Engineering, 2022, 14, 9-32

https://www.scirp.org/journal/eng
ISSN Online: 1947-394X
ISSN Print: 1947-3931

Optimizing Reverse Osmosis Membrane

Parameters through the Use of the
Solution-Diffusion Model: A Review
Farah Z. Najdawi, Kaleb T. Neptune

Department of Material Science Engineering, and Commercialization, Texas State University, San Marcos, TX, USA

How to cite this paper: Najdawi, F.Z. and Abstract

Neptune, K.T. (2022) Optimizing Reverse
Osmosis Membrane Parameters through When designing and building an optimal reverse osmosis (RO) desalination
the Use of the Solution-Diffusion Model: A plant, it is important that engineers select effective membrane parameters for
Review. Engineering, 14, 9-32. optimal application performance. The membrane selection can determine the
https://doi.org/10.4236/eng.2022.141002 success or failure of the entire desalination operation. The objective of this
work is to review available membrane types and design parameters that can
Received: November 8, 2021
Accepted: January 4, 2022 be selected for optimal application to yield the highest potential for plant op-
Published: January 7, 2022 erations. Factors such as osmotic pressure, water flux values, and membrane
resistance will all be evaluated as functions of membrane parameters. The op-
Copyright © 2022 by author(s) and
timization of these parameters will be determined through the deployment of
Scientific Research Publishing Inc.
This work is licensed under the Creative
the solution-diffusion model devolved from the Maxwell Stephan Equation.
Commons Attribution International When applying the solution-diffusion model to evaluate RO membranes, the
License (CC BY 4.0). Maxwell Stephan Equation provides mathematical analysis through which the
http://creativecommons.org/licenses/by/4.0/ steps for mass transfer through a RO membrane may be observed and calcu-
Open Access lated. A practical study of the use of the solution-diffusion model will be dis-
cussed. This study uses the diffusion-solution model to evaluate the effec-
tiveness of a variety of Toray RO membranes. This practical application con-
firms two principal hypotheses when using the diffusion-solution model for
membrane evaluation. First, there is an inverse relationship between mem-
brane and water flux rate. Second, there is a proportional linear relationship
between overall water flux rate and the applied pressure across a membrane.

Keywords
Reverse Osmosis Membrane, Solution-Diffusion Model, Maxwell Stephan
Equation, Desalination Plants, Membrane Optimization

1. Introduction
Understanding the physical parameters of a reverse osmosis membrane can help

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F. Z. Najdawi, K. T. Neptune

engineers optimize desalination plant production. The optimization of plant

production can help meet the global demand for clean water. Mathematical
models can help resolve the optimization parameters of these systems which will
allow for effective improvements. Any effort that improves clean water produc-
tion inevitably contributes to the global demand for clean water which indirectly
betters the quality of life for many. This review analyzes developments in mem-
brane design and membrane parameters in order to illuminate the optimal pa-
rameters with the solution-diffusion model. First, an overview of reverse osmosis
systems will be provided, followed by an overview of the membrane structures
used in reverse osmosis. Next, the motivation for employing reverse osmosis
systems is outlined, followed by models for exploring mass transfer through
membranes. Then, the solution-diffusion model is examined in relation to how
it can help us optimize RO membrane parameters. Developments in thin, highly
permeable membranes are analyzed next, and then, finally, this review explores
practical applications of the solution-diffusion model relative to RO membrane
construction.

2. Reverse Osmosis Systems Overview

Reverse Osmosis (RO) is a method of purifying water using a semi-permeable
membrane which collects and removes ions, molecules, and some larger particles
to produce clean drinking water [1]. In the process of reverse osmosis, osmotic
pressure is overcome by an applied pressure, where osmotic pressure is a colliga-
tive property that is propelled by chemical potential difference between a solute
and solvent. Reverse osmosis used for water treatment removes several types of
dissolved and suspended species including bacteria from the water. Reverse os-
mosis is used in both industrial processes and clean potable water production.
When reverse osmosis occurs, the solute is held on the side of the membrane
that is pressurized, allowing the pure solvent to move through the membrane to
the other side. This membrane is selective enough so as not to allow larger mo-
lecules or ions to pass through the pores. However, these pores should allow for
smaller components like solvent molecules to move freely. In a typical osmotic
process, the solvent will pass from the region of lower solute concentration (or
higher water potential) through the membrane and to a region of lower solute
concentration (or lower water potential). The drop in the free energy of the sys-
tem is the force which propels the movement of the solvent when the difference
in solvent concentration on either side of the membrane is reduced. This creates
osmotic pressure from the solvent moving into the area of more concentrated
solution. Reverse osmosis is the application of an external pressure which re-
verses the natural flow of a pure solvent. Because reverse osmosis utilizes diffu-
sion, it can be reliant on pressure, flow rate, and other conditions that can be
evaluated and optimized [2].
A. Stages of RO treatment
A desalination plant is composed of four primary systems as shown in Figure
1. These are the following: 1) pretreatment system; 2) high pressure; 3) pumps

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 F. Z. Najdawi, K. T. Neptune

Figure 1. This diagram depicts the basic reserve osmosis system and subsystems [4].

and membrane systems; and 4) post-treatment. In the pretreatment system, all the
suspended solids are removed so that salt precipitation or microbial growth can be
prevented along the membranes. This process can involve conventional methods
such as a chemical feed, often proceeded by coagulation/flocculation/sedimentation
and sand filtration, or membrane feed processes like microfiltration and ultrafil-
tration. To achieve the pressure needed for the water to pass through the mem-
brane and reject the salt, high-pressure pumps are used. After pretreatment, the
water will travel to the pumped system where it will be pressurized to 17 to 27
bars for brackish water, and 52 to 69 bars for seawater [2]. Then the water will be
forces through the RO membrane system. The membrane systems contain a
pressure vessel and the semi-permeable membrane within. The water then will
go through the post treatment process. Post-treatment can sometimes require
adjusting the pH and disinfection depending on the quality of the water in the
permeate and the use of the permeate [2].
In addition to the membranes, reverse osmosis systems also contain other
methods of filtration, usually consisting of three, four, or five stages of filtration
depending on the individual system. These filters are referred to as prefilters or
postfilters based on if the water moves through them before or after it moves
through the primary membrane. The sediment filter reduces particles develop-
ment in the water, such as dust, dirt, and rust. The carbon filter reduces the
presence of volatile organic compounds, chlorine, and other pollutants which
would affect the water’s taste or color. Finally, the semi-permeable membrane
catches up to 98% of the total dissolved solids in the water [3].
B. Advantages of RO systems
There are eight principal advantages to employing reverse osmosis in processes
such as dilute aqueous wastewater treatment. These are: 1) Reverse osmosis sys-
tems are relatively easy to design and use, including lower maintenance needs
and modularity. RO systems can be expanded fairly easily; 2) The membrane fil-
tration processes at work in reverse osmosis allow for the removal of organic and
inorganic contaminants from the water; 3) The energy needs of reverse osmotic
systems are lower than other water filtration methods; 4) Reverse osmosis sys-

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F. Z. Najdawi, K. T. Neptune

tems provide for the reclamation and recycling of waste process streams, which
subsequently does not affect the quality of the material being recovered; 5) Re-
verse osmosis plants can typically be operated at ambient temperatures that re-
duce scale formation and corrosion problems, thus saving money in terms of
maintenance and repair costs; 6) Since reverse osmosis systems possess a com-
partmental, modular structure, there is an increased flexibility with building de-
salination plants in a wide range of capacities; 7) Reverse osmotic systems enjoy
a lower specific energy requirement; and 8) By using reverse osmosis processes,
water treatment plants can significantly lower the volume of waste streams, al-
lowing them to be treated in a more efficient and cost effective manner [2].
C. Disadvantages of RO systems
Household reverse osmosis units yield large amounts of water waste due to
low back pressure and they only treat 5% to 15% of the water that enters the
home. The rest will be purged as wastewater, and because this wastewater carries
the unwanted pollutants, it is not common practice to recover this water with
household systems. When wastewater is connected to the house drains it also
adds to the load on the house’s septic system. As an example, if a reverse osmosis
system is producing five gallows of clean water a day, it can discharge anywhere
between 20 and 90 gallons of wastewater per day. Another disadvantage of re-
verse osmosis system is that with their fine membrane construction, these sys-
tems can end up removing so many contaminants and foreign components from
the water supply that desirable minerals that may be naturally occurring in the
water are removed too. Some researchers have explored the ways in which our
drinking of demineralized water might have long-term health effects [2].
D. Applications of RO systems
The process of reverse osmosis is inherently advantageous because of its
membrane-based mechanism where concentration and separation can take place
without a change of state and without the use of chemicals or thermal energy.
This energy efficient characteristic makes reverse osmosis an ideal candidate for
recovery applications. Reverse osmosis has been used for a wide array of applica-
tions and in an equally wide range of industries, including the beverage industry,
spent wash from distilleries, groundwater treatment, recovery of phenol com-
pounds, drinking water purification, hydrogen production, window cleaning,
and even the reclamation of wastewater and seawater [5].

3. RO Membrane Structure Overview

Reverse osmosis membranes are often characterized by their structure, material,
geometric configuration, and the permeability. A variety of polymer materials
are used but these membranes can be divided into two main groups based off
their structures: conventional thin-film composites and thin-film nanocompo-
sites. Conventional thin-film composites can be further classified into two main
groups based off the materials used to make the membrane: Polyamide and cel-
lulose acetate [6]. These membranes are also divided into three main groups

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 F. Z. Najdawi, K. T. Neptune

based on the geometrical configuration of the membrane structure. These geo-

matical membrane configurations are hollow-fiber, spiral-wound, and flat-sheet.
The permeability of the membrane is divided into three types: porous, non-porous,
and dense.
A. Membrane structures
1) Conventional Thin-Film Composite Membrane Structure
The most widely used RO membranes are constructed of conventional thin-film
composite membrane. These membranes are either made of aromatic polyamide
(PA) or cellulose acetate (CA) thin films. The basic architecture of these mem-
branes consists three layers. The first is the semipermeable PA or CA thin-film,
typically only 0.2 micrometers thick, supported by a 0.025 to 0.05-mm micro-
porous layer. This microporous layer is cast on a third and final layer of rein-
forced fabric. The ultrathin polymeric film layer is the feature of this structure
that gives the RO membrane the salt rejection capabilities [6]. The other two
layers provide membrane reinforcement and help maintain integrity and dura-
bility of the structure. The semipermeable polymer film is constructed of a ran-
domly oriented molecular structure with a high density and no porosity. Since
this polymer has no porosity, the water molecules must transport though the
membrane film by diffusion. Due to the random orientation of the molecular
structure the path of the water molecules become multidimensional and curvili-
near [6]. This is the fundamental reason that solution-diffusion is applied for
analyzing the design of membrane structures.
2) Nanocomposite Membrane Structure
A novel membrane structure has been recently developed and provides evi-
dence of higher specific permeability than conventional RO membranes at com-
parable salt rejection rates. These are thin-film nanocomposite membrane struc-
tures. Nanocomposite membranes are made of either a porous film consisting of
an array of highly structured nanotubes densely and orderly packed or inorganic
nanoparticles dispersed into the traditional membrane polymeric thin-film, PA
or CA, membrane structures [7]. Nanocomposite membranes also have compa-
rable or lower fouling rates than conventional thin-film composite RO mem-
branes and can potentially be designed to remove specific ions. If these mem-
branes evolve to a point where the entire membrane structure is made of tubes
of uniform size, then these membranes could increase the water production ca-
pabilities by nearly 20% over conventional membrane structures [6].
B. Membrane materials
1) Aromatic Polyamide Membranes
Aromatic Polyamide membranes are the most widely use membrane of con-
ventional membrane structures. These membranes are used for both potable and
industrial water production. The ultrathin polyamide film is formed on the sur-
face of a thin microporous polysulfone support layer. The cohesion of the semi-
permeable thin film material with the microporous support layer is through in-
terfacial polymerization of monomers containing polyamine and immersed in
solvents containing a reactant to form a highly crosslinked combined structure

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F. Z. Najdawi, K. T. Neptune

[8]. PA membranes are preferred over CA membranes because they operate at

lower pressures with higher productivity. PA membranes also allow lower salt
passage than CA membranes. PA membranes have a negative charge when the
pH level is greater than 5. This electronegativity amplifies the co-ion repulsion
and results in higher salt rejection. A disadvantage of PA membranes is when
the systems pH level is below 4, the charge of the membrane changes to positive
and the rejection of slat is reduced significantly. In the case of a system with pH
levels below 4, CA membranes are more effective at salt rejection then PA mem-
branes. The effective operating pH range for PA membranes is from 2 to 12,
which is much wider than the 4 to 6 pH range for CA membranes. This wider
range allows ease of maintenance and cleaning of PA membranes. PA mem-
branes are also non-biodegradable. Their usage life ranges from 5 to 7 years in
comparison to a 3-to-5-year life usage range of CA membranes [8]. Unfortu-
nately, PA membranes are highly susceptible to degradation by the oxidation of
chorine and other oxidants. Chorine exposure can cause permanent damage to
the thin-film structure which will result in significant reduction of salt rejection
performance. Since most water processing systems use oxidants for biofouling
control, the feed water to PA membranes must be dechlorinated prior to the RO
separation stage.
2) Cellulose Acetate Membranes
The structure of CA membranes differs from PA membraned such that the
top two layers are made of the same CA polymer but with different material
characteristics. The entire thickness of a CA membrane is 100 µm which is less
than that of a PA membrane which is 160 µm. One important benefit of CA
membranes is their surfaces have little charge and are usually considered as un-
charged membranes. This makes CA membranes much less susceptible to catio-
nic fouling [6]. CA membranes also have a smoother surface than PA mem-
branes, further rendering their foul resistances. As mentioned before, one limi-
tation of CA membranes is the small effective pH operating range. This is ac-
companied by a limiting operation temperature as well. CA membranes exposed
to temperatures above 40˚C caused compaction and lead to failure. To keep the
pH levels in an effective operating range, feed water to the CA membranes must
be reduced during normal plant operations resulting in additional processing
cost. CA membranes also experience accelerated deterioration when exposed to
microorganisms which can bioassimilate the membrane material. CA mem-
branes, however, have a high tolerance to chorine which is often used to counter
act the rate of destruction due to microbial activity [8]. The unique structure of
CA membranes makes them denser than PA membranes. The high density leads
to high head loss across CA membranes. Higher head loss across CA membrane
system means higher operating pressures yielding increased operating cost.
Since CA membranes have a high tolerance to oxide, they are ideal for municipal
applications with high fouling potential. CA membrane’s oxide tolerance also
makes these membranes the superior choice when ultrapure water is needed
such as for pharmaceutical and semiconductor industries [6].

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C. Membrane geometric configurations

1) Hollow-Fiber
Until the mid-1990’s, hollow-fiber elements were the most prevalent technol-
ogy used for desalination. The semipermeable thin films described above are ap-
plied as a coating on the surface of a hollow fiber. These hollow fibers have and
internal diameter of approximately 40 µm and an outer diameter of approx-
imately 80 µm. These fibers are bundled in sections with thicknesses ranging
from 4 to 8 inches. These bundles of fibers are typically folded in half forming a
single assembly with a length around 48 inches. The bundle of folded fibers is
placed inside a cylindrical housing that is usually 6 to 12 inches in diameter.
These housings are usually 50 to 54 inches long and epoxy sealed at both ends.
One end of the element will contain the looped end of these fiber bundles created
by the folding and the opposite end will have the open end of all the individual
fibers. Saline feed water is pumped into the cylindrical housing and the water
permeates through the membrane film coating into the inner side of the hollow
tubes [8]. The salt and impurities are contained on the external side of the hol-
low-tubes while the permeate is collected and conveyed to a production collec-
tion output. This membrane configuration allows the largest semipermeable
thin-film surface area exposure which makes them very suitable for high-salinity
waters. Since the membrane surface area of a hollow-fiber membrane is so high
the water flow regime is laminar. This low energy flow regime allows particulates
and biofilms to easily attach along the membrane surface. Accumulation on the
surface of these membrane structure leads to higher particulate fouling and bio-
fouling [6]. The hollow fiber membranes offer a unique advantage in salt passage
due to their high surface areas, but they require substantial amounts of pre-
treatments to keep them clean from accumulations.
2) Spiral-Wound
Today the desalination market is dominated by spiral-wound RO membrane
elements. Spiral-wound membrane elements are typically made from approx-
imately 40 individuals flat membrane sheets. These sheets are constructed form
the triple-layered PA and CA membrane structures described before. These flat
membrane sheets are assembled into membrane envelopes, each envelope con-
sisting of two membrane sheets separated by a thin plastic net, referred to as a
permeate spacers. The permeate spacers form a channel allowing evacuation of
the permeate fluid upon separation from saline feed water. The membrane en-
velopes are sealed together on three of four sides [8]. The fourth side is left open
to direct the permeate towards the central collection tube. The flat membrane
envelopes are evenly spaced by plastic feed spacers. The feed spacers allow ade-
quate flow and mixing of saline feed water though the entire length of the mem-
brane element. The assembly of these flat-sheet membranes, and associated
spacers, are wrapped around the perforated permeate collector tube to form a
spiral-wound assembly. The assembly is maintained by wrapping the wound
elements with tape and placing them in a fiberglass containment. Perforated
plastic caps are then placed at the ends of each element. The end caps serve as

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F. Z. Najdawi, K. T. Neptune

longitudinal containment structures for the element structures and as seal carri-
ers between membrane elements. They are perforated with specific patterns to
optimize saline feed flow distribution. Endcaps of membrane elements are de-
sign to mate from one membrane element to the next, providing sufficient seals
for multiple parallel membrane element configurations.
The typical configuration for commercial elements is seven elements per a
vessel. Spiral-wound RO membranes are commercially available in sizes ranging
from 2.5 inches in diameter to 19 inches in diameter. The most used commercial
spiral-wound RO membrane size is 8 inches in diameter and 40 inches in length.
These membrane elements have brine spacer thicknesses of 28 mils. The stan-
dard 8-in seawater element can produce anywhere from 3500 gal/day to 6500
gal/day. The standard 8-in brackish water element can produce anywhere from
7000 gal/day to 10,000 gal/day [6].
3) Flat-Sheet
Flat-sheet membrane elements are used in plate and frame RO systems. These
systems consist of flat membrane envelopes made of two membrane sheets and a
permeate spacer. The main difference between these element and spiral-wound
elements is the membrane envelope is stacked flat one on top of another with
feed water/brine spacer installed between each membrane envelope. The per-
meate spacers facilitate an envelope for permeate collection and prevent the
membrane sheets form collapsing. The feed water/brine spacers facilitate feed
water flow through the element.
Flat-sheet membrane elements have low membrane packing densities which
make them significantly larger and more costly than conventional spiral-wound
RO membrane elements. These elements are not widely utilized for municipal
water RO desalination due to cost and size [6]. However, since these systems can
be individually unpacked and cleaned, they have been used in food processing
where high-solids applications are present.
D. Membrane permeability
1) Porous Membranes
The first type is that of the porous membrane and is shown in Figure 2. These
membranes have a mean pore size diameter of 0.001 - 5 µm. With porous mem-
branes, molecules move based on a pressure-driven convective flow through the
tiny pores of the membrane, which are bigger than 10−9 m. The different com-
pound permeabilities is a result of the differences in steric hindrances between
the components molecules and the membrane material. Within a porous mem-
brane, the concentration of permeants is uniform, with the sole driving force
across the membrane being the pressure gradient [9].
The vast majority of the membranes identified in prior research are made from
prolypropylene (PP), polyvinylidene fluoride (PVDF), polyte-trafluoroethylene
(PTFE), polyethylene (PE) and polyethersulfone (PES). There are benefits to us-
ing this specific module, such as high mass transfer when non-wetted and lower
thermal conductivity, as well as disadvantages, such as sensitivity to wetting,

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 F. Z. Najdawi, K. T. Neptune

Figure 2. This diagram depicts the structure of a porous membrane.

scaling and intrapore salt precipitation, and capillary condensation. Figure 3

shows the basic structure of a porous membrane.
2) Non-Porous Membranes
The second type of membrane classified by the compounds of the liquid mix-
ture being able to move through the membrane based on their force and the
permeability of the membrane is that of the non-porous membrane and is shown
in Figure 4.
Non-porous membranes are typically employed in the processes of reverse
osmosis, nanofiltration, or molecular separation in the gas phase. With the
non-porous membrane, the membrane is a dense film where permeants can dif-
fuse through the membrane with pressure, concentration, or electrical potential
gradient. The permeability as well as the selectivity is affected by the polymeric
material. Differences in solubility and diffusivity allow for the separation process
to occur. One downside of using a non-porous membrane is low flux, and ac-
cordingly, the dense film is typically constructed to be extremely thin and is de-
posited on top of asymmetric membranes [10].
3) Dense Membranes
The third type of membrane classified here is the dense membrane, which
possesses a mean pore size diameter of less than 1 nm. In the case of dense mem-
branes, the molecules from the different compounds must first dissolve into the
membrane matrix, whereby they can then diffuse through the membrane under
a concentration gradient. It follows that the level of permeability of each species
is determined by the solubility of each compound into the membrane material,
which is the thermodynamic aspect, and by the rate at which each component
diffuses through the membrane, which is the kinetic aspect. With the case of
dense polymer membranes, the average pore diameter is within the thermal mo-
tion of the polymer chains, of which the membrane is constructed [9] (Figure
5).
With the process of desalination, salt is incapable of being vaporized, and it
will therefore not cross the membrane. Accordingly, water vapor is the only
compound which transfers across the membrane, like with the case of a porous
membrane being used for membrane distillation applications. There are a few

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F. Z. Najdawi, K. T. Neptune

Figure 3. This diagram depicts the structure of a porous distillation membrane [11].

Figure 4. This diagram depicts the structure of a non-porous membrane [9].

Figure 5. This diagram depicts the structure of a dense membrane [11].

benefits from applying this type of membrane, such as wetting protection, capil-
lary condensation prevention particles, and the removal of salt. However, the
disadvantages of using this type of membrane are increased thermal conductivi-
ty, unexplored concept, and issues with mechanical resistance [11].
Membranes are crucial for reverse osmosis purification systems to operate at
their maximum potential and remove the most unwanted compounds. Most of
the membranes in use at commercial reverse osmosis plants are made of cellu-
lose acetate, polyamide, polysulfonate, and polyoxadiazole. There are typically
0.25 microns of skin and 100 microns of a support layer, which help in the mem-

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 F. Z. Najdawi, K. T. Neptune

branes’ abilities to filter out contaminants. When these membranes are made of
cellulose acetate and polyamide, they possess strong salt rejection characteristics
in the case of inorganic salts. However, in the case of organic salts, the rejection
is observed to be lower and with a higher variability, showing a range of 0.3 to
0.96 [12] [13]. Membranes are usually rather pricey and can be expected to be of
successful use for a long time. The best membranes demonstrate higher water
flux (which means they are highly permeable to water) and ideally would allow
for the flow of fairly large quantities of water through their bodies dependent on
the total volume they occupy. The membrane should additionally be chemically,
physically, and thermally stable in saline waters, and tough enough to sustain
high pressures and fluctuations in the quality of the feed water.

4. Motivation for Use of RO Systems

Water scarcity is a worldwide and rapidly expanding crisis found in nearly every
region of the world. As of today, roughly 36% of the global populous lives in wa-
ter-scarce regions [14]. With a reverse osmosis system, the cleaning usually be-
gins once the normalized flux drops 10% to 15%, the normalized salt content of
the permeate rises by 10%, or when the pressure gradient in the pressure vessel
drops by 15% [2]. With the membrane distillation module, the liquid that is at
higher temperature in the feed is first evaporated at the liquid/vapor interface.
Next, the resultant water vapor crosses the pores of the membrane. This vapor is
a newly condensed compound on the permeate side. The principal force at work
in this process of membrane distillation is the vapor pressure difference between
the feed and the distillate. This is a product of the temperature and salt concen-
tration within the layers adjacent to the membrane. While membrane distillation
obviously holds great potential for its usage, there are some disadvantages that
are a result of the operating conditions and the characteristics of the membrane.
These disadvantages are the main factors which handicap the application of
membrane distillation in industrial development and commercialization. The
disadvantages are pore wetting, fouling, temperature and concentration polari-
zation, and scaling [15]. However, all hope is not lost. There have been various
innovations made to processes and materials which could potentially alleviate
the problems resultant in the processes of membrane distillation [11]. Addition-
ally, when attempting to optimize reverse osmosis desalination plants, the de-
velopers must choose the ideal membrane, which is of course dependent on the
type of water. The selection of the appropriate membrane type is the most criti-
cal factor in determining the desalination plant’s success. The goal of this review
is to offer a detailed analysis on how to optimize water flux through the mem-
brane by using the solution diffusion model.

5. Models for Mass Transfer through Membranes

There are assorted technologies which can be used to produce a generic separa-
tion process of a mixture, such as distillation, adsorption, absorption, or mem-

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F. Z. Najdawi, K. T. Neptune

branes. While each process possesses distinct transport equations, they can all
still be used to separate a generic (A, B) mixture into A and B. A membrane is a
selective barrier which permits the transport of certain components through its
walls and captures others in the liquid or gas mixture. The stream which enters
the membrane is known as the feed-stream, whereas the fluid that moves through
the membrane is called the permeate. The fluid which holds the captured com-
ponents is known as the retentate or the concentrate [9].
The identifying characteristic of membranes applied to separation applica-
tions is their ability to determine the permeation of varying species. There are
two primary models most used to define this process of permeation. There is
first the solution-diffusion model, in which permeants dissolve in the membrane
material and then diffuse through the membrane down a concentration gradient.
The different permeants observe a separation because of differences in the quan-
tity of material which will dissolve in the membrane, along with the rate at
which the material diffuses through the membrane. The second model is that of
the pore flow model. In this model, permeants are separated by pressure-driven
convective flow through tiny pores. The permeants separate since one of the
permeants is excluded or filtered from some of the pores in the membrane
through which other permeants move. Both of these models were first developed
in the 1800s, however, the pore-flow model, being closer to normal physical ex-
perience, was more popular until the mid-1940s [1]. By 1980, the proponents of
solution-diffusion became more popular. Today, there are not many modelers
who employ the pore-flow model to observe reverse osmosis [1].
The overall mass balance over the membrane modules, assuming from the
hypothesis that no chemical reaction occurs, is represented as follows [9]:
n f = n p + nr = ∑ i n f xi. f = ∑ i n p xi. p + ∑ i nr xi.r (1)

In (1), n f represents the total molar flow-rate in the feed stream, n p

represents the total molar flow-rate in the permeate stream, nr represents the
total molar flow-rate in the retentate stream, and xi represents the molar fraction
of component i.
When evaluating the overall mass balance of a single piece of membrane, as
shown in Figure 6, and factoring in a control volume which encapsulates the en-
tire membrane module, then the total mass flux across the membrane and into
the mass balance can be written as follows [9]:

Figure 6. Graphical representation of the mass balance over the membrane module.

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 F. Z. Najdawi, K. T. Neptune

n f = nr + n p = nr + ∫ JdA (2)

In (2), ∫J represents the total molar flux of the permeating species, Ji

represents the molar flux equation for species, i, across the membrane, and, A,
represents the membrane section area where mass transfer occurs.
Mass transport across membranes requires differing forces to propel its ac-
tion. Non-equilibrium thermodynamics (NET) is the framework used to de-
scribe the wide range of behaviors which result from these disparate driving forces.
NET employs four postulates above and beyond those of equilibrium thermo-
dynamics: 1) The equilibrium thermodynamic relations apply to systems that are
not in equilibrium, as long as gradients are not too large (local equilibrium); 2)
All fluxes in the system may be written as linear relations involving all the driv-
ing forces; 3) No coupling of fluxes and forces occurs if the difference in tensori-
al order of the flux and force is an odd number (Curie’s Postulate); 4) In the ab-
sence of magnetic fields, the matrix of the coefficients in the flux-force relations
is symmetric (Onsager’s reciprocal relations).
Mass transfer can be described when multiple driving forces are present. This
is through the benefit of the Maxwell-Stefan Equation. The first calculation
needed to process the Maxwell-Stefan equation is the entropy balance equation
used to interpret irreversible processes (under the local equilibrium assumption,
entropy remains a valuable state function in non-equilibrium). The Max-
well-Stefan Equation is the total summation of the terms for concentration, dif-
fusion, pressure, force, and thermal diffusion. To simplify the Maxwell-Stefan
Equation, the following constraints are found to be necessary: 1) Negligible cur-
vature: Rcurv  1 (mass transport is unidirectional and perpendicular to the
membrane surface); 2) Immobility of the matrix: Vm = 0 ; 3) pseudosteady beha-
vior: (∂c_)/∂t = 0 (diffusional terms within the membrane are short compared to
those in the adjacent solution); 4) No thermal diffusion. The resultant Max-
well-Stefan Equation can be written thusly:
 δα , m 
N RT
∑ β =1 Ð ( xβ Nα − xα N β ) =− xα RT ∇ ln aα − zα F ∇V +  − Vα  ∇p (3)
αβ c  ρm 
In (3), Nα and N β represent the molar fluxes, δα ,m represent the Kro-
necker delta Vα , the partial molar volume of α. Ðαβ is the Maxwell-Stefan
diffusivities [9].
In the following sections, the model mass transfer for each module membrane
distillation will be discussed.
A. Model of mass transfer through porous membrane
The porous network is what provides for the transport, whereas the mem-
brane polymer itself is not instrumental in the transfer. With the case of porous
membranes, there is an equilibrium present between the fluids on each side of
the membrane and the material. This suggests a discontinuity in the concentra-
tion profiles at the interfaces. This equilibrium is governed by the solubility of
these compounds in the polymer.

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F. Z. Najdawi, K. T. Neptune

The Darcy Equation is a useful tool for expressing the molar flux over the
porous membrane. It can be written as follows:
Ðαβ dp
Jα =− vα cα ∇p =−cα K ′ (4)
RT dz
dp
In (4), represents the pressure gradient, cα represents the concentration
dz
of component A in the medium, and K' represents the permeability of the me-
dium. To describe the mass transfer, a combination of Knudsen diffusion and
Poiseuille flow can be used [16]. The membrane permeability coefficient ℘ is
then calculated as follows:
rpor ε  M 0.5 2
rpor ε MPpor
=℘ 1.064   + 0.125 (5)
τδ  RT  τδ µ por RT

In this equation, rpor represents the radius of the pores (m), µ represents the
viscosity for the pore (Pa∙s), R represents the gas constant (J∙K−1∙mol−1), Ppor
represents the membrane permeability for the pore (kg∙m−2∙s−1∙Pa−1), T represents
the temperature (in Kelvin),ẟrepresents the membrane thickness (m), M represents
the molecular weight (g∙m−1), τ represents the tortuosity, and ε represents the po-
rosity. This can also be referred to as the void fraction, which represents the void
space in materials. Mathematically speaking, this is the ratio of the volume of
interstices of a material to the volume of its mass. As we can see from (5), the
permeability coefficient relies heavily on the properties of the membrane materi-
al: porosity e, membrane thickness d, tortuosity s and pore diameter. In most
cases, the pore diameter should be 0.3 lm or smaller in order to avoid wetting.
Additionally, the optimal membrane thickness is known to be between 20 and
200 µm. The slimmer the membrane, the higher the flux, in spite of the fact that
a thinner membrane could cause higher loss of heat via conduction. The porosi-
ty should be as high as possible; e > 75%; which will ensure a high insulation,
and thus a high thermal efficiency. For this case, a lower tortuosity is recom-
mended, something around 1.1 to 1.2. When a high porosity is attained, the tor-
tuosity is assumed to be sufficiently low. In order to avoid wetting, the adequate
LEP is around 2:5 bar. This value is based on the material properties and the hy-
drophobic character of the membrane [17]. A contact angle of roughly 120 de-
grees is recommended to ensure the hydrophobicity of the membrane [11].
B. Model of mass transport through dense membrane and non-porous
membrane
In the case of a dense and non-porous membrane, a solution-diffusion process
produces the separation, and it requires the sorption of the compound at the up-
stream interface of the membrane, followed by its diffusion through the materi-
al, and then its desorption downstream of the membrane. Water permeability is
determined by two factors according to the solution-diffusion mechanism. First,
there is the solubility (S), which relies on the interaction of the polymer matrix
with water. Then, there is diffusivity (D), which is primarily determined by the

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 F. Z. Najdawi, K. T. Neptune

diameter of the components to be separated and by the mobility of the polymer

chains [11]:
P = DS (6)
The concentration gradient supplies the driving force of transport through a
dense membrane, and in the case of membrane distillation, this concentration
gradient creates a variance in vapor pressure on both sides of the membrane. In
order to facilitate transport, a lower permeate vapor pressure than that of the
feed side must be maintained [11]. The mass transfer resistance present in a
self-supporting dense membrane is always much higher than that of a dry mi-
croporous membrane of the same thickness. Because there is an absence of po-
rosity, the effective diffusion coefficients of the transported molecules are many
orders of magnitude lower than those observed in a microporous membrane.
Because of this rule, the thickness of the dense material must be brought to a
very low value so that competition with the performances of dry microporous
membranes can be achieved.

6. The Solution Diffusion Model

When it comes to transport models for permeation in a polymer membrane, the
solution-diffusion model has gained the most traction amongst researchers and
engineers. This model provides for the following membrane separation processes:
reverse osmosis, gas separation, and pervaporation [1].
Transport can only happen through diffusion in the solution-diffusion model.
For it to be successfully transported, the component must dissolve in the mem-
brane first [11]. Within the solution-diffusion model, the pressure within the
membrane does not change at the high-pressure value (pr) and is thus taken as
constant, and the gradient in chemical potential across the membrane is ex-
pressed as a smooth gradient in solvent activity. This can be seen in Figure 7. In
the solution-diffusion model, the permeants dissolve (sorption) in the mem-
brane material at the upstream interface when a concentration gradient in

Figure 7. This diagram depicts the solution-diffusion permeation model for mass transfer
through the membrane.

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F. Z. Najdawi, K. T. Neptune

present that permits permeants to diffuse through the membrane and be de-
sorbed on the downstream interface side. These different permeants will sepa-
rate due to the fact that each material has a different diffusion rate in the mem-
brane [18].
When we return to the Maxwell Stephen Equation (3), and assume that no
pressure gradient exists within the membrane and no forces act on the mem-
brane, the molar flux of the component can be written as follows:
Jα =
−c Ðαβ xα ∇ ln aα (7)

Additionally, when we introduce the definition of activity in accordance with

the hypothesis of perpendicular flux, the Fick Equation can be seen below [9]:
dxα
Jα =−c Ðαβ xα ∇xα =−cDα , β nˆ (8)
dz
Here, Ðαβ = Dα , β in an ideal mixture.
With the framework of the solution-diffusion model, the goal is to connect the
flux equation and the continuity equation to the conditions in the mixture bath-
ing the membrane. The continuity equation is represented mathematically below
[9]:

c
Dxα
Dt
(
= −∇ ⋅ Jα + Rα − xα ∑ β Rβ
N
) (9)

Thus, it’s necessary to consider the conditions at the membrane interfaces:

equilibrium assumption between the membrane surface and the mixture on the
retentate or permeate of the membrane has been made [9]. In examining the flux
equations of Fick and Darcy, and substituting them into the continuity equation,
the solution-diffusion model can be expressed mathematically as follows [9]:
d dx 
cDα , β α  = 0 Solution-Diffusion Model (10)
dz  dz 

The following boundary conditions are applied to solve the solution-diffusion

model: At z = 0, xα = xα , R and z = L , xα = xα , P and yields:
I I

xαI , R − xαI , P
Jα = cDα , β (11)
δ
In this case xα , R , xα , P , cα , R , cα , P represent molar fractions and composi-
I I I I

tions for components within the membrane, but either at the feed or permeate
interface, and membrane thickness. The values of xα , R , xα , P can be seen in
I I

(12) and (13) [9]:

γ α ,r
xαI , r = xα , r (12)
γ αI , r
γ α , p   vα ,l  
=
xαI , p xα , p exp  −
γ α , p   RT
I ( pr − p p )   (13)
 
When we substitute these values in the solved solution-diffusion model and
assume that the ratio between the activity coefficient is the same at the retentate

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 F. Z. Najdawi, K. T. Neptune

or at the permeate side, this will yield the following arrangement [9]:
cDα , β γ α , r   vα ,l  
Jα ≈
δ γ α , r 
I  xα , r − xα , p exp  − ( pr − p p )   (14)
 RT  
Here, the subscripts r and p identify the retentate and permeate conditions,
respectively. In the solved solution diffusion model, the results confirmed that
flux rate is proportional to a gradient in the chemical potential and pressure
drop. As previously stated, reverse osmosis is primarily employed for the desali-
nation of saltwater. In this arrangement, membranes that are permeable to water
yet impermeable to salt are exploited. The objective of water desalination is the
production of fresh water at the permeate side. In Figure 8, the schematic of a
membrane module for water desalination is presented. Because a pressure dif-
ference is administered across the membrane, a liquid mixture at both sides can
be expected. Pressurized water which possesses dissolved salts contacts the feed
side of the membrane. At the same time, water that has had its salt removed is
withdrawn as a low-pressure permeate. This section seeks to express the flux
equations in terms of the pressure gradient through the membrane and render
them linear.
It is possible to rewrite (14) in terms of the change from the molar fraction to
the concentration below:
vw
( p f − p p ) − ∆π 
Qw
=Jw xw, f (15)
δ RT  

In looking at (15) and considering the ∆π = pr − p p , three potential scena-

rios can be drawn for a dense solution-diffusion membrane:
1) pr − p < ∆π . J w < 0 . Normal osmosis takes place. The water flows from
the pure-water side to the sea-water side, as seen in Figure 9.
2) pr − p = ∆π , J w = 0 . Here, the osmotic equilibrium is reached, and no
flux occurs due to the fact that the osmotic pressure is counterbalanced by the
pressure difference, as seen in Figure 10.
3) pr − p > ∆π , J w > 0 . Reverse osmosis takes place. The water flows from
the sea-water side to the pure-water side, as seen in Figure 11.

7. Thin, Highly Permeable Membrane

It is worth noting that recent studies and prior research have affirmed the possi-
bility of creating such a thin, highly permeable membrane, such as the study

Figure 8. Schematic of a membrane module for reverse osmosis [19].

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F. Z. Najdawi, K. T. Neptune

Figure 9. Schematic of an osmosis solution-diffusion membrane [9].

Figure 10. Schematic of an osmotic equilibrium solution-diffusion membrane [9].

Figure 11. Schematic of reverse osmosis solution-diffusion membrane [20].

done by Soyekwo in 2017 where a cellulosic composite membrane with a thick-

ness of 64 to 111 nm was synthesized [21]. A smooth, dense, ultrathin PEI bar-
rier was detected on the surface of this cellulosic membrane that had an esti-
mated thickness of around 10 nm. Further, another study revealed that several

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 F. Z. Najdawi, K. T. Neptune

nanometric thin films were fabricated using block copolymers, PEO and PBT.
The thickness of the membranes varied between 80 and 500 nm. These mem-
branes were applied to the CO2 absorption, finding a higher permeability than
commercial membranes [22]. Self-standing nanofilms of polysulfones doped
with sulfonate polysulfones were also prepared via solvent evaporation obtaining
a self-standing film of 46 nm thickness [23]. In another study issued by Karan et
al. in 2015, 10 nm-thick polyamide membranes were produced using controlled
interfacial polymerization, and it was found that the nanofilms were sufficiently
rigid [24].

8. Practical Application of the Solution-Diffusion Model

A study performed by Maddah and Almugahwi in 2017, applied the diffu-
sion-solution model to determine the appropriate membrane for a RO plant
[18]. This study provides an example of the practical application of this model
for plant optimization. With water-salt solution, the reverse osmosis permeation
expression used in the study can be simplified and easily be related to the pre-
vious equation (15). The specific equations for this study are (16) and (17) [1]
[25]:
J=
i A ( ∆p − ∆π ) (16)

Pc
i io vi
A= (17)
RTl
In (16), Ji is the membrane flux component i for water in (gfd), ∆p is the ap-
plied pressure drop across the membrane in (psi), ∆π is the osmotic pressure
drop across the membrane in (psi), A is the water permeability constant in
(cm/atm*s). In (17), Pi is the permeability of component i in water in (cm2/s), cio
is the initial mole concentration of water in (ppm), vi is the water molar volume
in (cm3/mol), T is the water temperature in (K), R is the gas constant (m3atm/
mol*K), and l is the membrane thickness which is assumed to be similar to the
spacer thickness in (mil).
Table 1 provides the data from the Abqaiq 500 RO plant applied to determine
the values for osmotic pressure drop for the RO membrane from (16) and (17).
To calculate the osmotic pressure for seawater sources, the same information of
Shedgum/Abqaiq groundwater was applied at Abqaiq 500 RO plant, except for
flux and salinity values, for the treatment of either Arabian Gulf or Red Sea wa-
ters [25]. Water permeability was determined to be approximately 9.5 × 10−7
cm2/s [28]. Membrane resistance constant for each BWRO Toray membrane can
be determined by using (18) below [28].
∆p
Ji = (18)
kRm
In (18), k is the dynamic viscosity of water in (lb*s/ft2) and Rm is the mem-
brane resistance in (t−1). The Van’t Hoff [29] osmotic pressure (π) formula is
useful for estimating the osmotic pressure of an aqueous solution from its molar

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F. Z. Najdawi, K. T. Neptune

Table 1. Data of RO membrane process at abqaiq 500 plant and the two seawater studied
scenarios [1] [26] [27].

Shedgum/Abqaiq Arabian Gulf Red Sea

Parameter
Groundwater Water Scenario Water Scenario
Membrane type Toray TM720D-400 with 8''

RO Module 72 parallel membranes × 8 units

Membrane thickness (  ) Assumed to be like spacer thickness of 34 mil

Membrane area (Area) 400 ft2

Max pressure drop
~60 psi
per vessel (ΔP)
Max pressure drop
~20 psi
per membrane (ΔP)
Water salinity (cio) ~2800 ppm ~41,070 ppm ~42,070 ppm

Membrane water flux (Ji) ~18 gfd ~12 gfd ~12 gfd

Water temperature (T) ~25˚C

Water permeability constant (Pi) 9.5 × 10−7 cm2/s

Water molar volume (ѵi) 18 cm3/mol

Gas constant (R) 8.2057 × 10−5 m3 atm/mol K

concentrations of dissolved species. In the three various water sources in (19),

the overall required osmotic pressure drop (Δπ) for a water treatment plant was
explored [18].
π = T (19)
In (19),  is the molar concentration of dissolved species in (mol/L),  is
the Ideal gas constant, 0.08206 L atm/mol K. Equation (20) can be used to de-
termine the fitness of a membrane in being able to separate salt from the feed
solution. This is known as membrane removal percentage and represented by, χ.
This fitness increases with the applied pressure. Three sources from Table 1 de-
rive the feed TDS concentration, while the outlet TDS concentration can be cal-
culated using (20). The water molecular weight of 18 (g/mol) is useful in con-
verting our ppm values to molar concentrations of TDS [28].
 c jo − c jl 
=X   ∗100 (20)
 c jo
 
In (20), X is the membrane removal percentage, cjo is the initial mole concen-
tration of component, j, which is salt in (ppm), and cjl is the final mole concen-
tration of component j in (ppm).
Altaee’s study demonstrates how permeate flow, pressure, and recovery rate
are distributed in a manner very similar to membranes per RO vessel [30]. Addi-
tionally, another field study proved a stronger performance by rearranging the
elements in pressure vessels so that the pressure drop and permeate conductivity

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 F. Z. Najdawi, K. T. Neptune

across the vessel can be reduced [31]. The traditional flux rates and maximum
recovery values for the groundwater and the two studied water source scenarios
(Arabian Gulf and Red Sea waters) at Abqaiq 500 RO plant are on display in Ta-
ble 2.
The applied pressure drop and suggested flux values are calculated for each of
the different types of membranes. The same osmotic pressure drop for each case
is used to determine the results of different Toray BWRO membrane types at
high, low, and standard operating pressures. The applied pressure drop should
be greater than the calculated osmotic pressure in order to create a positive flux
[18].
(16) and (17) permitted the calculation of the osmotic pressure drop (Δ𝜋𝜋) for
each water source. These calculations are evidenced in Table 3, where the os-
motic pressure of the groundwater source is lower than Arabian Gulf and Red
Sea water sources. This is due to the flux rates and water salinity. The flux rates
for Arabian Gulf and Red Sea waters are approximately half that of the ground-
water source, but water salinity of the groundwater source is significantly lower
than the other sources. It follows that the required applied pressure drop must
be greater in the case of seawater sources. This is because of the higher deter-
mined osmotic pressure values of these sources. Because the plant configuration
has 8 elements per vessel, we should have a maximum osmotic pressure of 60 psi
or less per vessel. This is equivalent to a max pressure of 7.5 psi per membrane if
the pressure is distributed equally on membranes per vessel. The selected applied
pressure range for this analysis is 6.5 to 7.5 psi. The maximum pressure values
are assigned to the different membranes’ dependent on their category.
Maddah and Almugahwi in their study find the relationship between the ap-
plied pressure drops and the overall water flux rates for the groundwater source.

Table 2. Characteristics of groundwater sources and studied water sources at Abqaiq 500
RO plant.

Shedgum/Abqaiq Arabian
Water Source Red Sea
Groundwater Gulf
Feed silt density index SDI < 3 SDI < 4 SDI < 4
Typical target flux, gfd 18 12 12
Max. element recovery, % 19 14 14

Table 3. Calculated osmotic pressure drop (Δπ) for each water source form (16) and (17),
[18].

A Ji Ji/A Δπ Δπ Δπ per
Water Source
(cm/atms) (cm/s) (atm) (atm) (psi) vessel < 60 (psi)
Shedgum/Abqaiq
0.00808 0.00083 0.10288 0.441 6.48 51.84
groundwater
Arabian Gulf water 0.00755 0.00056 0.07417 0.470 6.90 55.21
Red Seawater 0.00754 0.00056 0.07430 0.470 6.90 55.20

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F. Z. Najdawi, K. T. Neptune

They find that the maximum possible flux for the groundwater in the standard
membranes is around 11 gfd. The greatest groundwater flux that can be obtained
is 8 gfd at the high-pressure and low-membranes thickness. Also, the maximum
flux observed for low-pressure membranes is nearly 15 gfd. This observation is
relative to the membrane thickness, where the smallest membrane thickness (28
mm) was able to produce the highest flux. This finding proves that an inverse
relationship exists between the membrane thickness and the water flux rate, and
a linear relation between the applied pressure drop and the overall water flux can
be realized as well [18]. Finally, the membrane resistance for the three water types
is investigated. The study shows that seawater sources have greater membrane re-
sistances than groundwater sources. This is due to having lower flux and higher
TDS. The highest membrane resistance is obtained because of its low-pressure
category, and it has the greatest membrane thickness of 31 mm [18].

9. Conclusions
The solution-diffusion model can be applied to determine the optimum opera-
tional parameters of a variety of membranes. As seen in the example of the Ab-
qaiq plant, the osmotic pressure of an array of Toray membranes was evaluated
for the optimum configuration. The osmotic pressure values were calculated for
Arabian Gulf and Red Sea waters to estimate flux rates in the membranes for use
with saline water.
A linear relationship can be seen to exist between the water flux and the ap-
plied pressure drops, and thus it is confirmed that membrane flux decreases with
the increase in membrane thickness when the pressure drop is constant. The
findings from the Abqaiq 500 RO plant examples show that the lowest mem-
brane resistance and the highest overall water flux are the best membrane to se-
lect. Maddah and Almugahwi example reveals the effectiveness of the use of the
solution-diffusion mode for determining optimal membrane parameters. These
findings reveal the effectiveness of the use of the solution-diffusion model for
determining optimal membrane parameters. Ultimately, the design of more ef-
fective membrane parameters will mean that RO and other membrane-based
desalination systems can expect longer operational lives with fewer membrane-based
concerns, like scaling or fouling. Future research endeavors should be lent to-
wards exploring new ways to prolong membrane life, along with additional ex-
ploration into the effects that solvents have on membrane health.

Conflicts of Interest
The authors declare no conflicts of interest regarding the publication of this pa-
per.

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