Desalination 168 (2004) 383–390

Effect of salt type on mass transfer in reverse osmosis thin film

composite membranes

M. Khayet*, J.I. Mengual

Department of Applied Physics I, Faculty of Physics, University Complutense of Madrid
Av. Complutense s/n, 28040, Madrid, Spain
Tel./Fax +34 (91) 3945191; email: khayetm@fis.ucm.es

Received 30 January 2003; accepted 12 February 2004

Abstract

Reverse osmosis separation of inorganic salts in aqueous solutions has been studied using polyamide thin film
composite membrane, in spiral wound configuration. Various inorganic salts involving monovalent and divalent
ions have been studied. The solute transport through the membrane and the mass transfer coefficient at the high
pressure feed side of the spiral wound module were determined for each type of salt. The mass transfer coefficient
of each inorganic salt was predicted from the experimental data for the reverse osmosis separation of sodium
chloride as reference and the mass transfer empirical correlations. The values obtained were compared with the
experimental ones. The free energy parameters for monovalent cations, monovalent anions and divalent cations
have been calculated. These parameters were used to predict the reverse osmosis performance of inorganic salts in
spiral wound reverse osmosis module. It was observed that the free energy values of the cations are negative while
those of the anions are positive, suggesting that the surface of the membrane used is positively charged.

Keywords: Reverse osmosis; Inorganic salts; Desalination; Thin film composite membranes; Spiral wound module

1. Introduction desalination, while spiral wound modules are

widely used for commercial applications, ranging
Aromatic polyamide membranes constitute
from reverse osmosis (RO) to ultrafiltration (UF).
one of the successful membranes developed for
Therefore, the knowledge of the transport charac-
teristics of such membranes and the predictability
*Corresponding author.

Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation
between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European
Desalination Society and Office National de l’Eau Potable, Marrakech, Morocco, 30 May–2 June, 2004.

0011-9164/04/$– See front matter © 2004 Elsevier B.V. All rights reserved
384 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390
of their mass transfer coefficient in spiral wound
modules are of practical interest.
In RO processes, preferential sorption at mem-
brane–solution interface is one of the factors
governing solute separation. It is a function of the
membrane material, solute and solvent inter-
actions together with the experimental conditions.
These interactions arise in general from the ionic,
steric, polar, and/or non-polar character of each
one of the above three components of the system
involved. In fact, RO separations of inorganic salts
in aqueous solutions have been discussed from
different points of view, including partition
coefficient of solute between membrane and liquid
phases, enthalpy of hydration of ions in the bulk
phase solution, partial molar free energy of
hydration and entropy of ions in the bulk phase
solution, or relative free energy parameters for
ions and solutes [1]. The latter approach was
applied in this study using various inorganic salt
types involving monovalent cations, monovalent
anions and divalent cations.
On the other hand, it is well known that the
RO transmembrane water flux leads to the appear-
ance of the concentration polarization phenomenon
even when the separation of the solute from the
solvent is not perfect [2]. The solute concentration
at the membrane surface becomes higher than that
in the bulk phase. Most of the models used in
characterization of RO membranes make use of
mass transfer correlations in order to calculate the
solute concentration at the membrane surface [2].
The most used correlations are those based on the
Chilton-Colburn and Deissler analogies between
heat and mass transfer. In this study, the mass
transfer coefficient in the feed side of spiral wound
module, k, and the solute transport through
polyamide thin film composite membrane (DK/
δ) were evaluated based on RO transport equations
[3]. The obtained value of k, for each inorganic
salt, was compared with the predicted one based
on the mass transfer empirical correlations [1,4].
The concept of free energy parameter govern-
ing RO separations of ionic solutes in aqueous
solutes was established earlier and has been dis-
cussed extensively with respect to inorganic or
organic solutes [4]. The approach is based on a
modified form of the Born expression for free
energy of ion-solvent interaction to both the bulk
solution phase and the membrane-solution
interface where water is preferentially sorbed. The
utility of the free energy of ions for predicting
solute separations in RO was illustrated with
particular reference to cellulose acetate mem-
branes [4]. The object of this part of the work was
to obtain data on free energy for different
monovalent and divalent ions in aqueous solutions
with respect to polyamide thin film composite
membrane used in spiral wound configuration and
to compare such data with the corresponding ones
applicable for cellulose acetate and polyamide
membranes reported earlier [4–6]. The theoretical
approach developed by Matsuura et al. [1,4], based
on free energy parameter, is applied in this study
to predict the RO solute separation of polyamide
thin film composite membrane arranged in spiral
wound module for inorganic salts in aqueous
solutions.
2. Experimental
The experimental study was carried out using
a pilot plant ROI-2 provided by Osmonics [7]. A
stainless steel spiral wound module S2521
(Osmonics), containing polyamide thin film
composite membrane, was employed in this study.
The effective membrane area of the membrane
module was 1.2 m2.
The inorganic solutes used are listed in Table 1,
along with some relevant physiochemical data.
In this study, prior to each salt aqueous solution
test, the membrane module was initially subjected
for pure water experiment to measure the pure
water membrane permeability. All the experiments
were conducted at fixed feed flow rate of about
(171 kg/h), feed pressure of 1378.9 kPa and feed
temperature of approximately 22ºC. The solute
concentrations used were in the range of 0.09–
 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390 385

Table 1
List of solutes used with some physicochemical and experimental dataa

Solute DS Product flow rate f k DK/δ Σ(∆∆G/RT)i

(10–11 m2/s) (10–6 m/s) (%) (10–5 m/s)b (10–8m/s)c
LiCl 136.67 7.72 99.17 3.92 5.32 –0.624
NaCl 161.10 7.95 98.70 4.25 8.71 –0.130
KCl 199.48 7.66 98.23 4.77 11.77 0.171
NaBr 162.63 7.89 98.20 4.17 11.96 0.187
NaI 161.59 7.66 97.55 4.29 16.14 0.487
LiBr 137.77 7.76 98.81 3.86 7.65 –0.3068
KBr 162.63 8.06 97.50 4.20 17.08 0.4877
MgCl2 125.02 5.98 99.76 3.66 1.21 –2.067
MnCl2 125.62 6.18 99.47 3.78 1.18 –1.137
CaCl2 133.55 6.42 98.67 3.80 1.18 –0.274
MgBr2 126.25 5.76 99.58 3.64 2.08 –1.4338

a
A ≈ 8.88×10–12 m/sPa; bCalculated from Eq. (8); cCalculated from Eq. (6).

0.1 mol/l. The solute concentrations in the feed is pure water, both π2 and π3 are zero, and therefore
and product solutions were measured with a con-
ductivimeter 712 ΩMetrohm and a 692 pH/Iono- J s = A ( P2 − P3 ) (3)
meter ΩMetrohm with the corresponding ion
selective electrode. In each experiment, the solute The solute permeation flux, Jd, is written as:
separation f, was calculated using the following
DK
equation: Jd = ( c2 X 2 − c3 X 3 ) (4)
δ
Solute conc. in feed − Solute conc. in product
f = (1) (DK/δ) is called the solute transport parameter,
Solute conc. in feed the quantity K is the equilibrium constant inde-
pendent of salt concentration, X2 is the solute mole
3. Theoretical approach fraction of the feed solution at the membrane
The following basic equations for RO transport surface, X3 is the solute mole fraction of permeate
have been derived and discussed extensively with solution, c2 and c3 are the total molar concentration
respect to single solute aqueous solution systems including solute and solvent in feed and permeate,
for the case where water is preferentially sorbed respectively.
at the membrane–solution interface [1]. The By using Eq. (4) and the following relation:
solvent flux is given as:
Jd
X3 = (5)
J s = A ⎡⎣( P2 − P3 ) − ( π2 − π3 ) ⎦⎤ (2) Jd + Js

where A is the pure water permeability constant, the solute transport parameter can be calculated
(P2 – P3) is the transmembrane hydrostatic pressure as:
difference, π2 and π3 are the osmotic pressures of DK X3
( c2 X 2 − c3 X 3 )
−1
the feed and the permeate solutions at the mem- = Js (6)
brane surface, respectively. When the feed liquid
δ 1− X3
386 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390

The equation for the concentration polarization where DS and DS,NaCl represent the diffusivities of
is given by the film model [1,2]: the solute under consideration and sodium
chloride solute in water, respectively.
⎡ X − X3 ⎤ Jd + Js The concept of free energy parameter govern-
ln ⎢ 2 ⎥= (7) ing RO separations of ionic solutes in aqueous
⎣ X1 − X 3 ⎦ kc1
solutions has been discussed previously [1,4]. The
where k is the mass transfer coefficient at the feed following relationships have been derived by
side of the membrane module. Matsuura et al. [4] to calculate the free energy
Eq. (7) can be solved for k parameter, assuming parameter of ions:
a constant total molar concentration c = c1 = c2 = c3.
⎛ ∆∆G ⎞ ∆Gm ,i − ∆GB ,i
⎛ X − X3 ⎞ −⎜ ⎟ =
Js ⎝ RT ⎠i RT
k= ln ⎜ 1 ⎟ (8) (12)
c (1 − X 3 ) ⎝ X 2 − X 3 ⎠
−1 ⎧⎪⎛ Em ⎞ ⎛ EB ⎞ ⎫⎪
= ⎨⎜ ⎟−⎜ ⎟⎬
On the other hand, the mass transfer coefficient RT ⎩⎪⎝ ri + ∆ m ⎠ ⎝ ri + ∆ B ⎠ ⎭⎪
used in the concentration polarization equation
[Eq. (7)] may be obtained from Sherwood corre- where ∆G represents the free energy of solute–
lation [2] solvent interaction (i.e. the free energy of hyd-
ration of solute in the present study), R is the gas
Sh = α Reβ Sc γ (9) constant, T is the absolute temperature, the sub-
scripts m and B the membrane solution interface
where Sh, Re and Sc are the Sherwood, Reynolds and the bulk solution phase, respectively; the
and Schmidt numbers, respectively and α, β and subscript i refers to the particular ion under con-
γ are characteristic constants, which depend on sideration and E is defined as:
the hydrodynamic conditions of each system. For
spiral wound modules, the following correlation ( zi e0 )
2
⎛ 1⎞
has been reported in [1]. E=N ⎜1 − ⎟ (13)
2 ⎝ εs ⎠
1/ 2
⎛ h f ηsp ⎞ where N is the Avogadro number, zi is the valence
Sh = 1.065 ⎜ ⎟⎟ Re1/ 2 Sc1/3 (10)
⎜ Lsp 2 − ηsp of the ion, e0 is the electronic charge, ri is the radius
⎝ ⎠
of the ion and εs is the dielectric constant of solvent.
where hf is the thickness of feed flow channel, ηsp The free energy parameter is a function of the
and Lsp are the mixing efficiency of spacer and chemical nature of the solute, solvent, and mem-
the spacer mesh width, respectively. brane material. With respect to completely ionized
According to the above correlation, at a given inorganic solutes in water, it has been shown that
Reynolds number, the quantity (Sh/Sc1/3) is a con- the solute transport parameter is related to the free
stant. Matsuura et al. [4], based on Eqs. (9) and energy parameter for the ions by the expression:
(10), stated that when k for NaCl is known, k for
other solutes in dilute solutions can be obtained DK ⎧ ⎛ ∆∆G ⎞ ⎛ ∆∆G ⎞ ⎫
from the following relation: = C * exp ⎨nc ⎜ ⎟ +⎜ ⎟ ⎬ (14)
δ ⎩ ⎝ RT ⎠c ⎝ RT ⎠ a ⎭
2/3
⎛ DS ⎞ where nc and na represent the number of moles of
k = k NaCl ⎜ ⎟⎟ (11)
⎜D cations and anions, respectively and C* depends
⎝ S ,NaCl ⎠
only on the morphological structure of the membrane
 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390 387

and is independent of the nature of solute. If the solute diffusivities. The pairs of values (k, DS)
free energy parameters of the ions Na+ and Cl– were fitted to a potential function by the least
are known, the value of C* can be calculated from squares method. From Eq. (11), k was calculated
Eq. (13) using experimental data on solute trans- taking sodium chloride as reference solute. The
port parameter. results are also presented in Fig. 1. The agreement
The calculated values of the solute transport between the mass transfer coefficients calculated
parameter and the mass transfer coefficient in the by Eq. (8) and Eq. (11) may be considered good
feed side of the membrane module for each solute (i.e. the discrepancy is less than 4.9%). However,
may then be used to obtain the solute separation, for spiral wound modules the applicability of the
f, using the following expression [4]: empirical mass transfer correlations is not
−1
recommended as both the membrane type and the
DK J d + J s 1 − f ⎡ J + Js ⎤ spacer used in the high-pressure side of the mem-
= ⎢ exp d (15)
δ S f ⎣ Sk ⎥⎦ brane module may cause large errors.
The solute transport parameter (DK/δ) was
where S is the effective membrane area. calculated from Eq. (6). The results are also shown
in Table 1. It can be observed that the solute
transport parameters of the salt involving divalent
4. Results and discussion
ions are lower than those of the monovalent ions.
The concentration of the solute at the mem- Ghiu et al. [6] studied the importance of para-
brane surface was calculated from Eqs. (1)–(3). meters like ionic size, ionic hydrated size, diffus-
Then, the mass transfer coefficient, k, was ivity in solution, enthalpy and entropy of hydration
evaluated from Eq. (8). The obtained values on salt permeation. It was reported that the
together with the data involved in the calculations crystallographic radii cannot explain the order of
are summarized in Table 1. The mass transfer salt type permeation and the hydrated radii must
coefficient is, in general, higher for the inorganic be considered instead of the crystallographic radii.
salt having higher diffusion coefficient. Fig. 1 In fact, the enthalpy of hydration (∆H) as well as
shows the k values obtained as functions of the the entropy of hydration (∆S) represent more
precise quantification of the degree of hydration.
5.0 Both thermodynamic parameters ∆H and ∆S are
0.5444
integrated in the bulk Gibbs free energy (∆G).
y = 0.2658x
4.5 2
R = 0.9733
Furthermore, the interaction ion-solvent must be
taken not only in the bulk feed solution but also
k (10 m/s)

at the membrane surface. All these observations

4.0
-5

Eq. (8) were considered by the free energy parameter

Eq. (11) defined in Eq. (12).
3.5 In this study, values of EB, ∆B, Em and ∆m were
determined as stated earlier in [4]. The calculated
3.0 values of E B and ∆ B were respectively
100 120 140 160 180 200 220 182.0 kcal Å/mol and 0.86 Å for monovalent
D s (10
-11 2
m /s) cations, 120.5 kcal Å/mol and –0.20 Å for mono-
Fig. 1. Mass transfer coefficients calculated from Eqs. (8) valent anions and 746.3 kcal Å/mol and 1.03 Å for
and (9) vs. diffusion coefficient of the inorganic salts. divalent cations. Em and ∆m were 181.8 kcal Å/mol
The solid curve refers to the fitting of the k values obtained and 0.90 Å for monovalent cations,
from Eq. (8). 126.6 kcal Å/mol and –0.13 for monovalent anions
388 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390

and 750.5 kcal Å/mol and 1.05 Å for divalent
cations, respectively. These data were used to
calculate the free energy of solute-solvent
interaction ∆G at the membrane solution interface
and at the bulk solution phase of ionic solutes,
together with the free energy parameter of each
ion type. The results are shown in Table 2.
Using the experimental data (DK/δ) for NaCl
given in Table 1 and the data on (–∆∆G/RT)i for
Na+ and Cl– ions given in Table 2, the value of C*
was calculated from Eq. (14). A value of
9.92×10–8 m/s was obtained. It can be observed
that the quantity (∆∆G/RT)i is negative for all
cations and positive for all anions. This indicates
that the anion is attracted and the cation is repelled
divalent cations. Also, Table 2 shows that the
values of (∆∆G/RT)i for the halide anions increase
with the increase in ionic radius. This means that
with respect to solutes involving halide anions,
(DK/δ) increases, and hence solute separation
decreases, with the increase of the ionic radius
(Table 1).
Fig. 2 shows the plot of ln(DK/δ) as function
of Σ(∆∆G/RT)i. A straight line can be plotted
between the two parameters which indicates that
the procedure used can be applied also for spiral
wound configuration. It must be mentioned here
-15

by the membrane surface which means that the -15.5

membrane surface is positively charged and hence -16
y = 1.0496x - 16.126
2
it acts as an acid (proton donor). This result R = 0.9971
ln (DK /δ )

-16.5
confirms the observation made earlier for
polyamide material [5,6]. In contrast, an opposite -17

sign of (∆∆G/RT)i was observed for cellulose -17.5

acetate membranes used in RO [4]. Furthermore, -18
it was found that the values of the ionic parameter
-18.5
for divalent cations are lower than those for the -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
monovalent cations. This results in lower values
Σ(∆∆G /RT )i
for (DK/δ) and hence higher values for solute
separations with respect to solutes involving Fig. 2. Correlation of ln(DK/δ) vs. Σ(∆∆G/RT)i.

Table 2
Free energy parameters for some monovalent cations, monovalent anions and divalent cations

Ions Ionic radius ∆GB,i ∆Gm,i ∆∆G (∆∆G/RT)i

(Å) (kcal/mol) (kcal/mol) (kcal/mol)
Monovalent cations
Li+ 0.60 –123.5 –121.2 0.907 –1.5463
Na+ 0.95 –98.3 –98.3 0.617 –1.0527
K+ 1.33 –80.8 –81.5 0.441 –0.7518
Monovalent anions
Cl– 1.81 –75.8 –75.4 –0.541 0.9228
Br– 1.95 –72.5 –69.6 –0.727 1.2395
I– 2.16 –61.4 –62.4 –0.903 1.5396
Divalent cations
Mg++ 0.65 –455.5 –441.9 2.295 –3.9129
Mn++ 0.80 –370.1 –406.1 1.749 –2.9827
Ca++ 0.99 –380.8 –368.2 1.243 –2.1195
 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390 389

that, for a given membrane, a lower value for in Fig. 1. Fig. 4 shows the variation of both the
Σ(∆∆G/RT)i may result in a lower value for (DK/δ) experimental and the calculated solute separation
and better solute separation can be obtained. with the algebraic sum Σ(∆∆G/RT)i. The predicted
In addition, by using the value of C* and the solute separation (solid line) did not differ
data on (–∆∆G/RT)i for different ions given in significantly from the experimental one. The
Table 2, the values of (DK/δ) for the different highest difference in data on solute separations
inorganic solutes were calculated from Eq. (14). was within 0.2% for CaCl2. The agreement between
The results are presented in Fig. 3 as a function the calculated and experimental results confirms
of the previously obtained values determined from the practical validity of the prediction technique
Eq. (6). Good agreement can be observed between and the numerical values of the free energy used
both values, which indicates that the procedure in this study.
used is adequate.
The values of (DK/δ) calculated from Eq. (14)
5. Conclusions
were used to obtain data on solute separation, f,
using Eq. (15) and the applicable value of mass The transport of various inorganic salts in
transfer coefficient, k, on the high-pressure side aqueous solutions through polyamide thin film
of the membrane obtained from the straight line composite membrane in spiral wound

16

14
DK /δ (10 m/s) from Eq. (14)

12

10

8
Monovalent cations
-8

6
Monovalent anions
4 Divalent cations

0 Fig. 3. Comparison of the calculated solute

0 2 4 6 8 10 12 14 16 transport parameters from Eq. (14) and the
-8
DK /δ (10 m/s) from Eq. (6) ones calculated from Eq. (6).

100

99.5
Experimental

99 Predicted
f (%)

98.5

98

97.5

97 Fig. 4. Theoretical and experimental solute

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 separation vs. Σ(∆∆G/RT)i . The solid curve
Σ(∆∆G /RT )i refers to the predicted values.
390 M. Khayet and J.I. Mengual / Desalination 168 (2004) 383–390
configuration has been studied using reverse
osmosis process. The mass transfer coefficient of
each inorganic salt at the high pressure feed side
of the spiral wound module was determined by
means of two methods and little discrepancy
between them was detected. In general, it was
found that the mass transfer coefficient is higher
for the inorganic salt having higher diffusion
coefficient.
It was also observed that the solute transport
parameter of the salt involving divalent ions is
lower than that of the monovalent ions. The free
energy parameters for monovalent cations,
monovalent anions and divalent cations have been
calculated and the obtained values were employed
to predict the reverse osmosis performance of each
inorganic salt. The free energy values of the
cations are negative while those of the anions are
positive, suggesting that the surface of thin film
composite membrane used in this study is
positively charged. Good agreement between the
predicted reverse osmosis solute separation and
the experimental one was obtained.
Acknowledgement
The authors of this work gratefully acknow-
ledge the financial support of the “Comunidad de
Madrid” through its project Nº 07M/0059/2002.
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