j o u r n a l of MEMBRANE SCIENCE

ELSEVIER
Journal of Membrane Science 107 (1995) 1-21

The solution-diffusion model: a review
J.G. Wijmans, R.W. Baker *
Membrane Technology and Research, Inc., 1360 Willow Road, Suite 103, Menlo Park, CA 194025-1516, USA
Received 28 December 1994; accepted 3 April 1995

Abstract
The solution-diffusion 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 solution-diffusion 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 solution-diffusion membrane and a pore-flow membrane seen in nanofiltration membranes and some gas permeation membranes.
Keywords: Solution-diffusion model; Transport equations; Pore-flow; 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 solution-diffusion 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 pressure-driven 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) 328-2228. Fax: (415) 3286580. 0376-7388/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved SSD10376-7388(95)00102-6

other permeants move. Both models were proposed in the nineteenth century, but the pore-flow model, because it was closer to normal physical experience, was more popular until the mid-1940s. However, during the 1940s, the solution-diffusion model was used to explain transport of gases across polymeric films. This use of the solution-diffusion model was relatively uncontroversial, but the transport mechanism in reverse osmosis membranes was a hotly debated issue in the 1960s and early 1970s [ 1-16]. By 1980, however, the proponents of solution-diffusion had carried the day; currently only a few die-hard pore-flow 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 solution-diffusion model. W e show that these diverse processes can all be described by a single unified approach based on the solution-diffusion model. The experimental evidence that supports the solution-dif-

2

J.G. Wijmans, R.W. Baker~Journal of Membrane Science 107 (1995) 1-21

fusion model as it applies to these processes is reviewed, and the transition region between pure solution-diffusion and pure pore-flow 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 p-t--Pisat (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 solution-diffusion and pore-flow models differ in the way the chemical potential gradient in the membrane phase is expressed [8,9,15,17]: The solution-diffusion 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 pore-flow 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.

W. Baker~Journal of Membrane Science 107 (1995) 1-21 3 Solution-diffusion model High-pressure solution Chemical potential IJ i Pressure p Membrane Low-pressure solution Solvent activity 7 I c I Pore-flow model Chemical potential Pl Pressure p Solvent activity 7 i e i Fig. 1. the pressure difference produces a smooth gradient in pressure through the membrane. but the solvent activity (•iCi) remains constant within the membrane. The existence of two pressure gradients is a consequence of the two-phase nature of the pore-flow model. in the pore-flow model. the pressure gradient exists only in the fluid-filled pores. with Eqs. which compares pressure-driven permeation of a one-component solution by solutiondiffusion and by pore-flow 2. that solution-diffusion membranes transmit pressure in the same way as liquids. Combining Eqs. the pressure everywhere within the membrane is constant at the high-pressure value.G. Pressure-driven permeation of a one-component solution through a membrane according to solution-diffusion and pore-flow transport models 2. In both models. The solutiondiffusion model on the other hand assumes that. R. Consequently. In the pore-flow model. ( 1 ) and (2). ( 1 ) and (2) providing the mathematical link between pressure and concentration. No pressure gradient exists within the membrane matrix material. 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) . Wijmans. when z At this point it is worth noting that. in effect.J. Consider the pore-flow model first. This assumes. the difference in pressure across the membrane (Po-Pe) produces a gradient in chemical potential according to Eqs. the pressure difference across the membranes is expressed as a concentration gradient within the membrane. The consequences of these two assumptions are illustrated in Fig. 1. which is at the feed pressure throughout.

the terms i andj represent components of a solution.~c~) = vi(Po-Pe) RT - viA 7r .4 J. and the gradient in chemical potential across the membrane is expressed as a smooth gradient in solvent activity (y~c~). the pressure within the membrane is constant at the high-pressure value (Po).e.D i ~ ( 10 ) and integrating over the thickness of the membrane then gives 3 J i : D i ( ci°' "~ .oi(Po-pe) (12) Using osmosis as an example. and g is the membrane thickness. ( P o . but. the gradient of salt (component j) is not shown in this figure. The pressure within and across the membrane is constant (i. Eq. There is a discontinuity in pressure at the permeate side of the membrane. water passes across the membrane from right to left.vi(po . and the terms o and e represent the positions of the feed and permeate interfaces. equal to Lv. Equating the chemical potential on either side of the permeate interface. the pressure difference. As a result. 3 In the equations that follow. where the pressure abruptly falls frompo to Pe. that RTIn[ 1 . when sufficient pressure has been applied to the saline side of the membrane to bring the flow across the membrane to zero. Osmosis according to the solution-diffusion model Fig. 2(b). The difference in concentration across the membrane results in a continuous. For simplicity. Po =Pro = P e ) . Wijmans. but we assume the membrane to be very selective. across the membrane balances the solvent activity difference A (y~c~) across the membrane. (1) can be written.P e ) = A ~r. As shown in Fig. 2(a) shows a semipermeable membrane separating a salt solution from pure solvent.zifon the water side to IXio on the salt side. and the flow is zero. . The activity. because no pressure gradient exists within the membrane. . the pressure within the membrane is assumed to be constant at the high-pressure value Po. respectively. the pressure on the solvent side of the membrane. The subscript m is used to represent the membrane phase.G. The flow that occurs down this gradient is again expressed by Eq. 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~. 2.1. smooth gradient in chemical potential of the water (component i) across the membrane from ~. We can also define A (yici) by yie~m)Cie~m~= (yieCie) -. (14) reduces to (14) A(~. %. . (13) into Eq. . by combining Eqs. on substituting Eq.W.A (y~ci) ] = . Thus the term % represents the concentration of component i in the fluid (gas or liquid) in contact with the membrane at the feed interface. so the concentration of salt within the membrane is small. The pressure is the same on both sides of the membrane. Eq. (5) we obtain R/In('yif(m)Cif(m)) -- RTIn ('YieCie) = . as RTLi dci J~ . This pressure difference ( P o .A (yici) (13) and. from Eq. Fig. we can discuss concentration and pressure gradients according to the two models in a somewhat more complex situation. Consider the application of the solution-diffusion model to osmotic membranes first.P e ) is equal to the osmotic pressure difference A 7r. and chemical potential gradients within this type of membrane are illustrated in Fig. R. Thus: Ji = . 2 (b) shows the situation at the point of osmotic equilibrium. . pressure. it follows. B a k e r / J o u r n a l of Membrane Science 107 (1995) 1-21 This equation can be integrated across the membrane to give Darcy's law J k(po-pe) g (8) where k is the Darcy's law coefficient. (12).RT (15) Thus. and the solvent activity gradient (yici) falls continuously from the pure water (solvent) side to the saline (solution) side of the membrane. Thus.P e ) Since A (yici) is small.Cie(~) ) ( 11 ) f 2. In the solution-diffusion model. since (TieCie) ~ 1. ( 1 ). ( 1 ) and (2).~ is the concentration of component i in the membrane at the feed interface (point o). of the membrane.°.

2.G. 3.J. 2. resulting in a flow from left to right. This is the process of reverse osmosis. and pressure gradients within an osmotic membrane according to the pore-flow model are illustrated in Fig. then the solvent activity difference across the membrane increases further. Osmosis according to the pore-flow model The activity. The pressure in the membrane is uniform and equal to the high-pressure value. so the chemical potential gradient within the membrane is expressed as a concentration gradient. 2 and shows the gra- . 2(c). This figure is the pore-flow equivalent of Fig. Chemical potential. W. chemical potential. R. as shown in Fig. Baker~Journal of Membrane Science 107 (1995) 1-21 Dense solution-diffusion 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. Wijrnans. 2. pressure. and solvent activity profiles in an osmotic membrane according to the solution-diffusion model. If a pressure higher than the osmotic pressure is applied to the feed side of the membrane.

Fig. Wijmans.G. Chemical potential. pore-flow 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. so the chemical potential gradient in the membrane is expressed as a pressure gradient.W. 3. when a sufficient pressure has been applied to the solute solution side of the membrane to bring the flow across the membrane to zero. Baker~Journal of Membrane Science 107 (1995) 1-21 Porous. and there is a discontinuity in pressure at the feed side interface where the . R. pressure and solvent activity profiles in an osmotic membrane according to the pore-flow model. The concentration within the membrane is assumed to be uniform. 2 ( b ) . 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. 3 ( b ) shows the situation at the point of osmotic equilibrium. Fig. dients when a very selective semipermeable porous membrane separates a solute solution from a pure solvent. As in Fig.6 J. the pressure gradient within the membrane is at the permeate-side value.

By rearranging these equations. (5) gives /z° + RTIn("YioCio)+ vi(po --P&at) = t ~ + RTln( %. Eq.1. The concentration gradient across the membrane causes a flow of solute and solvent from one side of the membrane to the other.. the same procedure can be followed. Flow through this type of membrane is expressed by Fick's law. 3(c). In the next section.m. (5) and (6)..Go. This pressure difference ( P o . = Ki'cio (20) On the permeate side of the membrane. 3 is that.(m . Wijmans.<. The resulting equations linking the driving forces of pressure and concentration with flow are then shown to be consistent with experimental observations. and Eq.~..(Po -. For many systems. leading to an equivalent expression Cie~m.cie ) (22) The product Di. Application of the solution-diffusion model to specific processes In this section. In("YioCio) = In( Yio~m)ci. the pressure gradient within the membrane increases further. gas permeation. The general approach is to use the first assumption of the solution-diffusion model. When a pressure higher than the osmotic pressure is applied to the feed side of the membrane.W. (8).Pi~a. a membrane is used to separate two solutions of different compositions. Eq. ) + V~.. only a pressure gradient exists. ( 11 ). Flow through this type of membrane is expressed by Darcy' s law. and pervaporation membranes are derived. Dialysis To illustrate the application of the general procedure described above.. thus ci.. although the fluids on either side of a membrane may be at different pressures and concentrations. From this assumption...G. 2 Fig. the appropriate quantitative expressions describing flow through solution-diffusion membranes are derived by calculating the concentration gradient within the membrane and then substituting this gradient into the Fick's law expression. the appropriate equations for the solution-diffusion model for transport in dialysis. namely.) which leads to 17) 3. R.. Oi. to give the familiar expression describing permeation through dialysis membranes D~Ki Ji = T ( Ci° . and solvent flow is from left to right. (19) becomes Ci. g i and . P~. = Ki. as shown in Fig..P e ) is equal to the osmotic pressure A 7r. which is the simplest application of the model because only concentration gradients are involved. reverse osmosis.. Eq.. 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. K~ is normally referred to as the permeability coefficient. within a perfect solution-diffusion membrane only a concentration gradient exists.cie (21) The concentrations of permeant within the membrane phase at the two interfaces can then be substituted from Eqs.°>) and. ( 11 ). (20) and (21) into the Fick's law expression. 3. These values for Cio~m~and ci~m~ can then be substituted into the Fick's law expression. Ki. Within a perfect pore-flow membrane. to give the transport equation for the particular process. Following the general procedure described above. 1 Fig. that the chemical potential of the feed and permeate fluids are in equilibrium with the adjacent membrane surfaces. we will derive the appropriate solution-diffusion model transport equation for dialysis.J.)~lio(m) 18) "cio 19) The ratio of activity coefficients y~/y~. Baker~Journal of Membrane Science 107 (1995) 1-21 7 pressure difference Zip across the membrane occurs. 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. In dialysis. The important conclusion illustrated in Fig.) is the sorption coefficient.. ( 11 ). Eq. the chemical potential in the fluid and membrane phases can be equated using the appropriate expressions for chemical potential given in Eqs..

(qo .. the pressure in the feed solution and within the membrane are identical [as shown in Fig. the nature of the solvent used in the liquid phase is also important.. against the concentration difference across the membrane. The permeability calculated from these plots varies from 9.5 X 10 -7 cm2/s for water to 6. if a permselective membrane (i. From Eq. From Eq. water will pass through the membrane from the pure-water side of the membrane into the side less concentrated in water (salt side). is a constant as shown in Fig.) which leads to In(y~c~. depending only on the permeant and the membrane material. we are usually dealing with two components.8 J. (19).c~). silicone oil. the flow of water can be retarded and. (20) ] cio. respectively. Thus. gives the expression cie.. in fact. At the feed interface. water (i).. and salt (j). m.p ( . which combined with the approximation ')/i- separate a salt solution from pure water.e. but much less permeable to salt) is used to Rearranging and substituting for the sorption coefficient. Some experimental data illustrating this effect are shown in Fig. Reverse osmosis Reverse osmosis and normal osmosis (dialysis) are directly related processes.) = tx° + RTln( Yie~m)Cie~. a pressure difference exists [as shown in Fig. J~. the slope of this line is the permeability. R. 4(d). Three sets of permeation experiments are reported. Baker~Journal of Membrane Science 107 (1995) 1-21 thus Pe are concentration dependent. then the flow of water is reversed. (22) implies the use of values for Di. which is a plot of the progesterone flux times the membrane thickness. in which the solvent used to dissolve the progesterone is water. This process is called reverse osmosis and is an important method of producing pure water from salt solutions.~) + v i ( p o . Equating the chemical potentials at this interface gives the same expression as in dialysis [cf. 23. This difference reflects the activity term yi in Eq..~ocm2/s for PEG 600. 4 [ 18]. (22). the flow ceases. (23). Eq. Eq.vi(Po--Pe) ] ] R-T: (30) . 2(b)] from Po within the membrane to Pe in the permeate solution.. P~csat. The hydrostatic pressure required to stop the water flow is called the osmotic pressure (A ~). 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. This result is also in agreement with Eq. = Ki "fit" e x. and water begins to flow from the salt solution to the pure water side of the membrane.= P~(sat = Substituting the appropriate expression for the chemical potential of an incompressible fluid [Eq. Ki and Pi that are averaged over the membrane thickness. Equating the chemical potentials across this interface gives ~i~ = ~i~'(m) (27) 1 Csat (24) yields Pi . = Ki'ci.~) = 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. Ki. the chemical potentials at both sides of the membrane are first equated. In reverse osmosis.s. The permeability coefficient P~ is often treated as a pure materials constant. In simple terms.W.P. and polyethylene glycol MW600 (PEG 600). a membrane freely permeable to water.. 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. 3. but.2. e. Wijmans. (5)] yields Di (25) Ti Ti(m) /~o + RTIn("yieCie)"31-vi(pe --Pis. If a hydrostatic pressure is applied to the salt side of the membrane. Pg. (26) At the permeate interface.G. when the applied pressure is sufficient. Following the general procedure. However.. 2(b)].5 x 10. This process is called normal osmosis.

~"-I I I I I I 0 100 200 300 400 500 600 700 Progesterone concentration. Eq.25 1.50 0. All the data can be rationalized onto a single curve by plotting the thickness-normalized flux against fractional progesterone saturation as described in the text and shown in (d)..i - c.000 20.8 1. ~ . ( 2 6 ) and ( 3 0 ) can n o w be substituted into the F i c k ' s law expression. 0 2 4 6 8 10 12 14 Progesterone concentration.sec)] 0. Ac(pg/ml) (b) Progesterone flux x membrane thickness. l [10 -11 x (g.50 Saturated 1. Ac (pg/ml) (c) Progesterone flux x membrane thickness. and (c) polyethylene glycol (PEG 600). R. J-I [10 "11 x (g. Permeation of progesterone through polyethylene vinyl acetate films.cm/cm2.z~ Water .0 1..f) is plotted against the progesterone concentration across the membrane. to yield J' = .25 .sec)] 9 2.J.5[ f.2 0.000 15. 4. Because of the different solubilities of progesterone in these solvents. (22) vary 1000-fold.Z 0. (b) silicone oil. the permeabilities calculated from these data through Eq.cm/cm2-see)] 1 5 l- .6 0.~" [] Silicone oil (Dow 360) ¢o" o Poly(ethylene glycol) (PEG 600) 0 j ~ .G.5 0 ~. Baker~Journal of Membrane Science 107 (1995) 1-21 (a) Progesterone flux x membrane thickness.2 Fractional progesterone saturation. The expressions for the concentrations within the m e m b r a n e at the interface in Eqs..0 t Water 1..cm/cm2. (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 . The thickness-normalized progesterone flux (jr.cm/cm2.. ( 11 ). J-l [10 -11 x (g.5 l 2. or DJ%(m). Ac/csa t Fig. and is independent of the fluid used as the solvent. W. ~ . J-I [10 "11 x (g. The slope of this line Pfsa.0 Saturated solut!o~.. is a materials property dependent only on the membrane material and the permeant...0t Saturated 0 5.sec)] 15L " | Saturated solution ~ c 0.00 Progesterone concentration. I 0 0. Ac [ 18].00 Progesterone flux x membrane thickness..4 0.000 10.~ . Wijmans.~. Ac(pg/ml) (d) 1. J . The solvent phase used to dissolve the progesterone is (a) water. --- (31) Eq.75 0.

In the reverse osmosis literature. R. Baker~Journal of Membrane Science 107 (1995) 1-21 osmosis membrane in terms of the pressure and concentration difference across the membrane. while the Jj=~[Cjo-Cjeexp(-V~(~TPe))] (38. and Eq. where Ap is the difference in hydrostatic pressure across the membrane (Po-Pe).exp(x) ~ x as x--* 0 can be used. (37).3. whereas according to Eq.G. However. 5. The rejection coefficient increases with applied pressure as shown in Fig. when Zip = 100 atm.14]). (29) can be written to a very good approximation as Ji = Digici°ui( A p . 5. but the salt flux does not. (38) is close to one. (33) and (31) can be combined to yield J~= or o c/o[ f 1 .06. based on diffusion coefficient data from gas separation and pervaporation. (31 ): The rejection coefficient is a measure of the ability of the membrane to separate salt from the feed solution. At the point at which the applied hydrostatic pressure balances the water activity gradient. that is.exp. because the water flux increases with pressure. Similarly. Also shown in this figure is a term called the rejection coefficient. starting with the equivalent to Eq.vi(Zlp . Consider the water flux first. DiK.W.[Cioand. the constant A is usually called the water permeability constant. For a perfectly permselective membrane. (38) can then be written as oj~ Jj= ~---( Cjo. (31) becomes Because the term ..ATr) (37) where A is a constant equal to the term DiKiC~oV~/fRT. the solution-diffusion model has also been used by many workers to obtain diffusion and partition coefficient data. through the membrane can be derived. (40). Gas separation In gas separation. the salt flux is essentially independent of pressure./17r= 10 atm. Eq. 3. cie = % and R = 0%. and vi = 18 cm 3. the flux of water across the membrane is zero. [ Ci~ ex ~( - vi( A ~-).Zi 7r)/RTis small under the normal conditions of reverse osmosis. the simplification 1 .°j/~j (41) At hydrostatic pressures higher than A ~-.10 J. which is defined as = (1-cJetXlO0%-~cjoj (42) (36) fRT This equation can be simplified to J~=A( Ap-. thus. a gas mixture at a pressure Po is applied to the feed side of the membrane. . and for a completely unselective membrane.Zi 7"i") Predictions of salt and water transport can be made from this application of the solution-diffusion model to reverse osmosis (first derived by Merten and co-workers [13. the exponential term in Eq. Eqs. Under these conditions.Cjt) or (39) Ji = 0 =---{-. As well as predicting the general form of the salt and water transport through reverse osmosis membranes. According to Eq. a simplified expression for the salt flux.]] RT ]J (32) Jj=B(Cjo-Cje) (40) where B is usually called the salt permeability constant and has the value (33) fie= % e x p ( ~ ) B . (31 ) can be simplified further. Some typical results are shown in Fig. For example. 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. the term v~(zip . cje = 0 and = 100%. Wijmans. the point of osmotic equilibrium in Fig.ZI ~r)/RT is about 0.vj(po -Pc)/RT is small. These data appear to be self-consistent and reasonable. A trial calculation shows that the term . and Eq.- ~-~ (34) ji-DiKeici°[1-exp(--vi(A-~T-ATr))] (35. K. Eq. Jj. 2.

G.2oo Applied pressure (psig) Fig.) Plsat (43) which rearranges to Po o -'F ~i Po [--lYi(Po--Pi~at)'~ .6oo 1. . Baker~Journal of Membrane Science 107 (1995) 1-21 11 30 25 Water 20 Water flux 15 (L/m2-h) 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. whereas Eq.5% sodiumchloride) in a good qualityreverse osmosis membrane(FilmTec Corp.. increaseswith pressure. at zero flux. (40). the Chemical potential for the gas phase is given by Eq. Wijmans.RTln( Tio~. and. R. is essentiallyconstantand independentof pressure. Substitution of these equations into Eq. (16) at the gas/membrane feed interface yields /X + RTln(3%cio) ° + R T l n . W. FF30 membrane)as a functionof pressure. however. The salt flux. meets the pressure axis at the osmotic pressure of sea water ~ 350 psi.in accordancewithEq. The water flux. 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. (37).~Cio~. (6) for a compressible fluid. permeate gas at a lower pressure Pe is removed from the downstream side of the membrane.= l~i d.. As before. (5) for an incompressible medium is applied to the membrane phase.J. 5. This time. in accordancewith Eq.n) P/sat (44) ..)) vi(Po-Pisa. .. Flux and rejectiondata for a model seawater solution (3. CioeXp~ --~ j ci°(m) = ~io(. .

a limited affinity for the gas phase (high Yi). 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."Y~o(m)) is the sorption coefficient / ~ 5. there is a gradient in concentration within the membrane but no gradient in pressure. 4 While evaluating this exponential term (the Poynting correction). (20) and the gas-phase coefficient ~ defined by Eq. this derivation explicitly clarifies the assumptions behind this equation. but. (42). the concentration of component i at the membrane/permeate interface can be shown to be Cie(~) = g~i Pi e (48) Combining Eqs. thus. the concept of permeability as a materials constant must be treated with caution. (45) then simplifies to Cio(m ) -- Yio . -Pio "Yio(m) Pisat (46) However. 4 earlier. (51 ) is not a commonly used expression for gasphase membrane permeability. Eq.. (11). (50) is a long-winded way of arriving at a trivial result. even for very large pressures Po. a high affinity for the membrane material (small ")li(m)). 5 The superscripts G and L are used here and later in Eq. significant deviations from ideality of the vapor's activity coefficient can also occur at high partial pressures. Pio. it is important to recognize that vi is not the molar volume of i in the gas phase. Eq. P ~. For example. defined . Ti. (50) is widely used to accurately and predictably rationalize the properties of gas permeation membranes. and a low saturation vapor pressure (Pisat)" P~ is close to being a materials constant. Eq. Wijmans. even for gases. First. the permeability of vapors at partial pressures close to saturation often increases substantially with increasing partial pressure. Similarly. the decrease in diffusion coefficient far outweighs other effects. then gives JiDiI~i (Pio . in which the Poynting correction was assumed to be one. and permeabilities fall significantly as molecular weight increases [ 19]. R.r by Eq. (58) to distinguish between the liquid-phase sorption coefficient K. This is related to the approximation made in Eq. Baker~Journal of Membrane Science 107 (1995) 1-21 Because the exponential term is again very close to one 4.) in Eq. leading to the familiar expression Ji Pi (Pio--Pie) e G (50) Eq. The permeability coefficient P~ can be written as The term T~o/(Pisa. (45) and (46) with the Fick's law expression. In rubbery polymers. P~ and ~ have different dimensions but can be easily interconverted as shown in the pervaporation section that follows. the two effects are more balanced.G. However. we will use P~ for the permeability coefficient for gases to distinguish from P~ for liquids. Eq. but the molar volume of i dissolved in the membrane material. Eq. For molecular weights up to 100. W.12 J. are usually close to unity. which is approximately equal to the molar volume of liquid i. It might be thought that the derivation leading to Eq. (51 ). but it is interesting because it shows that large permeability coefficients are obtained for compounds with a large diffusion coefficient ( D i ) . This is in sharp contrast to the permeability constant for liquids as described in the discussion centered on Fig. Second. In glassy polymers. on the other hand. relatively independent of the composition and pressure of the feed and permeate gases because gas-phase activity coefficients. permeability generally increases . This effect is commonly ascribed to plasticization and other effects of the permeant on the membrane changing Di and Ti(. (47). (51) is also a useful way of rationalizing the effect of molecular weight on permeability.P i e ) (49) The product DiKe/is often abbreviated to a permeability coefficient. (44) reduces to Cio(m ) -- "YioCio Po • -~/io'(m) (45) Pisat The term % "Po is the partial pressure of i in the feed gas. 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. The permeant's saturation vapor pressure Pisat and diffusion coefficient both decrease with increasing molecular weight creating competing effects on the permeability coefficient.

6 [20]. the molecular weight term gradually becomes dominant. The equivalent expression for the chemical potentials in each phase is then . Wijmans. Some data for permeation of simple alkanes in silicone rubber membranes that illustrate this behavior are shown in Fig. Above pentane.000 Permeability.4.01 i i t 0. and activity across the membrane are illustrated in Fig. Baker~Journal of Membrane Science 107 (1995) 1-21 100. 6. with increasing molecular weight because Piss. where Ki is the liquid-phase sorption coefficient defined in Eq. W. 7. Eq. Plsat (stm) i 100 1. the pressure drops from Po in the membrane to Pe in the permeate vapor. the trend is reversed. At the permeate gas/membrane interface. (5) then gives /x° + RTIn(~/ioCio) ~. pressure. is larger than the effect of increasing size or Di.Pi~a.ui(Po -Pi~. so that the permeating components are removed as a vapor mixture..Permeabilitydata from [20]. Pervaporation preferentially permeates one or more of the components. and permeabilities fall with increasing molecular weight of the permeant. 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. At the liquid solution/membrane feed interface. PI G (Barrer) 1. Chemical potential.. and activity profiles through a pervaporation membrane following the solution-diffusion model.~3H8 C10H22 ~6 Increasing diffusion coefficient Increasing molecular weight "~H4 100 0.~ which leads to an expression for the concentration at the feed-side interface ~/ioCio Cio(.000 C5H12 C8H18~"~4H10 i~.~---~lio(m) Ki'Cio (53) Fig.J.1 1 10 Permssnt saturation vapor pressure. G.~ 'IP C6H14 ~.. PermeabilitycoefficientP~ of n-alkanes in polydimethylsiloxaneas a functionof saturation pressure.) . Above molecular weight 100.. A partial vacuum is maintained on the permeate side of the membrane. the effect of the decrease in Pisa. 7. the chemical potential of the feed liquid is equilibrated with the chemical potential in the membrane at the same pressure. 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 --.001 i 0. R.000 Fig. As the molecular weight increases from CH 4 tO CsHI2.--. is the dominant term. The gradients in chemical potential.) =/x ° + RTIn( y~o~>C~o. pressure. (19) in the dialysis and reverse osmosis sections. however. 3.000 13 10...

Wijmans.) • fie'-- Pe P is~.. The arrows on the lower axis represent the saturation vapor pressures of the feed solution at the temperature of these experiments. The interconversion of these two coefficients can be handled by considering a hypothetical vapor in equilibrium with feed solution [21 ]. However.. thus = ~i "~ R/In( yico• c G) + R / I --isar o (58) Cie(.y ~ ..t (56) The product cie "Pe can be replaced by the partial pressure term Pie. G. the concentration at the permeate side interface is: Cie(m) : where K~ is the gas-phase sorption coefficient defined in Eq. (54) to (57). ( 11 ) (Fick's law) to obtain an expression for the membrane flux..)) +vi(Po--Pisa.14 J. e x ~ . (58) becomes . Baker~Journal of Membrane Science 107 (1995) 1-21 400 300 Permeate flux (g/m2.) ")lie Pie "}lie(m) Pisat K~i "Pie (57) Following the same steps as were taken from Eq. (53) is a liquid-phase coefficient whereas the sorption coefficient in Eq. (54) gives "}lie Cie(m) (54) "Yif(m. 15 (cmHg) Fig. thus.Plsat I 0 I.P i s = ) l "~ "J (55) AS before. W. 8... the sorption coefficient in Eq. the exponential term is close to 1...lO I • I •t I 5 10 Permeate pressure • •~ . (53) and (57) can be substituted into Eq. The effect of permeate pressure on the water flux through a silicone rubber pervaporation membrane.h) 200 C 100 - • • 40°C ? .v i ( P o . Eq.. Pisat Pe C i e .) Rearranging Eq. (47) in the gas separation section. (57) is a gasphase coefficient. R.. This vapor-liquid equilibrium can then be written Id~io -~-R / i n ( ~io " C~o) + l"i(Po --Pi~at) Tie Tie(. /zo + R / i n ( ~liecit ) -~RTh~-~J "¢" i s a t / =tz°+R/in(Y~e¢m~C~e¢.. The concentration terms in Eqs.

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. The flux decreases with increasing permeate pressure. The explanationfor this behavioris the transport Eq.(1977) e 1.m. The straight lines in Fig. 8 indicate that the permeability coefficient of water in silicone rubber is constant. for example. / ~ is sometimes referred to as the Henry's law coefficient. reaching a minimum value when the permeate .G. As the permeate pressure (Pie) increases. therefore (62) ef Pi= eiG" Hi as (63) and. 9. pressure 0.~-p.0 0 5 10 15 20 Permeate pressure (cmHg) 25 0 5 1'0 1'5 2'0 Feed pressure (atm) 25 Fig.o. however.0 flux (kg/m2. The driving force could equally well have been expressed in terms of concentration differences. [ 19] have studied the effect of feed and permeate pressure on pervaporation flux in some detail. the dependence of flux on permeate pressure in pervaporation is in accordance with Eq. W. reaching zero flux when the permeate pressure is equal to the feed-liquid vapor pressure (Pio) at the temperature of the experiment. ~. shows data for the pervaporation of water as a function of permeate pressure.pi ° Tio~m~ Pi~= (60) Combining Eqs. -n. As Fig.PisalPio (59) Pi Ji =-~( Cio-Pie/Hi) (64) wherepio is the partial vapor pressure of i in equilibrium with the feed liquid.R.p i s a . The term ~ . (61) expresses the driving force in pervaporation in terms of the vapor pressure. 8. (11) gives Ji = T ( P i o G -Pie) (61) =~(C. this has been amply demonstrated experimentally [21. (61 ). Baker/Journal of Membrane Science 107 (1995) 1-21 (a) From: Greanlaw et 15 (b) sl. Thompson et al.o" Hi-pi~) From Eq. (53) yields c. as an alternative to Eq. (61). Wijmans. As a practical matter. Cio ~io. Hi. the use of vapor pressure leads to much more useful results. Some illustrative results are shown in Fig.h) 0.5 Hexane1.19]. 9. Fig.pJ~.~) =--g(C.J. 9(a) shows. YiCo Pio K~. (59) into Eq.5 ~ e ¢ Saturation vapor •. (61). (59) it follows that ~ = / ~ . Substitution of Eq. the flux can be written Eq. the water flux falls. The effect of feed and permeate pressure on the flux of hexane through a rubbery pervaporation membrane. (57) and (60) with Eq. The flux is essentially independent of feedpressure up to 20 atm but is extremelysensitiveto permeatepressure [ 19].o.

9 (a) shows that the permeability coefficient decreases with decreasing permeate pressure. . and partition coefficient data obtained over the past twenty years for these different processes are in good numerical agreement with one another. 1 and Fig. Also. as shown in Fig. The curvature of the line in Fig. E v i d e n c e f o r t h e s o l u t i o n . that is. controversial during the 1970s. Finally. As predicted by the solution-diffusion model and shown in Fig. This counter-intuitive effect is illustrated in Fig. This behavior is typical of membranes that are swollen significantly by the permeant. Measurements of Rosenbaumand Cotton [ 15] of the water concentration gradients in a laminated cellulose acetate membrane under applied pressures of 68 and 136 atm. This is because increased hydrostatic pressure produces a minimal change in the partial pressure of the feed liquid partial pressure (Pio). 4. 0 1 0 . gas separation. Baker/Journal of Membrane Science 107 (1995) 1-21 From: Rosenbaum and Cotton (1969) 0. such as the pore-flow model. 0 5 l Membrane thickness (cm) l High Low pressure pressure surface surface Fig. 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. 68 atm. 0 3 0 . Convincing examples of this type of experiment are the results of Rosenbaum and Cotton shown in Fig. the applied pressure decreases the concentration of water on the permeate side of the membrane. . ranging from diffusion of water in glassy cellulose acetate membranes to diffusion of organics in swollen rubbers [ 11. the concentration difference across the membrane . the hydrostatic pressure of the feed liquid can be increased to as much as 20 atm without any significant change in the flux. the permeate pressure is fixed at a low value. This agreement between theory and experiment is good evidence for the validity of the solution-diffusion model. the membrane was quickly removed from the cell. 10 [ 15]. 8 and Fig. W. Ph. decreases with a decrease in hexane concentration in the membrane. Moreover. 0 ' 0 . pressure equals the saturation vapor pressure of the feed.0110 O v difficult to explain by a pore-flow mechanism. and pervaporation. A number of workers have verified this prediction experimentally with a variety of polymer membranes. although this has been tried [ 22]. reverse osmosis. R. the large body of permeability. 57. placed in a high-pressure reverse osmosis cell.16 ].0105 Membrane water sorption (mols/g) 136 atm. l 0. the properties of pervaporation membranes illustrated in Fig. . 9(b). This universality and simplicity of the solution-diffusion model are its most useful features and are a strong argument for the validity of the model. The permeate was maintained at atmospheric pressure. It was not necessary to resort to any additional process-specific model to obtain these results. and the water concentration in each laminate measured. 9 are easily rationalized by the solution-diffusion model as given above but are much more In the discussion above. four thin cellulose acetate films were laminated together. 2. a number of direct experimental measurements can be made to distinguish between the solution-diffusion model and other models.G. One prediction of the solution-diffusion model.16 J. I I I I 0 0 . . Thus. In these experiments.d i f f u s i o n m o d e l 0. the true driving force shown in Eq. diffusion. and subjected to feed pressures of 68 or 136 atm. the solution-diffusion model was used to derive equations that predict the experimentally observed performance of the membrane processes of dialysis. Wijmans. After the membrane laminate had reached a steady state. 10.15. 0 2 0 . If on the other hand.

) experiments. Baker~Journal of Membrane Science 107 (1995) 1-21 17 Membraneconcentrationgradients Concentration Concentration Concentration 0 I ~ 0 l ~From: Paul and Ebra-Lima 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..1 0.~.. Feed-side and permeate-side membrane concentrations. Wijmans. ell(m) i 0 12 From: Pauland PaciotU 10 8 n-Hexaneflux. From Paul and Paciotti [ 11 ]. W.Clt(m) Fig.. R. Maximum flux is obtained at the maximum concentration difference when the permeateside membrane concentration. the concentration gradient and the permeation fluxes approach their limiting values [7].e~o. cio.day) 6 4 2 / //" 0 Pervaporation • Reverseosmosis / 0 0. 11. Clo(m) . The change in the concentration gradient in the membrane as the applied pressure is increased is illustrated by the inserts. calculated from the operating conditions through Eqs.. Pressure permeation (reverse osmosis) of iso-octane and methyl ethyl ketone through crosslinked natural rubber membranes 265-/xm thick.J. dl (cm3/cm2.7 Hexane concentrationdifferencein membrane.5 06 0..G. c. At high applied pressures. ( 65 ) . Data taken from both pervaporation ( o ) and reverse osmosis ( .2 03 0. .4 0. and cj. Flux of n-hexane through a rubbery membrane as a function of the hexane concentration difference in the membrane.( 6 7 ) .equals zero. 12.

The hexane flux obtained in these two sets of experiments is plotted in Fig. but rejection of monovalent ions in the 20-50% range. reflects a decrease in diffusion coefficient as the swelling of the membrane decreases. These membranes are highly swollen by the organic solvents and. but it is not easily explained by a solutiondiffusion membrane. is also readily rationalized by the filtration-type mechanism of a pore-flow membrane.Ci#(. benzene. R. W. when operated in reverse osmosis fashion. no rejection by the ultrafiltration membrane. on the other hand. (30) and (56). We believe the difference between pore-flow and solution-diffusion mechanisms lies in the relative permanence of the pores. Baker~Journal of Membrane Science 107 (1995) 1-21 at 136 atm applied pressure is about twice that observed at 68 atm. it does not apply to ultrafiltration membranes used to separate proteins and other dissolved macromolecules from water. Transport in such membranes appears to be best described by a pore-flow model. For permeation of a single compound these equations can be simplified as follows. with membranes having good rejections to divalent ions and most organic solutes. and in reverse osmosis experiments with liquid at elevated pressures on the feed side and liquid at atmospheric pressure on the permeate side. large gradients develop through the membrane even at relatively modest applied pressures.vi(P°--Pe)l ~ ] (66) Pervaporation: 1 ci~<~) - Pe " . hence. 12 against the hexane concentration difference in the membrane (ci. In a solution-diffusion membrane. In a pore-flow membrane. (19). In other words.. The same transition range must also exist in gas-permeation membranes. Presumably.18 J. Wijmans. and carbon tetrachloride. whereas desalination-grade sodiumchloride-rejecting membranes clearly follow the solution-diffusion model [23. free-volume 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. the freevolume elements (pores) are relatively fixed and do not fluctuate in position or volume on the time scale of permeant motion. cio~.e.- ~/if(m)Pisat (67) Sorption data were used to obtain values for "Yi(m)"AS pointed out by Paul and Paciotti. The observation that many small solutes have the same permeation rate as water and.. Another series of papers by Paul and co-workers [711 ] focuses on the same phenomenon using rubber membranes and permeation of organic solvents such as hexane. the transition is in the nanofiltration range. 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. The . 11. Membranes that reject sucrose and raffinose but pass all micro-ions are clearly poreflow membranes. Fick's law. 12 show that reverse osmosis and pervaporation obey one unique transport equation. at the smaller values for Ci((m). The larger the individual free volume (65) Reverse osmosis: Ci¢(m) : ~/ie(m) ex 1 ~ .G.24]. 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. the data in Fig. i.~. 5.~ and Ci~. and the measured concentration on the permeate side is within 20% of the expected value calculated from Eq. were calculated from Eqs.. (28).m~.~. The transition region Although the solution-diffusion model appears to be a reliable method of describing transport in many membranes. These concentrations. Reverse osmosis and pervaporation: 1 Cio(m) : ")lio(m) decrease in the slope of the curve at the higher concentration differences. transport follows the solution-diffusion model. 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 solution-diffusion using reasonable values for the partition and diffusion coefficients of water.. Such data are shown in Fig.n) ). The transition between a pore-flow and a solutiondiffusion mechanism seems to occur with membranes having very small pores.

26]. These equations provide an accurate description of the behavior of these membranes and the dependence of membrane transport on pressure. has passed from being a polymer film with a distribution of transient free volume elements to an ultra-microporous membrane in which pore-flow transport occurs [25. This combination of extraordinarily high permeabilities. a small number for a glassy polymer but still more than would be expected for a simple pore-flow membrane. Nonetheless. together with the very high free volume. For example. because of its very high free volume. List of symbols Subscripts i. Gas permeabilities in PTMSP are orders of magnitude higher than those of conventional. The extremely high free volume provides a sorption capacity as much as ten times that of conventional glasses. diffusion coefficients are 103 to l06 times greater than those observed in conventional glassy polymers [27.4. j refer to components i and j Subscript m refers to the membrane phase Subscript o. More dramatically. f. means the concentration of component i in the membrane phase m at the permeate interface. (37)] B salt permeability constant [Eq. diameter.G. the ratio of the diffusion coefficients of oxygen and nitrogen (Do2/DN2) is 1. eventually producing capillary condensation in which the pores are partially or completely blocked by the absorbed vapor. A water permeability constant [Eq. basic principles without resource to process-specific factors. and pervaporation membranes. gas separation. hint at a poreflow contribution. for many years the most permeable polymer known. (20)1 . [30.26 ]. 7. the condensable vapor (CFC13) absorbs onto the walls of the small pores. The fundamental equations describing transport in all of these processes can be derived from simple. and are even substantially higher than those of polydimethylsiloxane. (41) ] c~. 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.28]. One interesting example that falls in this transition region is gas permeation through "superglassy" polymers. This blockage then prevents the flow of the noncondensed membrane. Wijmans. Dj Fick's law diffusion coefficient [Eq.. gases (nitrogen) through the 6. W. Jj membrane flux Ki.. K~ liquid phase/membrane phase sorption coefficient [ Eq. (61)1 Ji. The transport mechanism involved is then similar to that suggested by Barrer et al. and ci~ means the concentration of component i in the fluid at the permeate interface. PTMSP has an unusually high void volume. According to this mechanism. The best explanation for these unusual vapor permeation properties is to propose that PTMSP. reverse osmosis.J. the presence of as little as 1% Freon-11 (CFC13) in nitrogen lowers the nitrogen permeability of PTMSP more than 20-fold from the pure nitrogen permeability [29]. low-free-volume glassy polymers. Conclusions The solution-diffusion model is a good description for the transport through dialysis.~. PTMSP also has very unusual permeability characteristics with mixtures of condensable and non-condensable gases. As a rough rule of thumb. concentration and the like. R. the more likely they are to be present long enough to produce pore-flow characteristics in the membrane. ( 11 ) ] H Henry law coefficient [Eq. on the order of 25%. the transition between permanent (pore-flow) and transient (solution-diffusion) flow appears to be in the range 5 to 10 ~. Baker~Journal of Membrane Science 107 (1995) 1-21 19 elements (pores). such as poly(1-trimethylsilyl-l-propyne) (PTMSP) [ 25. cj mole concentration of components i and j Di.31 ] in the 1960s and 70s to rationalize gas flow in very finely microporous carbon membranes. Direct measurements of concentration gradients in membranes provide additional support for the model. and f refer to the feed and permeate interfaces Thus ci.

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. Sci. [3] H. 17 (1973) 433. a comprehensive parameter governing permeation of solutes through membranes.PjFUNCsat P~. Vol. [ 8] D. Polym. 5 (1970) 679. 1 (1976) 3.A. Kim and K. in H. 12 (1974) 1221. Appl. Sci. Pj p/C. Thompson. Bakish Materials Corp.. [18] F. Steady-state distribution of water in cellulose acetate membrane. New York.L.). J. J.20 J. MIT Press.. J. ( 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. R. The equivalent pore radius of dense cellulose acetate membranes. in R. Ind.D. Theeuwes.R. Merten and R.B. Pressure-induced diffusion of organic liquids through highly swollen polymer membranes. Baker. 21 (1960) 845. 8 (1970) 351. Ed. Glueckauf and P. U. Petterlin. P. Polym.G. Paul. Meares. W.B. Pervaporation Chem. Greenlaw. [2] E. Sourirajan. Paul. ( 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. Polym.W.). Reverse Osmosis. [12]D. Mauro.N. Diffusive transport in swollen polymer membranes. tzj vi A ~- y~. pj pO. Prince.R. [ 13 ] H. Permeability of Plastic Films and Coatings. J. PiFUNCsat.V. Sci. Meares. (42)] absolute temperature K chemical potential of c o m p o n e n t s i a n d j [ Eq. Rosenbaum and O. J.. Craig and J. Actual concentration profiles in membrane permeation. Phys. Theoretical and experimental study of pervaporation on the basis of pore flow mechanism. Yasuda. J. September 1992.M. Comments on the relationship between hydraulic permeability and diffusion in homogeneous swollen membranes. Pergamon. Cambridge.D. Matsuura. J. Baker~Journal of Membrane Science 107 (1995) 1-21 k Li 47 p Po. Sci. 13 (1974) 1215. Eur. 7 (1969) 101. Purif.. W.O. ( 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. J. Engelwood. Hopfenberg (Ed. Diffusion Processes. Appl.. Phys. 19 (1975) 1837. p ~ p/L. 1974. Paciotti and O. Riley. Sep. Merten. Sci. [ 14] U. Shelden and E. Polym. [5] P. [ 15 ] S. [ 16] S. Lonsdale. 2.G. [19] F.D.M. Academic Press. Ottawa. Driving force for hydraulic and pervaporation transport in homogeneous membranes. Polym.W. Ebra-Lima. Membrane Sci. Methods. On the mechanism of desalination by reverse osmosis flow through cellulose acetate membrane.. Ebra-Lima. Yasuda and A./xj tz °. J.N. Circulation. J. Product Data Sheet.. Transport properties of osmotic membranes. Okeda and T. Polym. Sixth Int. [9] D. Wijmans.. Diffusive and bulk flow transport in membranes. [4] A. [6] P. A simple predictive treatment of the permeation processes in pervaporation. 14 (1970) 2201. in Desalination by Reverse Osmosis. Paul and J. R. J. Appl.R. Appl.. Paul.. Polym. Membrane Sci. Desalination. 13 (1975) 1201..R. yj References [ 1] S. Sci. Sherwood. [ 21 ] J.J. Proc. 1970. Cotton. Further comment on the relation between hydraulic permeation and diffusion. Gordon and Breach.K. [7] D. p~ R R T /zi. p~. Webster. Hydraulic permeation of liquids through swollen polymeric networks: II Liquid mixtures. 2 (1966) 241. J. Conf.. Box 148. 9 (1965) 1344. Polym. Sci. [20]Mempro Company (Division of Oxygen Enrichment Company). (8)] coefficient ] Eq. Kammermeyer. 1991. 79 (1993) 101. 1966. Gale and R. Transference. W.M. Russell.R. Paul and O. J.). Polym.R.L. NJ.Y. Transport properties of cellulose acetate osmotic membranes. Bakish (Ed. Swinton (Eds. The effect of diffusive permeation rates by upstream and downstream pressures. [ 11 ] D. Diffusion and flow of water in homogeneous cellulose acetate membranes in J. 2 (1977) 141. Ed. Paul. MA. J. Baker.W. 1972. . The solution diffusion model for swollen membranes.. [17] A. Some properties of ionic and non ionic semipermeable membranes. Chadwick. Sci. Sci. Polym. Wijmans and R. New York. (47)] D a r c y ' s law c o e f f i c i e n t [Eq. [ 22 ] T. Membrane Sci. Muire and F. Petterlin and A. London. Sep.. R. [10] D.N.... Canada. 5 (1976) 33. A. Polym. Paciotti.

Sharma. H. Baker~Journal of Membrane Science 107 (1995) 1-21 [23] R. Srinivasan. Burban..B. [ 29 ] I. Pinnau and L.S.M. Private communication.. [25] R. Ash. Strathmann. Membrane Sci. [ 31 ] R.M. 34 (1987) 5.(trimethylsilyl). Membrane Sci... Eirich and H. 86 (1994) 67.C. Phys. Low pressure ultrafiltration of sucrose and raffinose solutions with anisotropic membranes. 21 [27] L. J. Royal Soc. Membrane Sci. R. Auvil and P.R.T. Proc. J.281. [28] Y. Gas separation processes. 1 (1966) 129.G. Elucidating the mechanism (s) of gas transport in poly [ 1. Ash. J.M.. Toy.G. Flow of adsorbable gases and vapors in microporous medium. R. . 5. 48 (1990) 321. [30] R..W. Barter and P. Thau. An investigation of the high gas permeability of poly(trimethylsilyl-l-propyne).G. Water transport in porous and nonporous membranes.A. [24] G. J. F. J. Chem. 271 (1963) 19. Sorption and transport of organic vapors in poly[(trimethylsilyl)-l-propyne]. Barter and C. Toy. Pinnau and R. R. Witchey-Lakshmanan.W. Pope. Bloch and O. W. Stem and T.1propyne] (PTMSP) membranes. Baker. Pat. S. Desalination. Ichiraku. U. S.J. [26] L. Nakagawa. R. Kedem. Membrane Sci.255 (25 January 1994). Sorption and flow of carbon dioxide and some hydrocarbons in a microporous carbon membrane. Wijmans. I. Bhem. 1 (1976) 17. Baker.R. Hopfenberg and R. 76 (1972) 238.

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