate a permeate flux of 44 L m2 h and
a true rejection of 98.5%. However, these manufacturer's guidelines
are established at significantly lower salt concentrations (0.5 g/L
NaCl) and this will contribute to the discrepancy.
3.2. Membrane performance
3.2.1. Effect of pH on rejection
Fig. 2 illustrates the performance of the AK membrane at pH values
from 3 to 10. For a sodium chloride solution, there is considerable
variation in the apparent rejection of both sodium and chloride. At pH
10 these rejection values are comparable at 95%. Rejection is also
stable at this value at pH 8 and then falls steadily until pH 5. The
sodium rejection reaches a minimum value at this point and then rises
again while the chloride rejection continues to fall.
This behaviour can be explained by studying the charge properties
of the membrane. The plot of zeta potential for the AK membrane in
sodium chloride solution is shown in Fig. 3. The membrane is
negatively charged at high pH due to the deprotonation of carboxylic
groups and adsorption of hydroxide ions on the membrane surface.
The charge changes only marginally when pH decreases throughout
the basic and neutral areas, but rises rapidly below pH 6 to reach the
isoelectric point (IEP) at pH 4.3. As pH decreases further, the zeta
potential becomes positive through the protonation of amine groups.
The negative charge at high pH repulses chloride ions resulting in
a high chloride rejection. The sodium rejection is also high to main-
tain the charge balance of the components in the solution. As the
isoelectric point is approached, rejection of both species falls, as these
charge effects are diminished. At pH values below this point, the
positive charge of the membrane repels the sodium ions, giving it a
high rejection. However, unlike the trend in the basic zone, chloride
rejection continues to decrease. In this case, the charge balance is
maintained by the permeation of the smaller hydronium ions through
the membrane. This is evident from Fig. 4 which shows that at
Fig. 2. The effect of pH on apparent rejection of ionic species in single salt solutions with
total ionic strength of 0.034 M. Crossflow velocity is 2 m/s; transmembrane pressure is
800 kPa.
101
Fig. 3. The zeta potential of an AK membrane in various salt solutions as a function of
pH. The ionic strength of all solutions was 0.002 M.
such pH values, the hydrogen rejection reaches a negative value of
−300% in an NaCl solution.
3.2.2. Effect of ionic charge
For a comparable solution of sodium sulfate (Fig. 5), the rejection
of sodium and sulfate are uniformly high at basic pH, reflecting
the strong repulsion of the large, doubly charged sulfate ion by the
negatively charged membrane. Due to electrical neutrality, sodium
rejection is also high. As pH is decreased and the membrane charge
weakens (Fig. 3), both ions permeate more readily. However, there is
no inflexion point in rejection observed for this system at low pH. This
may reflect a lower IEP for this case. While Fig. 3 suggests an IEP of
pH ∼ 3.9, other workers have shown that the IEP within the membrane
pores can differ from that determined from zeta potential measure-
ments, which only measure surface charge [9,27,28]. In addition, at
lower pH some of the sulfate ions will be protonated to form HSO− 4 .
Fig. 6 shows the expected speciation within the solution as a function
of pH. This data has been simulated using the Electrolyte NRTL
thermodynamic model within Aspen Plus© Version 2006.5. The more
weakly charged HSO− 4 species will permeate more readily leading to
lower rejection.
The pH dependence of the calcium rejection for the AK membrane
in a calcium chloride solution is similar to the sodium rejection in a
sodium chloride solution (Fig. 5). High values of calcium and chloride
rejection are achieved at high pH. They reduce gradually until pH 5,
drop suddenly at pH 4.5 then separate, with the calcium rejection
rising steeply and the chloride rejection decreasing. However, all
rejection values are higher than in NaCl solution. These results are
quite different from a report by Lipp et al. [2], who found that the
rejections of sodium and chloride in a sodium chloride solution for a
Fig. 4. The effect of pH on apparent rejection of H3O+ in solutions of total ionic strength
0.034 M. Crossflow velocity is 2 m/s; transmembrane pressure is 800 kPa.
102 T. Hoang et al. / Desalination 261 (2010) 99–103
Fig. 5. The effect of ion charge on apparent rejection in single salt solutions. Ionic
strength of 0.034 M, crossflow velocity of 2 m/s and transmembrane pressure of
800 kPa.
Dow FT-30 membrane were much higher than those of calcium and
chloride in a calcium chloride solution. They suggested that calcium
ions better screened the negative surface charge of the membrane
than sodium ions and therefore caused a decrease in chloride
rejection. Because of electrical neutrality, calcium would also be less
rejected in a single salt solution. Our results, however, are consistent
with the theory developed by Hall et al. [3], who reported a higher
rejection for calcium chloride solution than that of sodium chloride
[4]. They argued that the calcium concentration within the membrane
should be lower than that of sodium for the same feed concentration
since calcium is sterically larger and has a higher charge [4].
In a solution of mixed NaCl and CaCl2 at the same ionic strength the
sodium rejection is comparable to that of the single salt, except that
the minimum at the isoelectric point is not as prominent (Fig. 7).
Calcium on the other hand, achieves a higher rejection in the mixed
solution. As the smaller, less charged sodium ions will penetrate
through the membrane more readily, calcium ions are rejected more
strongly. The chloride rejection for the mixed salt falls between
the two single salt solutions, which is to be expected (Fig. 8).
3.2.3. Hydrogen rejection
In sodium and calcium chloride solutions as well as in their
mixtures, hydrogen rejection has negative values throughout the
whole pH range, indicated by the fact that the pH of the permeate is
lower than that of the feed solution. The three curves in Fig. 4 have the
same shape, with rejection becoming less negative as pH increases.
These values reflect the chloride rejection results presented in Fig. 8.
The mobile and relatively weakly charged hydronium ion follows the
Fig. 6. Speciation of sulfate species in acidic solutions for a sodium sulfate solution of
0.017 M.
Fig. 7. A comparison of cation rejection in single and binary salt solutions. Crossflow
velocity is 2 m/s; transmembrane pressure is 800 kPa.
chloride ion through the membrane to retain neutrality. Conversely,
the sulfate ion is larger and doubly charged so permeation is less
favourable. This is reflected in the hydrogen rejection which remains
positive at all pH values. The fall in rejection at low pH reflects the
increase in HSO− 4 speciation as discussed above.
Fig. 9 displays the comparable rejection behaviour of OH− at pH
values above 7. In this case, negative rejection behaviour is observed
in sodium sulfate solutions. The OH− ion will permeate in preference
to the sulfate ion due to its smaller size and lower charge. Conversely,
in chloride based systems, both anions are more comparable in size
and charge and so positive rejection is observed for both. The
fall in rejection at high pH values suggests that charge effects are
more substantial for the chloride ion than for the OH− as this ion does
appear to preferentially permeate when the membrane surface is
strongly charged.
3.2.3. Effect of pH on flux
For any particular single salt solution, there is little change in
permeate flux throughout the applied pH range (Fig. 10). Childress
and Elimelech also report a relatively constant flux of sodium chloride
solution over the entire pH range for a nanofiltration membrane with
the exception of a slight peak at the isoelectric point [9]. According to
these authors, the peak in flux may be caused by an increase in pore
size due to conformational changes of the cross-linked membrane
polymer structure at neutrality. Another reason may be the increased
water permeability due to a decrease in electroviscous effects. When
Fig. 8. A comparison of chloride rejection in single and binary salt solutions. Crossflow
velocity is 2 m/s; transmembrane pressure is 800 kPa.
 T. Hoang et al. / Desalination 261 (2010) 99–103
Fig. 9. The effect of pH on apparent rejection of OH− in solutions of total ionic strength
0.034 M. Crossflow velocity is 2 m/s; transmembrane pressure is 800 kPa.
an electrolyte solution is forced through a pore with a charged surface
there is a back flow of counterions and water in the double layer
adjacent to the pore surface. This effect is minimized at the IEP where
charge effects decrease.
While all fluxes are comparable at low and moderate pH values,
the permeate flux in doubly charged salt solutions increases relative
to NaCl at higher pH. A similar increase in water flux with increasing
pH was also reported by Mäntärri et al. [28] for several NF mem-
branes and justified by expansion of the membrane matrix due
to repulsion between like-charged dissociated functional groups
on the pore walls. It is possible that these effects are accentuated
with doubly charged ions such as calcium and sulfate due to their
higher charge and their tendency to adsorb onto the pore walls.
However, this is in direct conflict with the above argument of
Childress and Elimelech [9], who suggested that pore expansion
occurs at the IEP.
4. Conclusion
For the membrane studied in this work, the rejection behaviour is
generally consistent with the Donnan exclusion theory. Larger, more
strongly charged ions such as sulfate and calcium are more strongly
rejected than smaller ions such as sodium and hydronium. In
particular, the smaller size and charge of the hydronium ion lead to
rejections as low as −300%. Conversely, membrane flux is only
marginally affected by pH. A slight increase in flux at high pH in
doubly charged salt solutions may reflect conformational changes to
the membrane pore structure in this highly charged environment.
Fig. 10. Variation in normalized flux as a function of pH in single salt solutions.
Crossflow velocity is 2 m/s; transmembrane pressure is 800 kPa.
103
Acknowledgments
Financial support for this project is provided by the CSIRO
Water for a Healthy Country Flagship and this support is gratefully
acknowledged. The authors would also like to thank GE Water for
providing the RO membrane used in this work and for useful feedback
on the draft manuscript.
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