Nomenclature V+ = v/ Vu(0), dimensionless transyerse velocity

x = distance along longitudinal direction

A = membrane constant defined by Equation 6 X+ = x / u , dimensionless distance along longitudinal
U = half distance between membranes direction
B I , B2 = constant defined by Equations 2g and 8 Yn01) = eigenfunction in Equation 19
B(m, n) = beta function Y = transverse distance measured from center of channel
c = concentration of salt Y+ = y / u , dimensionless transverse distance
C,(O.y+) = concentration of salt a t inlet 2 = defined by Equation 23
= kth-order solution of perturbation solution D
DS = diffusion coefficient of salt in brine CY = defined as 2
a V w( 0 )
D?l = coefficients of Equation 20 = eigenvalue in Equation 19
fh = functions defined by Equation 15 = gamma function
K I , K2 = coefficients defined by Equation 24 = total pressure drop across membrane
Li,L z , La, Ld = coefficients defined by Equation 25 = constant
M I , M z , Ma, Mb, M E ,M 6 = coefficients defined by Equation = defined in Equation 31
26
ATl,-Y*, S a , A\74, S j , A T a , AV7,.V8 = coefficients defined by Equa-
tion 27 literature Cited
P I , Pz,Pa, P1, Pj, Pg, P7, Ps, Pg,Plo = coefficients defined by (1) Berman, A. C., J . Appl. Phys. 24, 1232 (1953).
Equation 28 (2) Dresner, Lawrence, “Boundary Layer Build-up in the De-
Po, = osmotic p r m u r e mineralization of Salt Water by Reverse Osmosis,” Oak Ridge
(P,J0 = osmotic pressure at concentration C, National Laboratory, Rept. 3621 (May 1964).
Q = volumetric rate of production defined by Equation (3) Sherwood, T. K., Brian, P. L. T., Fisher, R. E., “Salt Concen-
30 tration at Phase Boundary in Desalination Processes,” Desalina-
S = parameter defined by Equation 2f tion Research Laboratory, Department of Chemical Engineer-
U = velocity along longitudinal direction
ing, Massachusetts Institute of Technology, Rept. 295-1 (1963).
0 = buik velocity a t x = 0 RECEIVED for review October 17, 1964
U+ = u / U , dimmsionless velocity along longitudinal ACCEPTED April 22, 1965
direction IYork performed with the financial support of the Office of Saline
U = velocity along transverse direction Water under contract No. 14-01-0001-401. Numerical calcula-
VU = transverse water velocity across membrane tions supported in part by National Science Foundation Grant GP-
Vu(0) = transverse velocity a t x = 0 1137.

CON CENT RATIO N PO LA RIZATI 0 N I N

REVERSE OSMOSIS DESALINATION WITH
VARIABLE FLUX AND INCOMPLETE SALT
REJ ECT IO N
IP , L . T , B R I A N , Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Mass.

A finite-difference solution is obtained for salt concentration polarization in reverse osmosis with laminar
flow of brine between parallel flat membranes. The analysis accounts for the permeation flux falling off
as the salt concentration at membrane surface builds up, and the effect of incomplete salt rejection is also
included. The results are compared with the constant-flux solution, and it is found that the average polariza-
tion over the length of the membrane is very nearly the same’for the two cases, if the average permeation
fluxes are equal. This formed the basis of a simplified design procedure, based upon the constant-flux
solution, which accurately predicts polarization effects upon pressure drop requirements and product water
salinity.

N WATER desalinatiori by reverse osmosis, potable water is
I removed from a saline solution by permeation through a
semipermeable membrane which rejects the dissolved salts
more or less completely. The convective flow of the solution
carries salt u p to the membrane surface, and since the salt is
rejected by the membrme it must diffuse back into the bulk
saline solution. Thus the salt concentration a t the membrane
surface builds up to a value exceeding the bulk salt concentra-
tion until the back diffuijion of salt produced by this concentra-
tion gradient just counterbalances the convection of salt to the
membrane surface by iihe water flowing through the mem-
brane.
This salt concentration polarization has several effects which
are detrimental to the desalination process. First of all, the
osmotic pressure which must be overcome is that corresponding
to the salt concentration a t the membrane surface, and concen-
tration polarization results in this effective osmotic pressure
exceeding the osmotic pressure of the bulk saline solution.
I n addition, the concentration polarization has a detrimental
effect upon the salinity of the product water, because this
salinity will generally increase when the salt concentration
a t the membrane surface in the saline solution increases.
Likewise, the useful life of the osmotic membrane is often
shortened by increased salinity of the saline water, and con-

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 439

centration polarization will aggravate this effect. Finally,
most saline waters contain a t least one salt a t a concentration
level which is within a factor of 2 of its solubility limit. Thus,
excessive concentration polarization will often cause some salt
to concentrate a t the membrane surface to its solubility limit,
causing precipitation of this salt a t the membrane surface.
The problem of concentration polarization at the surface of a
reverse osmosis membrane has been discussed by Merten (3),
Merten, Lonsdale, and Riley ( 4 ) , and Sherwood. Brian,
Fisher, and Dresner ( 5 ) . Theoretical solutions are presented
(5)for concentration polarization effects for both turbulent and
laminar flo\\ in round tubes and for laminar flon in a t\vo-
dimensional channel. These results show that concentration
polarization effects are not insignificant when the water flux
rate is approximately 10 gallons per day per sq. foot, and
become increasingly important a t higher water flux rates.
Thus, as membranes are developed which permit operation
a t higher \\ater flux rates, concentration polarization Mill
become increasingly important and will be a major considera-
tion in the design and optimization of reverse osmosis systems.
The theoretical analyses for laminar flow (5) were based
upon the assumptions that the water flux rate through the
membrane N as uniform, independent of longitudinal position,
and that the salt rejection by the membrane was complete.
These idealizations are approached in desalination of brackish
waters of low salinity. but in such cases the effects of concen-
tration polarization are much less detrimental than in de-
salination of brines of high salinity. In desalination of sea
water, for example, the idealizations of uniform water flux and
complete salt rejection are not realized. Thus, this work
extends the theoretical analysis ( 5 ) for laminar flow between
flat osmotic membranes to assess the effects of water flux varia-
tion and of incomplete salt rejection upon concentration
polarization at the membrane surface.
Theoretical Model
The problem analyzed is concentration polarization in a
saline solution flou ing in a two-dimensional channel between
flat parallel osmotic membranes. The continuity equation for
salt conservation can be written in dimensionless form as
a ( CC) + 4 vc -
__
ax aY
[ = 0
This equation considers convection in the longitudinal direc-
tion and diffusion and convection in the transverse direction,
but neglects longitudinal diffusion. The normalized salt
concentration, C, is the local salt concentration divided by the
salt concentration in the brine feed a t the channel inlet, and
U and V represent the normalized velocity components in the
longitudinal and transverse directions, respectively. T h e
dimensionless coordinates, X and Y , represent dimensionless
distances in the longitudinal and transverse directions, respec-
tively; X would be numerically equal to the fractional water
removal a t a given longitudinal position if the water flux
through the membrane were to remain constant a t its value a t
the channel inlet. The normalized diffusion coefficient, a,,
is defined as the diffusion coefficient divided by the channel
half width and the flux through the membrane a t the channel
inlet, The boundary conditions to be imposed upon the
solution of Equation 1 are
At X = 0, any Y : C = 1 (2)
ac
At Y = 0, any: X-
dY
= 0 (3)
440 l&EC FUNDAMENTALS
At Y = 1, a n y X : cyo (E) = RVC (4)
Equation 2 represents the assumption that the salt concentra-
tion is uniform a t the channel inlet, and Equation 3 implies
symmetry with respect to the midplane ; this latter condition
is based upon the assumption that the t\vo osmotic membranes
forming the channel walls are identical in properties and are
therefore permeating a t equal rates. Equation 4 relates salt
diffusion and convection at the membrane surface to the salt
rejection, R, defined as 1 minus the ratio of the salt flux through
the membrane to the product of the permeation velocity a t the
membrane surface and the salt concentration a t the membrane
surface.
T o integrate this differential equation, the velocity field
must first be specified. Berman (7) has obtained a solution
for the velocity field for the case in which the water flux
through the membrane is uniform.
The quantity .\'I is a permeation Reynolds number, based
upon the half width of the channel and the permeation velocity,
and \+ill generally be so small in reverse osmosis desalination
applications that the terms involving it can be neglected.
With this simplification. Equation 5 reveals that the longi-
tudinal velocity varies in a parabolic fashion with transverse
position just as it does Lvhen there is no flux through the wall,
although in the present case the average velocity does vary
with longitudinal position as water is withdrawn through the
membrane. Similarly, the transverse velocity is simply equal
to the transverse velocity at the channel wall multiplied by a
cubic function of the transverse position.
A solution for the velocity field has not been obtained for the
general case in which the flux through the membrane varies
with longitudinal position. But when the permeation Reyn-
olds number, )TI, is small, the effect of a constant permeation
flux is simply to change the average longitudinal velocity
with longitudinal position; the parabolic profile is not dis-
torted. Thus, it seems reasonable to assume that the longi-
tudinal velocity profile can be represented by
3
u = -73 (1
2
- Y') (7)
even when the permeation flux varies with longitudinal position,
provided that the permeation Reynolds number is suitably
small. Similarly, it seems reasonable to assume that the
transverse velocity can be approximated by
u = uw (); (3 - Y2)
where uw is the permeation velocity a t the local longitudinal
position. Thus, the following analysis is based upon the
assumption that the velocity field can be approximated by
Equations 7 and 8. This implies the additional assumption
that the parabolic velocity profile is already developed a t
x = 0. Written in dimensionless form, these equations become
L7 = (4) (1 - A)(l - Y')
v = v,
(3 - (3 - Y*)
The quantity V, is the local value of the permeation velocity
divided by the permeation velocity a t the channel inlet. A is
the fractional water removal, obtained by integrating the
permeation velocity with respect to longitudinal position.
x 3 of ( 5 ) . T h e results for values of CY = 0.0677, 0.27, and 0.50
A = VwdX’
The permeation flux must now be related to the salt concen-
tration a t the membrane surface. Merten (3) reports that the
permeation velocity can be expressed by
U, = K(AP - AT) (12)
where AP is the pressure drop across the membrane, AT is the
difference between the osmotic pressures of the saline solution
a t the membrane surface and the product water, and K is the
membrane permeability constant. Assuming that the osmotic
pressure is directly proportional to the salt concentration and
that AP is essentially constant, Equation 12 may be written as
vu = 1 - P-f (13)
T h e constant 8, defined as
is a measure of the fraction of the pressure driving force which
is represented by the osmotic pressure of the feed solution.
T h e concentration polarization, y, is defined as
y c, - 1 (1 5)
and thus in Equation 13 represents the decrease in the
permeation rate due to the concentration polarization a t the
membrane surface.
The analysis that follows is for a brine containing a single
salt with a constant diffusion coefficient, and the volume change
upon mixing solutions of different salt concentrations is as-
sumed to be negligible. In considering membranes with
incomplete salt rejection, it has been assumed that the salt
rejection, R, is constant. This is a simplification; most
reverse osmosis membranes probably show a salt rejection
which decreases as the salt concentration a t the membrane
surface increases. Severtheless, the manner in which salt
rejection varies with salt concentration has not been studied
in detail nor well characterized, and thus the assumption of a
constant salt rejection seems to be most appropriate a t this
time. It should be adequate in order to indicate the effect
of incomplete salt rejection in a general way.
Solution of Differential Equation. T h e system of equations
represented by Equations 1 through 4, 9 through 11, and 13
was solved by a finite-difference method on a digital computer.
A description of the finite-difference method, a copy of the
Fortran program, and instructions for using the program are
presented by Brian (2, Appendix),
The degree of convergence of the finite-difference solution
could be judged by making standard convergence tests, in
which the increments in the longitudinal and transverse dis-
tances were decreased, and also by comparison with the
results of Sherwood, Brian, Fisher, and Dresner ( 5 ) for the case
in which the permeation. flux was constant and the salt rejection
was unity. Based upon these considerations, the finite-dif-
ference solutions are believed to be convergent to within less
than 0.5%.
Results and Discussion
A number of computer runs were made with a value of
= 0. For this case, according to Equation 13, the permea-
tion flux does not fall off as the concentration polarization
builds up, and thus this is the case of a uniform water flux.
The finite-difference solutions obtained with P = 0 and R = 1
are presented in Figure 1, plotted in the same manner as Figure
are in excellent agreement with the infinite series solution
presented in (5), and indeed the generation of the present
finite-difference results required considerably less computer
time than did the generation of the infinite series solutions.
Thus, this problem represents a n example in which a finite-
difference solution of the partial differential equation is more
readily obtained than is the infinite series solution. Shown
for comparison, as the dashed curve. is the approximate solu-
tion for the entrance region given by Equations 23 and 25 in
(5). The curve for each value of CY peels a\\ay from the en-
trance region solution as it approaches the limiting ’.far-down-
stream” polarization corresponding to that value of CY. Figure
1 shows that the approximate solution ne11 represents the
entrance region solution, although the approximate solution is
somewhat low a t low values of the abscissa in Figure 1. T h e
excellent agreement betxveen the finite-difference solution
obtained in the present work and the infinite series and approxi-
mate solutions reported previously lends considerable con-
fidence regarding the accuracy of these solutions. Since
Figure 1 contains the solution for a greater number of values
of CY than had been reported previously, it should be very
useful for quickly obtaining the concentration polarization of a
reverse osmosis membrane with a uniform permeation flux
and complete salt rejection.
Effect of Variable Flux. T h e effect of a variable permea-
tion flux is illustrated by the results of calculations performed
for CY, = 0.27, = 1, R = 1. T h e value of a, = 0.27 corre-
sponds to a permeation flux a t the inlet end of the membrane
equal to 10 gal./(day)(sq. ft.) if the membrane spacing is 0.1
inch-that is, if h = 0.127 cm.-or it corresponds to a permea-
tion flux of 100 gal./(day)(sq. ft.) if the membrane spacing is
only 0.01 inch. The value of p equal to unity corresponds to
a n applied pressure drop across the membrane equal to twice
the osmotic pressure of the feed brine; thus, a t the inlet end
of the channel, half of the pressure driving force is expended in
overcoming the osmotic pressure of the feed solution and half
is expended in overcoming the membrane permeation resist-
ance. These computations are for a membrane whichc om-
pletely rejects the salt. Figures 2, 3, and 4 present the results
of the calculation for this case.
The solid curve in Figure 2 shows the manner in which the
salt concentration a t the membrane surface increases with
450.0677
0.27
k
I
Figure 1 . Solution for constant flux and complete salt
rejection
VOL. 4 NO. 4 N0VEM:BER 1 9 6 5 441
 I .oL L A - u J
.'0 0.1 0.2 0.3
X
0.4 0.5 0.6
Figure 2. Concentration a t membrane sur-
face vs. longitudinal position
- = 0.27,6 = 1, R = 1
_...._.__
~~=0.933,P=O,R=1
longitudinal position. The salt concentration increases rapidly
a t first because of the high permeation flux near the channel
inlet. Then, as the concentration a t the membrane surface
approaches twice the feed concentration, the permeation flux
falls off drastically and the concentration curve flattens out.
At a value of X = 0.656, the salt concentration at the mem-
brane surface has reached a value of 1.797 times the feed
concentration.
The solid curve in Figure 3 displays the manner in which
the permeation flux falls off with increasing longitudinal
position. The values of V , are readily obtained from the
values of C, by use of Equation 13. At a value of X = 0.656,
the permeation flux has fallen to approximately 20% of its
value a t the channel inlet. The solid curve in Figure 4
presents the fractional water removal, A, as a function of
longitudinal position. X is numerically equal to the fraction
of the water that would have been removed if the permeation
flux had remained constant a t the inlet value. Figure 4 shows
that A = 0.19 when X = 0.656, and thus only 19% of the water
was removed in this membrane instead of the 6670 which
would have been removed if the concentration polarization
had not caused a reduction in the permeation rate. The
average value of the normalized permeation rate up to X =
0.656 is given by
yw -_0.19
_ = 0.2895
- because this would correspond to a negative value of the
0.656
and thus the average value of a is
0.27
s=-- - 0.933
0.2895
Comparison with Constant Flux Solution. Since the solu-
tion for a constant permeation flux and complete salt rejection
is well generalized according to Figure 1, it should be useful to
compare the results of the variable flux solution with those
for a constant flux and to inquire into the utility of the constant
442 I&EC FUNDAMENTALS
0.7 0
0 0.1 0.2 0.3
X
0.4 0.5 0.6 0.7
Figure 3. Permeation flux vs. longitudinal
position
cyo = 0.27, 6 = 1, R = 1
~
-- - - - - -- - CY = 0.933, 6 = 0, R = 1
flux solution for designing a variable flux system. The most
logical way to compare the two solutions is a t a common value
of the average permeation flux over the entire membrane.
Thus, the constant flux solution was generated for a = 0.933,
/3 = 0, R = 1. This corresponds to a case in which the
permeation flux is constant a t a value equal to 29y0 of the
permeation flux a t the channel inlet for the variable flux
example considered previously. The dashed line in Figure 3
represents the permeation flux for this case. The dashed
curve in Figure 2 presents the salt concentration a t the mem-
brane surface as a function of longitudinal position (normalized
with the value of uwo for the variable flux problem). Near the
channel inlet the concentration polarization for the constant
flux case is lower than that for the corresponding variable
flux case because the permeation flux is lower in the con-
stant flux case. At larger values of X approaching 0.656,
the reverse is true. The dashed line in Figure 4 presents the
fractional water removal as a function of longitudinal position
for the constant flux example. At a value of X = 0.656, 19%
of the water has been removed in both example problems.
Figure 2 reveals that the concentration polarization be-
havior in the constant flux example is different from that in the
variable flux example, as would be expected. Indeed, a t X =
0.656, C, has slightly exceeded 2 in the constant flux example,
and this could never happen in the variable flux example
permeation flux, according to Equation 13. Nevertheless,
it is logical to inquire into how the average polarization in the
constant flux example compares with that in the variable flux
example and how useful might the constant flux solution be for
designing a membrane system with a variable flux. Thus, for
the constant flux example shown in Figures 2, 3, and 4, the
average value of the concentration polarization up to X =
0.656 was computed according to

0 1.0
0 0.1 0.2 0.3 0.4 0.5 0.6
X X
Figure 4. Water removal vs. longitudinal
position
- #za= 0.27,9, = 1 , R = 1
I-..-..--cy = 0,933, p = 0,R = 1 ....-..cy = 0.838, = 0,R = 0.9
and the resulting value was found to be 0.6725. This value
can be used with Equati.on 13, modified to the average form
in order to form the basis of a design procedure based upon
the constant flux solution. Inserting values of 0.2895 and
0.6725 for p, and 7,r'espectively, in Equation 19, the calcu-
lated value of is 1.057, which is 6% greater than the actual
value. This corresponds to a required pressure drop equal to
1.95 times the osmotic pressure of the feed solution, instead of
the actual value of exactly twice the osmotic pressure of the
feed solution.
This example sugger,ts that the constant flux solution is
useful for preliminary design calculations of the effect of
concentration polarization when the permeation flux is in fact
variable according to E,quation 13. A constant flux solution
for a given average permeation flux can be used to obtain the
average polarization according to Equation 18. Equation 19
can then be used to calculate the pressure drop required to give
that permeation flux (on the average) in the presence of the
concentration polarization. For the example presented above,
this approximate design calculation predicts a required pres-
sure drop only 2.5% lower than the actual pressure drop re-
quired. Furthermore, the conditions in the example problem
presented a rather severe test of this approximate design
procedure, corresponding to a situation in which the permea-
tion flux fell off by a factor of approximately 5 owing to the
concentration polarization. At lower values of A in the
example case cited, the permeation flux has not fallen off as
much, and the approximate design procedure is even more
accurate.
This approximate design procedure has been tested for
several other conditions. One such condition is cyo = 0.5,
/3 = 1, R = 1, and A = 0.274. At this water removal, the
permeation flux had fallen to of its value a t the channel
5
0
1 l 1 l l l l l 1 l I l I
0.7 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Figure 5. Concentration a t membrane sur-
face vs. longitudinal position
-cyo = 0.27,p = 1, R = 0.9
._
inlet. Another condition tested is cio = 0.27, p = 0.5, R = 1,
and A = 0.359. At this point, V , had fallen to 0.26. For
both of these conditions, the approximate design procedure
was found to be as accurate as for the example cited previously,
the calculated value of p being within 6% of the actual value.
Thus, it is concluded that this approximate design procedure,
based upon the constant flux solution, should be useful in
predicting the excess pressure drop requirements due to
concentration polarization a t the reverse osmosis membrane.
T h e integration required to obtain the average value of y
according to Equation 18 can conveniently be avoided by
simply approximating the average value of y for the constant
flux calculation by the value of y a t the midpoint of the channel.
For example, in the case shown in Figures 2 through 4, a n
approximation to the average value of y can be obtained by
reading the dashed curve in Figure 2 a t a value of X = 0.328.
This yields a value of 0.702, and inserting this into Equation
19 with 8, = 0.2895 yields a calculated value of 13 equal to
1.01, a n error of only 1yo as compared to 670 when the integral
average value of y was computed according to Equation 18.
I n all examples which were examined, the use of the concen-
tration polarization a t the midpoint of the channel in place
of the integral average value resulted in a more accurate
calculation of according to Equation 19; since it is also much
simpler, it is the preferred method of calculation.
Effect of Salt Rejection. T h e solid curve in Figure 5
depicts the salt concentration buildup as a function of longi-
tudinal position for a case in which cyo = 0.27, p = 1, and R =
0.9. These conditions are similar to those for the example
shown in Figure 2, but in the present case the membrane
has a 90% salt rejection. Furthermore, while p is equal to
unity for both cases, in the present case this corresponds to a n
over-all pressure drop equal to 1.8 times the osmotic pressure
of the feed solution instead of twice this osmotic pressure.
Figure 5 shows that, a t X = 0.656, the salt concentration a t
the membrane surface has built up to a value equal to 1.768
times the feed concentration, and therefore the permeation
VOL. 4 NO. 4 NOVEMBER 1 9 6 5 443
 10, i -4
~2~0.0677
t A
A/3a2
Figure 6. Solution for constant flux, R = 0.9
flux has fallen to 2370 of its value a t the channel inlet. At this
point A = 0.211, and thus vm
= 0.322 and E = 0.838. The
salinity of the product water can be computed by the formula
and, a t X = 0.656, (c,/c,) is found to be 0.164.
The dashed curve in Figure 5 shows the result of a computa-
tion for cy = 0.838, p = 0, and R = 0.9. This represents the
case of a constant flux membrane operating at the same
average flux as that for the variable flux case shown as the
solid curve in Figure 5. As in the variable flux case, the
constant flux case is for a membrane with a 90% salt rejection.
The comparison between the constant flux results and the
variable flux results is seen to be similar to that shown in Figure
2. Using Equation 18, the value of a t X = 0.656 for the
constant flux example was found to be 0.651. Using this
value together with = 0.322 in Equation 19 yields a cal-
culated value of p equal to 1.04, only 4% greater than the
actual value. The value of y a t the midpoint of the channel,
X = 0.328, is read from the dashed curve in Figure 5 as 0.682.
Using this value instead of 4 in Equation 19 yields a calculated
value of p = 0.994, only 0.6y0 lower than the actual value.
For this example calculation the use of the constant flux
solution to calculate the required pressure drop for the mem-
brane is just as accurate when the salt rejection is 90% as in
the preceding example with complete salt rejection.
The constant flux solution can also be used to predict the
salinity of the product water. For the special case in which the
permeation flux is constant, Equation 20 simplifies to
GP
- =
60
(1 - R)(Y + 1) (21)
Using 4 = 0.651 in Equation 21 results in a value of 0.165
for (cJc,), which is within O.6Y0 of the actual value. If,
instead of using the integral average value of y, the value of y
a t the channel midpoint is used, the resulting value of ( c B / c 0 )
is 0.168, which is 2.5% greater than the actual value.
Utility of Approximate Design Method. The preceding
examples show that the proposed approximate design method,
based upon the constant flux solution, yields accurate predic-
tions of the effects of concentration polarization on the required
pressure drop and on the salinity of the product water. The
method is simple, and a digital computer is not required.
Therefore, the method should be very useful, a t least for
making preliminary design and optimization calculations.
444 I&EC FUNDAMENTALS
1
I
0.1
0.001 0.0I 0.I I 10 IO0
A/3a2
Figure 7. Solution for constant flux, R = 0.8
Furthermore, the general conclusion that the average polariza-
tion is relatively insensitive to the manner in which the permea-
tion flux varies would be expected to apply to cases not treated
in this study-for example, the tubular membrane analyzed in
( 5 ) . Consider also a brine containing a mixture of salts with
different rejection values; the computer program developed
in this study is not applicable to this case without considerable
modification. But the approximate procedure can be applied
to each salt separately to determine its average polarization,
and the extra pressure drop requirement and the product
water salinity can be computed from the average polarization
of each salt. The problem of a salt rejection varying with
concentration or the problem of osmotic pressure not being
exactly proportional to concentration would be handled in a
similar manner.
T o furnish all requirements for the approximate design
method, it would be useful to provide a generalized description
of the constant flux solution for incomplete salt rejection similar
to that given in Figure 1 for the case of complete salt rejection,
Figures 6 and 7 present the calculated results for a number of
different values of cy and for salt rejection values of 90 and 80%,
respectively. The variables plotted in Figures 6 and 7 are the
same as those plotted in Figure 1, but the ordinate, defined as
(1 f y ) ( l - A) -1 (22)
does not have the same physical significance when the salt
rejection is incomplete as it does for complete salt rejection.
When salt rejection is complete, r represents the concentra-
tion polarization relative to the mixing-cup average salt concen-
tration, as described in (5). For incomplete salt rejection r
as defined by Equation 22 does not have this interpretation
because of the salt which leaked through the membrane.
Nevertheless, P as defined by Equation 22 is a more con-
venient variable to work with for the case of incomplete salt
rejection because it is simply related to y . Furthermore, the
use of this variable results in bringing together the curves for
different values of cy into a common curve for the entrance
region, facilitating interpolation with respect to cy. Thus, the
method of plotting shown in Figures 6 and 7 represents a con-
venient way of expressing the numerical solutions obtained
for concentration polarization of a constant flux membrane
with incomplete salt rejection.
Conclusions
Finite-difference solutions have been presented for the
concentration polarization of a reverse osmosis desalination
membrane with a variable permeation flux and incomplete .ii = average value of u over channel a t a given value of x ,
salt rejection. When these solutions are compared with the cm./sec.
solutions for a constant flux membrane operating a t the same
u = u/a,
u = velocity component in y-direction, cm./sec.
average permeation flux, it is found that the concentration 5, = average value of urn over channel length, cm./sec.
polarization is greater for the variable flux case near the y = u/uwo
channel entrance and lower near the channel exit. The Ve = average value of Vu over channel length
x = longitudinal distance from channel inlet, cm.
average polarization for the constant flux case is very nearly
X = (u~,/U,) (x/h)
equal to that for the variable flux case, even under the rela- = transverse distance from channel midplane, cm.
y
tively severe conditions examined in which the polarization Y = yjh
caused the permeation flux to fall off by a factor of 5 from the
GREEK
channel entrance to the channel exit. This formed the basis
of a simple design procrdure in which the constant flux solution f f = D,‘u,h for constant permeation flux
can be used to predict i he effects of concentration polarization
ff, = D, Gw,h
s = D,%,h
upon the required pressure drop and upon the product water P = R x o / ( 4 P - RT0)
salinity for a variable flux membrane. This simple procedure, r = defined by Equation 22
together with generaliied graphs of the constant flux solution Y = c, - 1
\vhich are presented, should be useful in the design and optimi- 4 = defined by Equation 18
A = fractional water removal at a given longitudinal position
zation of reverse osmosis processes. More accurate calcula- AP = pressure drop across membrane, p.s.i.
tions of the concentration polarization can be performed by Air = difference in osmotic pressure across membrane, p.s.i.
using the finite-difference method developed in this study, v = kinematic viscosity of solution, (sq. cm.)/sec.
described in the appendix to (2). x = osmotic pressure, p.s.i.

SUBSCRIPTS
Acknowledgment
o = channel inlet-Le., x = 0
The machine computations were performed a t the Massa- p = product water, mixed average over length of membrane
chusetts Institute of Technology Computation Center, and the w = channel wall-Le., membrane surface
author is grateful for the use of the center’s facilities. This SUPERSCRIPT
study is part of a research program on desalination supported ’ = dummy variable in definite integral
by the Office of Saline LVater, U. S. Department of the In-
terior.
literature Cited
Nomenclature (1) Berman, A. S., J . Appl. Phys. 24, 1232 (1953).
(2) Brian, P. L. T., M.I.T. Desalination Research Laboratory,
c = salt concentration, g./cc. Rept. 295-7 (May 1965).
c = c c:, (3) Merten, Ulrich, IND. END. CHEM. FUNDAMENTALS
(1 963).
2, 229
D = molecular diffusion coefficient of salt, (sq. cm.)/sec. (4) Merten, Ulrich, Lonsdale, H. K., Riley, R. L., Ibid., 3, 210
h = half xvidth of channel, cm.
(1964).
K = membrane permeability constant, (cm./sec.)/p.s.i. (5) Sherwood, T. K., Brian, P. L. T., Fisher, R. E., Dresner, L.,
v = hu,./u
-.r Ibid.,4, 113 (1965).
Ts = salt flux through membrane, g./’(sq. cm.) (sec.)
R = fractional salt rejection = 1 - iVs/ceu, RECEIVED
for review May 7, 1965
u = velocity component in x-direction, cm./sec. ACCEPTED September 3, 1965

LIQUID P E R M E A T I O N T H R O U G H
PLASTIC F I L M S
R . B. L 0 N G , Central Basic Research Laboratory, Esso Research and Engineering Co., Linden, N . J.

Liquid permeaition i s apparently a special case of ordinary diffusion and can be explained by a classical
diffusion model. The exponential concentration dependence of diffusivity leads to equations which are very
sensitive to the concentration of liquid in the upstream side of the film. Furthermore, the liquid concentration
gradient through the film shows that essentially all the resistance to diffusion i s at the downstream edge of
the film. The imodel has been experimentally tested for permeation of hydrocarbons through polypropylene
film and predicts the observed effect of downstream pressure as well as solvent absorption rate for bulk
plastic.

HE selective permeation of gases through plastic films has
Tbeen \vel1 documented in the literature and the possibility
of using this phenomenon to carry out practical separations
has frequently been suggested (2, 4, 77-73). More re-
cently Binning et al. ( 7 ) reported that permeating mixtures
from the liquid phase on one side of the film to the vapor phase
on the other side has good commercial separation potential.
He called this process liquid permeation. However, this
process is not yet understood. Binning has suggested a liquid
permeation model based on the existence of two zones in the
polymer film, where the upstream zone exists as a highly
swollen liquid solution and occupies the major portion of the

VOL. 4 NO. 4 NOVEMBER 1 9 6 5 445