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Journal of Membrane Science 107 (1995) 121
The solutiondiffusion model: a review
J.G. Wijmans, R.W. Baker *
Membrane Technology and Research, Inc., 1360 Willow Road, Suite 103, Menlo Park, CA 1940251516, USA
Received 28 December 1994; accepted 3 April 1995
Abstract
The solutiondiffusion model has emerged over the past 20 years as the most widely accepted explanation of transport in dialysis, reverse osmosis, gas permeation, and pervaporation. In this paper we will derive the phenomenological equations for transport in these processes using the solutiondiffusion model and starting from the fundamental statement that flux is proportional to a gradient in chemical potential. The direct and indirect evidence for the model' s validity will then be presented, together with a brief discussion of the transition between a solutiondiffusion membrane and a poreflow membrane seen in nanofiltration membranes and some gas permeation membranes.
Keywords: Solutiondiffusion model; Transport equations; Poreflow; Membrane mechanisms
1. Introduction
The principal property of membranes used in separation applications is the ability to control the permeation of different species. Two models are used to describe this permeation process. The first is the solutiondiffusion model, in which permeants dissolve in the membrane material and then diffuse through the membrane down a concentration gradient. A separation is achieved between different permeants because of differences in the amount of material that dissolves in the membrane and the rate at which the material diffuses through the membrane. The second is the poreflow model, in which permeants are separated by pressuredriven convective flow through tiny pores. A separation is achieved between different permeants because one of the permeants is excluded (filtered) from some of the pores in the membrane through which
* Corresponding author. Phone: (415) 3282228. Fax: (415) 3286580. 03767388/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved SSD103767388(95)001026
other permeants move. Both models were proposed in the nineteenth century, but the poreflow model, because it was closer to normal physical experience, was more popular until the mid1940s. However, during the 1940s, the solutiondiffusion model was used to explain transport of gases across polymeric films. This use of the solutiondiffusion model was relatively uncontroversial, but the transport mechanism in reverse osmosis membranes was a hotly debated issue in the 1960s and early 1970s [ 116]. By 1980, however, the proponents of solutiondiffusion had carried the day; currently only a few diehard poreflow modelers use this approach to rationalize reverse osmosis. In this review, the assumptions behind these two membrane models are discussed, and the appropriate transport equations for dialysis, reverse osmosis, gas permeation, and pervaporation are derived using the solutiondiffusion model. W e show that these diverse processes can all be described by a single unified approach based on the solutiondiffusion model. The experimental evidence that supports the solutiondif
2
J.G. Wijmans, R.W. Baker~Journal of Membrane Science 107 (1995) 121
fusion model as it applies to these processes is reviewed, and the transition region between pure solutiondiffusion and pure poreflow membranes is discussed.
where/x ° is the chemical potential of pure i at a reference pressure pO. In compressible gases, the molar volume changes with pressure; using the ideal gas laws in integrating Eq. (2) gives /zi =/x ° + RTIn(]/iCi) +RTIn p (4)
2. Concentration and pressure gradients in membranes
The starting point for the mathematical description of permeation in all membranes is the proposition, solidly based in thermodynamics, that the driving forces of pressure, temperature, concentration, and electromotive force are interrelated and that the overall driving force producing movement of a permeant is the gradient in its chemical potential. Thus, the flux, J~, of a component, i, is described by the simple equation
p7
To ensure that the reference chemical potential/~o is identical in Eqs. (3) and (4), the reference pressure pO is defined as the saturation vapor pressure of i, Pisae Eqs. (3) and (4) can then be rewritten as /x/=/z ° + RTln(y,ci) + vi(p P/sat)
(5 )
for incompressible liquids and the membrane phase, and as /~i = /z° + RTIn(yici) + RTIn ptPisat (6)
Ji =

Li~'~
( 1)
where d/zi/dx is the gradient in chemical potential of component i and Li is a coefficient of proportionality (not necessarily constant) linking this chemical potential driving force with flux 1. All the common driving forces, such as gradients in concentration, pressure, temperature, and electromotive force, can be reduced to chemical potential gradients, and their effect on flux expressed by this equation. This approach is extremely useful, because many processes involve more than one driving force, for example, pressure and concentration in reverse osmosis. Restricting ourselves to driving forces generated by concentration and pressure gradients, the chemical potential is written as
d/J, i = RTdln(")liCi) [
vidp
(2)
where Cgis the molar concentration (mol/mol) of component i, 7,. is the activity coefficient linking concentration with activity, p is the pressure, and vi is the molar volume of component i. In incompressible phases, such as a liquid or a solid membrane, volume does not change with pressure. Integrating Eq. (2) with respect to concentration and pressure gives /zi =/x ° + RTIn('yici) ~v~(p _pO)
(3)
J In this paper we ignore the cross coefficients of irreversible thermodynamics.
for compressible gases. A number of assumptions must be made to define any model of permeation. Usually, the first assumption governing transport through membranes is that the fluids on either side of the membrane are in equilibrium with the membrane material at the interface. This assumption means that there is a continuous gradient in chemical potential from one side of the membrane to the other. It is implicit in this assumption that the rates of absorption and desorption at the membrane interface are much higher than the rate of diffusion through the membrane. This appears to be the case in almost all membrane processes, but may fail, for example, in transport processes involving chemical reactions, such as facilitated transport, or in diffusion of gases through metals, where interracial absorption can be slow. The solutiondiffusion and poreflow models differ in the way the chemical potential gradient in the membrane phase is expressed [8,9,15,17]: The solutiondiffusion model assumes that the pressure within a membrane is uniform and that the chemical potential gradient across the membrane is expressed only as a concentration gradient. The poreflow model assumes that the concentrations of solvent and solute within a membrane are uniform and that the chemical potential gradient across the membrane is expressed only as a pressure gradient.
the difference in pressure across the membrane (PoPe) produces a gradient in chemical potential according to Eqs. In both models.G. 1. which is at the feed pressure throughout. ( 1 ) and (2). Wijmans. No pressure gradient exists within the membrane matrix material. In the poreflow model. which compares pressuredriven permeation of a onecomponent solution by solutiondiffusion and by poreflow 2. Baker~Journal of Membrane Science 107 (1995) 121 3 Solutiondiffusion model Highpressure solution Chemical potential IJ i Pressure p Membrane Lowpressure solution Solvent activity 7 I c I Poreflow model Chemical potential Pl Pressure p Solvent activity 7 i e i Fig. in the poreflow model. R. a pressure is applied across a dense membrane. ( 1) and (2) in the absence of a concentration gradient in the membrane gives J= Ldv ~p dx (7) . Consequently. the pressure difference across the membranes is expressed as a concentration gradient within the membrane. the pressure gradient exists only in the fluidfilled pores. with Eqs. Consider the poreflow model first. Combining Eqs. The consequences of these two assumptions are illustrated in Fig. This assumes. the pressure everywhere within the membrane is constant at the highpressure value. The existence of two pressure gradients is a consequence of the twophase nature of the poreflow model. Pressuredriven permeation of a onecomponent solution through a membrane according to solutiondiffusion and poreflow transport models 2. that solutiondiffusion membranes transmit pressure in the same way as liquids. the pressure difference produces a smooth gradient in pressure through the membrane. The solutiondiffusion model on the other hand assumes that. W. in effect. 1.J. when z At this point it is worth noting that. ( 1 ) and (2) providing the mathematical link between pressure and concentration. but the solvent activity (•iCi) remains constant within the membrane.
2(a) shows a semipermeable membrane separating a salt solution from pure solvent. The subscript m is used to represent the membrane phase. 2(b). on substituting Eq.P e ) = A ~r.Cie(~) ) ( 11 ) f 2. respectively.zifon the water side to IXio on the salt side. . where the pressure abruptly falls frompo to Pe. across the membrane balances the solvent activity difference A (y~c~) across the membrane. As shown in Fig. . it follows.vi(po . the pressure within the membrane is assumed to be constant at the highpressure value Po. Osmosis according to the solutiondiffusion model Fig. smooth gradient in chemical potential of the water (component i) across the membrane from ~. ( 1 ). For simplicity. when sufficient pressure has been applied to the saline side of the membrane to bring the flow across the membrane to zero.G. pressure. The difference in concentration across the membrane results in a continuous. but we assume the membrane to be very selective. We can also define A (yici) by yie~m)Cie~m~= (yieCie) . 2 (b) shows the situation at the point of osmotic equilibrium. Fig. Eq. as RTLi dci J~ . Wijmans.D i ~ ( 10 ) and integrating over the thickness of the membrane then gives 3 J i : D i ( ci°' "~ . . that RTIn[ 1 .P e ) is equal to the osmotic pressure difference A 7r. Thus.°. so the concentration of salt within the membrane is small. This pressure difference ( P o . water passes across the membrane from right to left. the gradient of salt (component j) is not shown in this figure. c~ dx (9) This has the same form as Fick's law where the term R T L J c i can be replaced by the diffusion coefficient D~. 2. The flow that occurs down this gradient is again expressed by Eq. Eq. There is a discontinuity in pressure at the permeate side of the membrane. the pressure difference.~ is the concentration of component i in the membrane at the feed interface (point o). The pressure within and across the membrane is constant (i. and the solvent activity gradient (yici) falls continuously from the pure water (solvent) side to the saline (solution) side of the membrane. ( 1 ) and (2). Consider the application of the solutiondiffusion model to osmotic membranes first. (1) can be written. we can discuss concentration and pressure gradients according to the two models in a somewhat more complex situation.~c~) = vi(PoPe) RT  viA 7r . . The activity.A (y~ci) ] = . %. and the flow is zero. but. ( P o . Equating the chemical potential on either side of the permeate interface.RT (15) Thus. 3 In the equations that follow. (13) into Eq. from Eq.1. since (TieCie) ~ 1. of the membrane.W. by combining Eqs. and g is the membrane thickness. (14) reduces to (14) A(~.oi(Pope) (12) Using osmosis as an example.4 J.P e ) Since A (yici) is small. In the solutiondiffusion model. Thus: Ji = . and the gradient in chemical potential across the membrane is expressed as a smooth gradient in solvent activity (y~c~). Thus the term % represents the concentration of component i in the fluid (gas or liquid) in contact with the membrane at the feed interface. equal to Lv. the pressure on the solvent side of the membrane. the terms i andj represent components of a solution.A (yici) (13) and. and the terms o and e represent the positions of the feed and permeate interfaces. because no pressure gradient exists within the membrane. As a result. B a k e r / J o u r n a l of Membrane Science 107 (1995) 121 This equation can be integrated across the membrane to give Darcy's law J k(pope) g (8) where k is the Darcy's law coefficient. R. the pressure within the membrane is constant at the highpressure value (Po). . and chemical potential gradients within this type of membrane are illustrated in Fig. (12). The pressure is the same on both sides of the membrane. (5) we obtain R/In('yif(m)Cif(m))  RTIn ('YieCie) = . Po =Pro = P e ) .e.
2. Wijrnans. This is the process of reverse osmosis. so the chemical potential gradient within the membrane is expressed as a concentration gradient. R. and pressure gradients within an osmotic membrane according to the poreflow model are illustrated in Fig.2. chemical potential. and solvent activity profiles in an osmotic membrane according to the solutiondiffusion model. 2.J. W.G. 3. Osmosis according to the poreflow model The activity. resulting in a flow from left to right. Baker~Journal of Membrane Science 107 (1995) 121 Dense solutiondiffusion membrane Solution Membrane Solvent (a) Osmosis Chemical potential Pl Pressure p Solvent activity 71 c I (b) Osmotic equilibrium Pi P Ap = Art %cl y (~ ci) = V i A r t RT (c) Reverse osmosis pl p %Cl o l Fig. 2(c). pressure. Chemical potential. The pressure in the membrane is uniform and equal to the highpressure value. 2 and shows the gra . If a pressure higher than the osmotic pressure is applied to the feed side of the membrane. as shown in Fig. This figure is the poreflow equivalent of Fig. then the solvent activity difference across the membrane increases further.
3. poreflow membrane Solution Membrane Solvent (a) Osmosis Chemical potential Pi Pressure p Solvent activity ! 7i ci (b) Osmotic equilibrium Pi Ap = A~ (c) Reverse osmosis Pl ~/i Ci o l Fig. Fig. 3 ( b ) shows the situation at the point of osmotic equilibrium. the pressure gradient within the membrane is at the permeateside value. 2 ( b ) . and there is a discontinuity in pressure at the feed side interface where the .G.6 J.W. Baker~Journal of Membrane Science 107 (1995) 121 Porous. As in Fig. Fig. The concentration within the membrane is assumed to be uniform. dients when a very selective semipermeable porous membrane separates a solute solution from a pure solvent. so the chemical potential gradient in the membrane is expressed as a pressure gradient. R. when a sufficient pressure has been applied to the solute solution side of the membrane to bring the flow across the membrane to zero. Chemical potential. pressure and solvent activity profiles in an osmotic membrane according to the poreflow model. Wijmans. 3 ( a ) shows the case of normal osmosis with no concentration gradient within the membrane but a pressure gradient induced by the concentration difference between the solutions on either side of the membrane.
Dialysis To illustrate the application of the general procedure described above.) which leads to 17) 3..1.cie ) (22) The product Di.~.W.) is the sorption coefficient. only a pressure gradient exists. Eq. to give the familiar expression describing permeation through dialysis membranes D~Ki Ji = T ( Ci° . The general approach is to use the first assumption of the solutiondiffusion model. Within a perfect poreflow membrane. namely. g i and .)~lio(m) 18) "cio 19) The ratio of activity coefficients y~/y~. These values for Cio~m~and ci~m~ can then be substituted into the Fick's law expression. = Ki. we will derive the appropriate solutiondiffusion model transport equation for dialysis. (5) and (6)...°>) and. thus ci. For many systems. to give the transport equation for the particular process. equating the chemical potentials at the feed side interface of the membrane gives ~ i o = ~'~io(m) (16) Substituting the expression for the chemical potential of incompressible fluids from Eq. the appropriate equations for the solutiondiffusion model for transport in dialysis. although the fluids on either side of a membrane may be at different pressures and concentrations. (19) becomes Ci. Eq. The concentration gradient across the membrane causes a flow of solute and solvent from one side of the membrane to the other... K~ is normally referred to as the permeability coefficient. the appropriate quantitative expressions describing flow through solutiondiffusion membranes are derived by calculating the concentration gradient within the membrane and then substituting this gradient into the Fick's law expression. gas permeation. the concentration of the differing species in the membrane at the fluids interface Cio~ and c~e~m~can be obtained in terms of the pressure and composition of the feed and permeate fluids. The resulting equations linking the driving forces of pressure and concentration with flow are then shown to be consistent with experimental observations. When a pressure higher than the osmotic pressure is applied to the feed side of the membrane. Eq.P e ) is equal to the osmotic pressure A 7r.Pi~a. Flow through this type of membrane is expressed by Fick's law. ( 11 ). In("YioCio) = In( Yio~m)ci. 3 is that.. Oi.G. (8). P~. 3(c). = Ki'cio (20) On the permeate side of the membrane. ( 11 ). From this assumption. This pressure difference ( P o .<.Go. the same procedure can be followed. and solvent flow is from left to right. the chemical potential in the fluid and membrane phases can be equated using the appropriate expressions for chemical potential given in Eqs..(m ... a membrane is used to separate two solutions of different compositions. R. 3. Eq. Wijmans. and pervaporation membranes are derived. ( 11 ). In dialysis. 1 Fig.. Following the general procedure described above.m. and Eq. (20) and (21) into the Fick's law expression. The important conclusion illustrated in Fig. that the chemical potential of the feed and permeate fluids are in equilibrium with the adjacent membrane surfaces. Flow through this type of membrane is expressed by Darcy' s law. In the next section. 2 Fig. reverse osmosis. Baker~Journal of Membrane Science 107 (1995) 121 7 pressure difference Zip across the membrane occurs.. as shown in Fig.cie (21) The concentrations of permeant within the membrane phase at the two interfaces can then be substituted from Eqs. By rearranging these equations. the pressure gradient within the membrane increases further.J..(Po . ) + V~. Application of the solutiondiffusion model to specific processes In this section. (5) gives /z° + RTIn("YioCio)+ vi(po P&at) = t ~ + RTln( %. leading to an equivalent expression Cie~m. which is the simplest application of the model because only concentration gradients are involved.. within a perfect solutiondiffusion membrane only a concentration gradient exists. Ki..
Some experimental data illustrating this effect are shown in Fig.5 x 10.8 J. In reverse osmosis. From Eq. Wijmans. Ki and Pi that are averaged over the membrane thickness.. we are usually dealing with two components. the slope of this line is the permeability. depending only on the permeant and the membrane material. 2(b)] from Po within the membrane to Pe in the permeate solution. the product of permeability and the progesterone saturation concentration of the solute. If pressures greater than the osmotic pressure are applied to the salt side of the membrane. a pressure difference exists [as shown in Fig. The permeability calculated from these plots varies from 9. 2(b)].p ( . (20) ] cio. water (i). but much less permeable to salt) is used to Rearranging and substituting for the sorption coefficient. a membrane freely permeable to water.. This process is called reverse osmosis and is an important method of producing pure water from salt solutions. However. Reverse osmosis Reverse osmosis and normal osmosis (dialysis) are directly related processes. silicone oil. J~. if a permselective membrane (i. Equating the chemical potentials at this interface gives the same expression as in dialysis [cf. P~csat. 3. which is a plot of the progesterone flux times the membrane thickness.. the chemical potentials at both sides of the membrane are first equated.) which leads to In(y~c~. Thus. At the feed interface. gives the expression cie. If a hydrostatic pressure is applied to the salt side of the membrane. 4 [ 18]. m. Eq. the flow of water can be retarded and. and polyethylene glycol MW600 (PEG 600). e.. (22) implies the use of values for Di. Eq.G.. (22). Pg.~ocm2/s for PEG 600. (23). respectively.) = tx° + RTln( Yie~m)Cie~. 23. In simple terms. but. and salt (j)..2. in which the solvent used to dissolve the progesterone is water.e.~) = ln(Yie~m~C~cm) + v~(po Pe) ) RT (29) (28) The term Di/")/i(m) and therefore the term P~c~t are determined solely by the permeant and the membrane material and are thus independent of the liquid phase surrounding the membrane. when the applied pressure is sufficient.s. = Ki "fit" e x. The permeability coefficient P~ is often treated as a pure materials constant. = Ki'ci. R. Three sets of permeation experiments are reported.5 X 10 7 cm2/s for water to 6. in fact. This result is also in agreement with Eq. Ki.= P~(sat = Substituting the appropriate expression for the chemical potential of an incompressible fluid [Eq. (5)] yields Di (25) Ti Ti(m) /~o + RTIn("yieCie)"31vi(pe Pis. (26) At the permeate interface.W. The hydrostatic pressure required to stop the water flow is called the osmotic pressure (A ~).. the flow ceases. This difference reflects the activity term yi in Eq. (qo .vi(PoPe) ] ] RT: (30) . Following the general procedure. From Eq. the pressure in the feed solution and within the membrane are identical [as shown in Fig.c~).~) + v i ( p o . against the concentration difference across the membrane. water will pass through the membrane from the purewater side of the membrane into the side less concentrated in water (salt side). Baker~Journal of Membrane Science 107 (1995) 121 thus Pe are concentration dependent. is a constant as shown in Fig.P. Equating the chemical potentials across this interface gives ~i~ = ~i~'(m) (27) 1 Csat (24) yields Pi . and water begins to flow from the salt solution to the pure water side of the membrane. P~ can be written as Pi = Di" ~/i/ ~li(m) (23) It is the presence of the term Yi that makes the permeability coefficient a function of the solvent used as the liquid phase. 4(d).. which combined with the approximation ')/i separate a salt solution from pure water. This process is called normal osmosis. (19). the nature of the solvent used in the liquid phase is also important. then the flow of water is reversed.
75 0.. Wijmans.6 0.sec)] 9 2.000 15..cm/cm2.f) is plotted against the progesterone concentration across the membrane. ~ . I 0 0.cm/cm2see)] 1 5 l . Eq. (31 ) and the equivalent expression for c o m p o n e n t j give the water flux and the salt flux across the reverse .cm/cm2.0 Saturated solut!o~.0 1. Because of the different solubilities of progesterone in these solvents.sec)] 15L "  Saturated solution ~ c 0.000 10. is a materials property dependent only on the membrane material and the permeant..J. The thicknessnormalized progesterone flux (jr.0t Saturated 0 5..0 t Water 1. Permeation of progesterone through polyethylene vinyl acetate films. or DJ%(m). The slope of this line Pfsa.5[ f.50 0. R.sec)] 0. ~ . 0 2 4 6 8 10 12 14 Progesterone concentration.2 Fractional progesterone saturation. ( 11 ). The solvent phase used to dissolve the progesterone is (a) water. All the data can be rationalized onto a single curve by plotting the thicknessnormalized flux against fractional progesterone saturation as described in the text and shown in (d).z~ Water . and is independent of the fluid used as the solvent. Ac [ 18].cm/cm2.G.00 Progesterone flux x membrane thickness..~" [] Silicone oil (Dow 360) ¢o" o Poly(ethylene glycol) (PEG 600) 0 j ~ . 4.. J .25 1.2 0.~ .. and (c) polyethylene glycol (PEG 600).8 1. Ac (pg/ml) (c) Progesterone flux x membrane thickness. JI [10 "11 x (g.5 0 ~.  (31) Eq..5 l 2. Ac(pg/ml) (d) 1. Ac(pg/ml) (b) Progesterone flux x membrane thickness. Jl [10 11 x (g.4 0.50 Saturated 1. l [10 11 x (g. The expressions for the concentrations within the m e m b r a n e at the interface in Eqs.Z 0. W. the permeabilities calculated from these data through Eq.25 .~"I I I I I I 0 100 200 300 400 500 600 700 Progesterone concentration. to yield J' = . (b) silicone oil. ( 2 6 ) and ( 3 0 ) can n o w be substituted into the F i c k ' s law expression.~. JI [10 "11 x (g.000 20.00 Progesterone concentration..i  c. Ac/csa t Fig. (22) vary 1000fold. Baker~Journal of Membrane Science 107 (1995) 121 (a) Progesterone flux x membrane thickness.
which is defined as = (1cJetXlO0%~cjoj (42) (36) fRT This equation can be simplified to J~=A( Ap.10 J. the solutiondiffusion model has also been used by many workers to obtain diffusion and partition coefficient data. a gas mixture at a pressure Po is applied to the feed side of the membrane. R. DiK. Baker~Journal of Membrane Science 107 (1995) 121 osmosis membrane in terms of the pressure and concentration difference across the membrane. when Zip = 100 atm.vi(Zlp . Eqs.3. K.ATr) (37) where A is a constant equal to the term DiKiC~oV~/fRT. Gas separation In gas separation./17r= 10 atm. that is.06. (37). As well as predicting the general form of the salt and water transport through reverse osmosis membranes. The rejection coefficient increases with applied pressure as shown in Fig. 5.[Cioand. At the point at which the applied hydrostatic pressure balances the water activity gradient.]] RT ]J (32) Jj=B(CjoCje) (40) where B is usually called the salt permeability constant and has the value (33) fie= % e x p ( ~ ) B . Eq. through the membrane can be derived. (31) becomes Because the term . cje = 0 and = 100%.G. 2.exp. Under these conditions.°j/~j (41) At hydrostatic pressures higher than A ~. the exponential term in Eq. whereas according to Eq.W. a simplified expression for the salt flux. According to Eq. the term v~(zip . Eq. while the Jj=~[CjoCjeexp(V~(~TPe))] (38. For example. 5. cie = % and R = 0%. the point of osmotic equilibrium in Fig.14]). and for a completely unselective membrane. the salt flux is essentially independent of pressure. Similarly.exp(x) ~ x as x* 0 can be used. (38) is close to one. For a perfectly permselective membrane. where Ap is the difference in hydrostatic pressure across the membrane (PoPe). and Eq. Consider the water flux first.Zi 7r)/RTis small under the normal conditions of reverse osmosis.Cjt) or (39) Ji = 0 ={. Some typical results are shown in Fig. [ Ci~ ex ~(  vi( A ~). but the salt flux does not. (38) can then be written as oj~ Jj= ~( Cjo.ZI ~r)/RT is about 0. (40). Also shown in this figure is a term called the rejection coefficient. the constant A is usually called the water permeability constant. (31 ) can be simplified further. Jj. 3. However. In the reverse osmosis literature. the water flux through a reverse osmosis membrane remains small up to the osmotic pressure of the salt solution and then increases with applied pressure. (29) can be written to a very good approximation as Ji = Digici°ui( A p . starting with the equivalent to Eq.vj(po Pc)/RT is small. and Eq. These data appear to be selfconsistent and reasonable. the flux of water across the membrane is zero. A trial calculation shows that the term .Zi 7"i") Predictions of salt and water transport can be made from this application of the solutiondiffusion model to reverse osmosis (first derived by Merten and coworkers [13. based on diffusion coefficient data from gas separation and pervaporation. because the water flux increases with pressure. thus. ~~ (34) jiDiKeici°[1exp(vi(A~TATr))] (35. and vi = 18 cm 3. the simplification 1 .. (31 ): The rejection coefficient is a measure of the ability of the membrane to separate salt from the feed solution. . (33) and (31) can be combined to yield J~= or o c/o[ f 1 . Wijmans.
and.6oo 1. meets the pressure axis at the osmotic pressure of sea water ~ 350 psi. the Chemical potential for the gas phase is given by Eq. The salt flux. Wijmans. is essentiallyconstantand independentof pressure. G. increaseswith pressure. permeate gas at a lower pressure Pe is removed from the downstream side of the membrane.. CioeXp~ ~ j ci°(m) = ~io(.= l~i d.RTln( Tio~.~Cio~. (40). . The water flux.. (6) for a compressible fluid. whereas Eq. (37). 5.. (16) at the gas/membrane feed interface yields /X + RTln(3%cio) ° + R T l n . (5) for an incompressible medium is applied to the membrane phase.) Plsat (43) which rearranges to Po o 'F ~i Po [lYi(PoPi~at)'~ . . FF30 membrane)as a functionof pressure. W.J. .n) P/sat (44) . however. in accordancewith Eq. Baker~Journal of Membrane Science 107 (1995) 121 11 30 25 Water 20 Water flux 15 (L/m2h) 5 / 10 5 / Osmotic / )ressure AR / ^ 4 flux [ I Salt 3 flux 2 (g/m2"h) 0 100 80 60 40 20 Salt rejection (%) I I I ! I I I I I I o 2oo 4oo coo 1. Substitution of these equations into Eq.5% sodiumchloride) in a good qualityreverse osmosis membrane(FilmTec Corp.. Flux and rejectiondata for a model seawater solution (3.)) vi(PoPisa. R. at zero flux. This time.in accordancewithEq.2oo Applied pressure (psig) Fig. As before. the starting point for the derivation of the gas separation transport equation is to equate the chemical potentials on either side of the gas/membrane interface.
significant deviations from ideality of the vapor's activity coefficient can also occur at high partial pressures. (50) is widely used to accurately and predictably rationalize the properties of gas permeation membranes. even for gases. This is in sharp contrast to the permeability constant for liquids as described in the discussion centered on Fig. the concentration of component i at the membrane/permeate interface can be shown to be Cie(~) = g~i Pi e (48) Combining Eqs. Eq. In rubbery polymers. relatively independent of the composition and pressure of the feed and permeate gases because gasphase activity coefficients. then gives JiDiI~i (Pio . (58) to distinguish between the liquidphase sorption coefficient K. In glassy polymers. Second. Ti. Baker~Journal of Membrane Science 107 (1995) 121 Because the exponential term is again very close to one 4. but the molar volume of i dissolved in the membrane material. this derivation explicitly clarifies the assumptions behind this equation. This effect is commonly ascribed to plasticization and other effects of the permeant on the membrane changing Di and Ti(. a high affinity for the membrane material (small ")li(m)). the decrease in diffusion coefficient far outweighs other effects.P i e ) (49) The product DiKe/is often abbreviated to a permeability coefficient. The permeability coefficient P~ can be written as The term T~o/(Pisa.12 J. there is a gradient in concentration within the membrane but no gradient in pressure. (45) and (46) with the Fick's law expression. Pio "Yio(m) Pisat (46) However. and permeabilities fall significantly as molecular weight increases [ 19]. we will use P~ for the permeability coefficient for gases to distinguish from P~ for liquids. (44) reduces to Cio(m )  "YioCio Po • ~/io'(m) (45) Pisat The term % "Po is the partial pressure of i in the feed gas.G. Eq. 5 The superscripts G and L are used here and later in Eq. thus. (51) is also a useful way of rationalizing the effect of molecular weight on permeability. 4 earlier. (20) and the gasphase coefficient ~ defined by Eq. 4 While evaluating this exponential term (the Poynting correction). (50) is a longwinded way of arriving at a trivial result. Eq. but. in which the Poynting correction was assumed to be one. the concept of permeability as a materials constant must be treated with caution. even for very large pressures Po. The permeant's saturation vapor pressure Pisat and diffusion coefficient both decrease with increasing molecular weight creating competing effects on the permeability coefficient. the absorption of a component into the membrane is proportional to its activity in the adjacent gas but is independent of the total gas pressure. the two effects are more balanced. it is important to recognize that vi is not the molar volume of i in the gas phase. It might be thought that the derivation leading to Eq. R. (45) then simplifies to Cio(m )  Yio . This is related to the approximation made in Eq. W. First. P~ and ~ have different dimensions but can be easily interconverted as shown in the pervaporation section that follows. However. the concentration of component i at the feed interface of the membrane can be written as Cio(m) = I~i P~ D"T~ Ti(m) "Pisat (51) "Pio (47) In exactly the same way. (42). Eq. (51 ). on the other hand.. Similarly. which is approximately equal to the molar volume of liquid i. defined . and a low saturation vapor pressure (Pisat)" P~ is close to being a materials constant. P ~.) in Eq. Eq. Pio. the permeability of vapors at partial pressures close to saturation often increases substantially with increasing partial pressure. (11). For molecular weights up to 100. a limited affinity for the gas phase (high Yi). Wijmans. For example. permeability generally increases . leading to the familiar expression Ji Pi (PioPie) e G (50) Eq. are usually close to unity."Y~o(m)) is the sorption coefficient / ~ 5.r by Eq. (47). but it is interesting because it shows that large permeability coefficients are obtained for compounds with a large diffusion coefficient ( D i ) . (51 ) is not a commonly used expression for gasphase membrane permeability.
Above pentane. 7.01 i i t 0.Permeabilitydata from [20]. and permeabilities fall with increasing molecular weight of the permeant. (5) then gives /x° + RTIn(~/ioCio) ~. G. Chemical potential. and activity across the membrane are illustrated in Fig. (19) in the dialysis and reverse osmosis sections.ui(Po Pi~.000 C5H12 C8H18~"~4H10 i~. however. The gradients in chemical potential. so that the permeating components are removed as a vapor mixture. Eq. R. Pervaporation preferentially permeates one or more of the components.. is larger than the effect of increasing size or Di. where Ki is the liquidphase sorption coefficient defined in Eq.. As the molecular weight increases from CH 4 tO CsHI2. pressure.J. The equivalent expression for the chemical potentials in each phase is then . PI G (Barrer) 1. and activity profiles through a pervaporation membrane following the solutiondiffusion model.Pi~a. the chemical potential of the feed liquid is equilibrated with the chemical potential in the membrane at the same pressure. with increasing molecular weight because Piss.000 Permeability. the trend is reversed. At the liquid solution/membrane feed interface. the molecular weight term gradually becomes dominant.4. the pressure drops from Po in the membrane to Pe in the permeate vapor.000 Fig. is the dominant term. PermeabilitycoefficientP~ of nalkanes in polydimethylsiloxaneas a functionof saturation pressure.. Some data for permeation of simple alkanes in silicone rubber membranes that illustrate this behavior are shown in Fig.) =/x ° + RTIn( y~o~>C~o... A partial vacuum is maintained on the permeate side of the membrane. Above molecular weight 100. Baker~Journal of Membrane Science 107 (1995) 121 100. W.~ which leads to an expression for the concentration at the feedside interface ~/ioCio Cio(.1 1 10 Permssnt saturation vapor pressure.~ 'IP C6H14 ~.) . v~(po Pi~t) (52) Pervaporation is a separation process in which a multicomponent liquid is passed across a membrane that Feed solution Membrane Permeate vapor IJl IJ i p . 3.. At the permeate gas/membrane interface.000 13 10. Transport through the membrane is induced by maintaining the vapor pressure of the gas on the permeate side of the membrane at a lower vapor pressure than the feed liquid. pressure. 6 [20]. Plsat (stm) i 100 1. 7.~3H8 C10H22 ~6 Increasing diffusion coefficient Increasing molecular weight "~H4 100 0. Wijmans.~~lio(m) Ki'Cio (53) Fig. the effect of the decrease in Pisa. 6..001 i 0.
. the exponential term is close to 1. R.v i ( P o .. G.. However. 8..Plsat I 0 I. W.) • fie' Pe P is~. Wijmans.. (53) and (57) can be substituted into Eq.t (56) The product cie "Pe can be replaced by the partial pressure term Pie. This vaporliquid equilibrium can then be written Id~io ~R / i n ( ~io " C~o) + l"i(Po Pi~at) Tie Tie(.)) +vi(PoPisa. (58) becomes .lO I • I •t I 5 10 Permeate pressure • •~ .. /zo + R / i n ( ~liecit ) ~RTh~~J "¢" i s a t / =tz°+R/in(Y~e¢m~C~e¢.. The effect of permeate pressure on the water flux through a silicone rubber pervaporation membrane.) ")lie Pie "}lie(m) Pisat K~i "Pie (57) Following the same steps as were taken from Eq.. (53) is a liquidphase coefficient whereas the sorption coefficient in Eq. thus.h) 200 C 100  • • 40°C ? . e x ~ .) Rearranging Eq. ( 11 ) (Fick's law) to obtain an expression for the membrane flux... thus = ~i "~ R/In( yico• c G) + R / I isar o (58) Cie(. (57) is a gasphase coefficient. (47) in the gas separation section. Eq.. Pisat Pe C i e . the sorption coefficient in Eq.14 J. 15 (cmHg) Fig. (54) gives "}lie Cie(m) (54) "Yif(m. The arrows on the lower axis represent the saturation vapor pressures of the feed solution at the temperature of these experiments. Baker~Journal of Membrane Science 107 (1995) 121 400 300 Permeate flux (g/m2.y ~ . The concentration terms in Eqs. (54) to (57). The interconversion of these two coefficients can be handled by considering a hypothetical vapor in equilibrium with feed solution [21 ]. the concentration at the permeate side interface is: Cie(m) : where K~ is the gasphase sorption coefficient defined in Eq.P i s = ) l "~ "J (55) AS before.
Cio ~io. The explanationfor this behavioris the transport Eq. (61). for example.o" Hipi~) From Eq. The term ~ .19]. the use of vapor pressure leads to much more useful results.0 flux (kg/m2. The driving force could equally well have been expressed in terms of concentration differences. Substitution of Eq.pJ~. therefore (62) ef Pi= eiG" Hi as (63) and. shows data for the pervaporation of water as a function of permeate pressure. (53) yields c. YiCo Pio K~. Hi. The flux decreases with increasing permeate pressure. The straight lines in Fig. reaching a minimum value when the permeate . This can be expected in this and similar systems in which the membrane material is a rubbery polymer and the permeant swells the polymer only moderately. n. The effect of feed and permeate pressure on the flux of hexane through a rubbery pervaporation membrane. 9(a) shows. (59) it follows that ~ = / ~ . Thompson et al. As the permeate pressure (Pie) increases. this has been amply demonstrated experimentally [21. (59) into Eq. As a practical matter.R. (57) and (60) with Eq. [ 19] have studied the effect of feed and permeate pressure on pervaporation flux in some detail. Baker/Journal of Membrane Science 107 (1995) 121 (a) From: Greanlaw et 15 (b) sl.pi ° Tio~m~ Pi~= (60) Combining Eqs. reaching zero flux when the permeate pressure is equal to the feedliquid vapor pressure (Pio) at the temperature of the experiment.o.J. 9. 8 indicate that the permeability coefficient of water in silicone rubber is constant.h) 0.5 ~ e ¢ Saturation vapor •.5 Hexane1.m. Fig. (61) expresses the driving force in pervaporation in terms of the vapor pressure. the water flux falls.(1977) e 1.G. (61 ).p i s a . / ~ is sometimes referred to as the Henry's law coefficient. ~.PisalPio (59) Pi Ji =~( CioPie/Hi) (64) wherepio is the partial vapor pressure of i in equilibrium with the feed liquid.~p.0 0 5 10 15 20 Permeate pressure (cmHg) 25 0 5 1'0 1'5 2'0 Feed pressure (atm) 25 Fig. 8. (11) gives Ji = T ( P i o G Pie) (61) =~(C. As Fig. the dependence of flux on permeate pressure in pervaporation is in accordance with Eq. Some illustrative results are shown in Fig. Wijmans.~) =g(C. W. as an alternative to Eq.o. The flux is essentially independent of feedpressure up to 20 atm but is extremelysensitiveto permeatepressure [ 19]. pressure 0. however. the flux can be written Eq. (61). 9.
the hydrostatic pressure of the feed liquid can be increased to as much as 20 atm without any significant change in the flux. gas separation. 0 1 0 . I I I I 0 0 . although this has been tried [ 22]. 57.d i f f u s i o n m o d e l 0. decreases with a decrease in hexane concentration in the membrane. After the membrane laminate had reached a steady state. a number of direct experimental measurements can be made to distinguish between the solutiondiffusion model and other models. placed in a highpressure reverse osmosis cell. This counterintuitive effect is illustrated in Fig. Thus. If on the other hand. 0 2 0 . 0 3 0 . l 0. This is because increased hydrostatic pressure produces a minimal change in the partial pressure of the feed liquid partial pressure (Pio). This agreement between theory and experiment is good evidence for the validity of the solutiondiffusion model. 9 are easily rationalized by the solutiondiffusion model as given above but are much more In the discussion above. four thin cellulose acetate films were laminated together. is that the action of an applied pressure on the feed side of the membrane is to decrease the concentration of the permeant on the lowpressure side of the membrane. ranging from diffusion of water in glassy cellulose acetate membranes to diffusion of organics in swollen rubbers [ 11. As predicted by the solutiondiffusion model and shown in Fig. the properties of pervaporation membranes illustrated in Fig. R. A number of workers have verified this prediction experimentally with a variety of polymer membranes. 4. the concentration difference across the membrane .16 ]. such as the poreflow model. the large body of permeability. pressure equals the saturation vapor pressure of the feed. Wijmans. and pervaporation. 8 and Fig. Ph. Also.G. the applied pressure decreases the concentration of water on the permeate side of the membrane. The curvature of the line in Fig. . reverse osmosis. as shown in Fig. the permeate pressure is fixed at a low value. . the solutiondiffusion model was used to derive equations that predict the experimentally observed performance of the membrane processes of dialysis.15. 1 and Fig. . Moreover. E v i d e n c e f o r t h e s o l u t i o n . This universality and simplicity of the solutiondiffusion model are its most useful features and are a strong argument for the validity of the model. 0 ' 0 .16 J. 2. Finally. . This behavior is typical of membranes that are swollen significantly by the permeant. the true driving force shown in Eq. The permeate was maintained at atmospheric pressure.0110 O v difficult to explain by a poreflow mechanism. Measurements of Rosenbaumand Cotton [ 15] of the water concentration gradients in a laminated cellulose acetate membrane under applied pressures of 68 and 136 atm. 68 atm. 10 [ 15]. and partition coefficient data obtained over the past twenty years for these different processes are in good numerical agreement with one another. controversial during the 1970s. It was not necessary to resort to any additional processspecific model to obtain these results. diffusion. 9 (a) shows that the permeability coefficient decreases with decreasing permeate pressure. One prediction of the solutiondiffusion model. 9(b). and the water concentration in each laminate measured. W. 0 5 l Membrane thickness (cm) l High Low pressure pressure surface surface Fig. and subjected to feed pressures of 68 or 136 atm. In these experiments.0105 Membrane water sorption (mols/g) 136 atm. that is. Baker/Journal of Membrane Science 107 (1995) 121 From: Rosenbaum and Cotton (1969) 0. 10. the membrane was quickly removed from the cell. Convincing examples of this type of experiment are the results of Rosenbaum and Cotton shown in Fig.
G. dl (cm3/cm2. Clo(m) .J. Pressure permeation (reverse osmosis) of isooctane and methyl ethyl ketone through crosslinked natural rubber membranes 265/xm thick.e~o.1 0.equals zero.2 03 0.. ell(m) i 0 12 From: Pauland PaciotU 10 8 nHexaneflux. Wijmans. and cj. . R. 12. calculated from the operating conditions through Eqs.7 Hexane concentrationdifferencein membrane. The change in the concentration gradient in the membrane as the applied pressure is increased is illustrated by the inserts.day) 6 4 2 / //" 0 Pervaporation • Reverseosmosis / 0 0. the concentration gradient and the permeation fluxes approach their limiting values [7]. Baker~Journal of Membrane Science 107 (1995) 121 17 Membraneconcentrationgradients Concentration Concentration Concentration 0 I ~ 0 l ~From: Paul and EbraLima 0 I ~ (1970) Limiting flux 4 Volume flux (cmJ/cm2day) 3 2 1 I I I I "~e" Limiting flux 0 100 200 300 Applied pressure (psi) 400 Fig. Data taken from both pervaporation ( o ) and reverse osmosis ( .. c. ) experiments.( 6 7 ) .~. cio. Flux of nhexane through a rubbery membrane as a function of the hexane concentration difference in the membrane..4 0. At high applied pressures. From Paul and Paciotti [ 11 ]. Feedside and permeateside membrane concentrations.. ( 65 ) .. 11. W.Clt(m) Fig. Maximum flux is obtained at the maximum concentration difference when the permeateside membrane concentration.5 06 0.
In a poreflow membrane. at the smaller values for Ci((m). with membranes having good rejections to divalent ions and most organic solutes. (19). the freevolume elements (pores) are relatively fixed and do not fluctuate in position or volume on the time scale of permeant motion. R. The transition region Although the solutiondiffusion model appears to be a reliable method of describing transport in many membranes. 12 show that reverse osmosis and pervaporation obey one unique transport equation. (28). but it is not easily explained by a solutiondiffusion membrane. The larger the individual free volume (65) Reverse osmosis: Ci¢(m) : ~/ie(m) ex 1 ~ . Reverse osmosis and pervaporation: 1 Cio(m) : ")lio(m) decrease in the slope of the curve at the higher concentration differences. The . Baker~Journal of Membrane Science 107 (1995) 121 at 136 atm applied pressure is about twice that observed at 68 atm.Ci#(.~. Paul and Paciotti [ 11] then took this work a step further by measuring the flux of a liquid (hexane) through a membrane both in pervaporation experiments with atmospheric pressure on the feed side of the membrane and a vacuum on the permeate side.vi(P°Pe)l ~ ] (66) Pervaporation: 1 ci~<~)  Pe " . The transition between a poreflow and a solutiondiffusion mechanism seems to occur with membranes having very small pores. (30) and (56). freevolume elements (pores) that exist in the membrane are present as statistical fluctuations that appear and disappear in about the same time scale as the motions of the permeants traversing the membrane..18 J.. transport follows the solutiondiffusion model. 11. and in reverse osmosis experiments with liquid at elevated pressures on the feed side and liquid at atmospheric pressure on the permeate side.~ and Ci~. ~/if(m)Pisat (67) Sorption data were used to obtain values for "Yi(m)"AS pointed out by Paul and Paciotti. In other words. whereas desalinationgrade sodiumchloriderejecting membranes clearly follow the solutiondiffusion model [23.e. These membranes are highly swollen by the organic solvents and. reflects a decrease in diffusion coefficient as the swelling of the membrane decreases. The same transition range must also exist in gaspermeation membranes. These concentrations. This means that the concentration in the membrane on the permeate side drops to zero and the flux through the membrane reaches a limiting value as feed pressure is increased. Membranes that reject sucrose and raffinose but pass all microions are clearly poreflow membranes. is also readily rationalized by the filtrationtype mechanism of a poreflow membrane. Another series of papers by Paul and coworkers [711 ] focuses on the same phenomenon using rubber membranes and permeation of organic solvents such as hexane. were calculated from Eqs. We believe the difference between poreflow and solutiondiffusion mechanisms lies in the relative permanence of the pores. Transport in such membranes appears to be best described by a poreflow model.~. 12 against the hexane concentration difference in the membrane (ci. In a solutiondiffusion membrane. but rejection of monovalent ions in the 2050% range..G. The hexane flux obtained in these two sets of experiments is plotted in Fig. on the other hand.n) ). it does not apply to ultrafiltration membranes used to separate proteins and other dissolved macromolecules from water. 5. W. cio~. the transition is in the nanofiltration range. The observation that many small solutes have the same permeation rate as water and. hence. Presumably. benzene.24]. Fick's law. i. no rejection by the ultrafiltration membrane. and carbon tetrachloride. and the measured concentration on the permeate side is within 20% of the expected value calculated from Eq.m~. Wijmans.. Even ultrafiltration membranes able to separate solutes as small as sucrose and raffinose from water have water fluxes 100 times the value that can be obtained by solutiondiffusion using reasonable values for the partition and diffusion coefficients of water. when operated in reverse osmosis fashion. Such data are shown in Fig. For permeation of a single compound these equations can be simplified as follows. large gradients develop through the membrane even at relatively modest applied pressures. the data in Fig.
the transition between permanent (poreflow) and transient (solutiondiffusion) flow appears to be in the range 5 to 10 ~. PTMSP has an unusually high void volume.. concentration and the like. for many years the most permeable polymer known.26 ]. the condensable vapor (CFC13) absorbs onto the walls of the small pores. Conclusions The solutiondiffusion model is a good description for the transport through dialysis. The fundamental equations describing transport in all of these processes can be derived from simple. j refer to components i and j Subscript m refers to the membrane phase Subscript o. lowfreevolume glassy polymers. List of symbols Subscripts i. reverse osmosis. basic principles without resource to processspecific factors. gases (nitrogen) through the 6. More dramatically. together with the very high free volume. [30. because of its very high free volume. ( 11 ) ] H Henry law coefficient [Eq. This blockage then prevents the flow of the noncondensed membrane. W. Nonetheless. cj mole concentration of components i and j Di. Baker~Journal of Membrane Science 107 (1995) 121 19 elements (pores).J. PTMSP also has very unusual permeability characteristics with mixtures of condensable and noncondensable gases. and f refer to the feed and permeate interfaces Thus ci. K~ liquid phase/membrane phase sorption coefficient [ Eq.~. a small number for a glassy polymer but still more than would be expected for a simple poreflow membrane. on the order of 25%. the ratio of the diffusion coefficients of oxygen and nitrogen (Do2/DN2) is 1. gas separation.G. has passed from being a polymer film with a distribution of transient free volume elements to an ultramicroporous membrane in which poreflow transport occurs [25. and ci~ means the concentration of component i in the fluid at the permeate interface. Dj Fick's law diffusion coefficient [Eq. diameter. (41) ] c~. eventually producing capillary condensation in which the pores are partially or completely blocked by the absorbed vapor. The general agreement of transport coefficients derived in all of these processes with each other and the general universality of the approach are strong indications of the models reliability. 7. hint at a poreflow contribution. (20)1 . Direct measurements of concentration gradients in membranes provide additional support for the model..4. and pervaporation membranes. R. means the concentration of component i in the membrane phase m at the permeate interface. The extremely high free volume provides a sorption capacity as much as ten times that of conventional glasses.26]. f. One interesting example that falls in this transition region is gas permeation through "superglassy" polymers. and are even substantially higher than those of polydimethylsiloxane. A water permeability constant [Eq. Jj membrane flux Ki. the presence of as little as 1% Freon11 (CFC13) in nitrogen lowers the nitrogen permeability of PTMSP more than 20fold from the pure nitrogen permeability [29]. the more likely they are to be present long enough to produce poreflow characteristics in the membrane. The transport mechanism involved is then similar to that suggested by Barrer et al. Gas permeabilities in PTMSP are orders of magnitude higher than those of conventional.31 ] in the 1960s and 70s to rationalize gas flow in very finely microporous carbon membranes. As a rough rule of thumb. According to this mechanism. This combination of extraordinarily high permeabilities. These equations provide an accurate description of the behavior of these membranes and the dependence of membrane transport on pressure. Wijmans. The best explanation for these unusual vapor permeation properties is to propose that PTMSP. (37)] B salt permeability constant [Eq. such as poly(1trimethylsilyllpropyne) (PTMSP) [ 25. diffusion coefficients are 103 to l06 times greater than those observed in conventional glassy polymers [27.28]. For example. (61)1 Ji.
Vol. W..N. 1970. Sci. Polym. [10] D. ( 2 ) ] s t a n d a r d state c h e m i c a l potential of components i and J molar volume osmotic pressure difference across a s e m i p e r m e a b l e membrane activity coefficients o f components i andj pi. [ 16] S. Diffusive transport in swollen polymer membranes. Proc. J.. Ed. 2 (1966) 241. Purif. (8)] coefficient ] Eq.R. 12 (1974) 1221. EbraLima. A simple predictive treatment of the permeation processes in pervaporation. Sci. [ 13 ] H. Russell. Glueckauf and P. Sherwood. R. Appl.. Sci. ( 2 3 ) gas c o n s t a n t salt r e j e c t i o n c o e f f i c i e n t [Eq. [12]D. J. The equivalent pore radius of dense cellulose acetate membranes. 13 (1975) 1201. [5] P. in Desalination by Reverse Osmosis. Appl. W. [17] A. [ 15 ] S. [3] H. MIT Press.. in R. [18] F. W. in H. Desalination. 5 (1976) 33.. Membrane Sci. Chadwick. NJ. J.. Polym. Transport properties of cellulose acetate osmotic membranes. Paul and J.. Diffusion and flow of water in homogeneous cellulose acetate membranes in J. Canada. [19] F. [ 11 ] D. Theeuwes. Merten and R. Thompson. Baker~Journal of Membrane Science 107 (1995) 121 k Li 47 p Po. [ 14] U. Polym. Comments on the relationship between hydraulic permeability and diffusion in homogeneous swollen membranes. Polym.). Cambridge. Wijmans. 21 (1960) 845.W. Polym. 17 (1973) 433. The effect of diffusive permeation rates by upstream and downstream pressures.G. 1974. Phys. Box 148.M. P. Okeda and T. Eur. [6] P. Transference. Appl. Ed.W. J. London. Diffusive and bulk flow transport in membranes. Paciotti and O. 1 (1976) 3. Ottawa..R. (47)] D a r c y ' s law c o e f f i c i e n t [Eq. J. On the mechanism of desalination by reverse osmosis flow through cellulose acetate membrane. [7] D. 1966. a comprehensive parameter governing permeation of solutes through membranes. Hopfenberg (Ed. Transport properties of osmotic membranes. Engelwood. Prince.. 19 (1975) 1837. Sep. Craig and J.R. Kim and K. 14 (1970) 2201. Petterlin and A. Sep..PjFUNCsat P~. J. J. Polym. Membrane Sci.. Diffusion Processes. Polym.N.. Cotton. New York.R. Yasuda. Conf. Petterlin. 1972. Polym. The solution diffusion model for swollen membranes. Baker.M. J.. Sci. Meares. pj pO. p~ R R T /zi. Reverse Osmosis. J. Meares. Sourirajan. A. MA. [2] E. Polym. Lonsdale. Permeability of Plastic Films and Coatings..W. Sixth Int. R.O.L.J.R. Kammermeyer. R. Membrane Sci. Paciotti. Baker. Pervaporation Chem.B. Actual concentration profiles in membrane permeation. Academic Press. Rosenbaum and O. [9] D. Paul. [ 22 ] T. Pressureinduced diffusion of organic liquids through highly swollen polymer membranes./xj tz °.D. J. Yasuda and A. [ 21 ] J.B. Driving force for hydraulic and pervaporation transport in homogeneous membranes. Appl. PiFUNCsat. Paul. Sci. Gale and R.N. (42)] absolute temperature K chemical potential of c o m p o n e n t s i a n d j [ Eq. J. Mauro. Sci. 13 (1974) 1215. yj References [ 1] S. [20]Mempro Company (Division of Oxygen Enrichment Company). Polym. Steadystate distribution of water in cellulose acetate membrane.M. J.20 J. Sci. Phys. Pe gas p h a s e / m e m b r a n e p h a s e s o r p t i o n coefficient [Eq. J. . tzj vi A ~ y~. Matsuura. 2.. Theoretical and experimental study of pervaporation on the basis of pore flow mechanism. Swinton (Eds. Wijmans and R.R. Bakish (Ed.. New York. Sci. Bakish Materials Corp. Gordon and Breach.D. Some properties of ionic and non ionic semipermeable membranes. Polym.Y. 79 (1993) 101. 7 (1969) 101. U.. September 1992. Circulation. Merten.). 8 (1970) 351. p~.D. Paul.L.A. J. 9 (1965) 1344. Product Data Sheet. Pergamon. 1991. Paul and O.). 2 (1977) 141.G. Methods. Sci. Shelden and E. [4] A. Riley. p ~ p/L. Greenlaw.V. Muire and F. Paul. EbraLima. Ind. Webster. [ 8] D. Hydraulic permeation of liquids through swollen polymeric networks: II Liquid mixtures. Pj p/C. 5 (1970) 679. ( 1 ) ] membrane thickness pressure p r e s s u r e in the fluids at the feed a n d p e r m e a t e i n t e r f a c e s partial p r e s s u r e s o f components i andj s t a n d a r d state p r e s s u r e s o f components i andj saturation vapor pressures of components i andj permeabilities of components i and j permeabilities of components i andj permeability of components i a n d j as defined b y Eq. Further comment on the relation between hydraulic permeation and diffusion.K.
Baker. Strathmann. [24] G. S. F.. Phys. [28] Y. 21 [27] L..G. Sharma. Ash.M. J. H.. Proc. Private communication. Membrane Sci.W. Pinnau and L.R. Sorption and transport of organic vapors in poly[(trimethylsilyl)lpropyne]. Toy.G. Ash. J.W. Baker~Journal of Membrane Science 107 (1995) 121 [23] R. Wijmans. J.M. Eirich and H. [25] R. 1 (1976) 17.1propyne] (PTMSP) membranes. 48 (1990) 321..J. Barter and C. [ 31 ] R. . I.M. Gas separation processes.281. Pinnau and R. Elucidating the mechanism (s) of gas transport in poly [ 1. An investigation of the high gas permeability of poly(trimethylsilyllpropyne).C..B. Stem and T. [26] L. WitcheyLakshmanan. J. J. 5. Ichiraku. Chem. Burban. Membrane Sci. Auvil and P. [ 29 ] I. R. R.T. R. 1 (1966) 129. Water transport in porous and nonporous membranes. [30] R. Low pressure ultrafiltration of sucrose and raffinose solutions with anisotropic membranes. Membrane Sci. 76 (1972) 238. Barter and P.R. Bloch and O. Toy.255 (25 January 1994). U.(trimethylsilyl).S. Baker.. W. 34 (1987) 5. Nakagawa. 86 (1994) 67. Bhem. Kedem. Sorption and flow of carbon dioxide and some hydrocarbons in a microporous carbon membrane. Srinivasan.G. Pope. 271 (1963) 19. Hopfenberg and R. Desalination. Thau. Membrane Sci. Royal Soc. Flow of adsorbable gases and vapors in microporous medium. R. Pat. S.A.
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