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Transport Properties of Nafion® Membranes in Concentrated Solution

Environments

Article in Journal of The Electrochemical Society · January 1982

DOI: 10.1149/1.2123797

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Transport Properties of Nafion® Membranes in Concentrated Solution

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VoL 129, No. I
125, 1981 (1978).
6. R. N. Fleck, D. N. Hanson, and C. W. Tobias, L a w -
fence R a d i a t i o n Laboratory., Berkeley, CA,
UCRL-11612 ( S e p t e m b e r 1964).
7. L. Lapidus, "Digital C o m p u t a t i o n for Chemical E n -
gineers," p. 153, M c G r a w - H i l l , New York (1962).
8. A. J. Ahlberg, E. N. Nilson, a n d J. L. Walsh, "The
C H A N G I N G ELECTRODE P R O F I L E S 85
T h e o r y of Splines a n d T h e i r Applications," A c a -
demic Press, New York (1967).
9. G. A. P r e n t i c e and C. W. Tobias, AIChE J., In press.
1O. O. Kardos, Plating, 61, 129 (1974).
11. G. A. Prentice, Ph.D. Dissertation, U n i v e r s i t y o f
California, Berkeley, L a w r e n c e B e r k e l e y L a b o r a -
tory, LBL-11694 ( D e c e m b e r 1980).

Transport Properties of Nafion R Membranes

in Concentrated Solution Environments
H. I..Yeager,* B. O'Dell, and Z. Twardowski
Department oi Chemistry, University oJ Calgary, Calgary, Alberta, Canada T2N 1N4

ABSTRACT
The t r a n s p o r t p r o p e r t i e s of perfluorinated cation exchange m e m b r a n e s in
c h l o r - a l k a l i cell solution e n v i r o n m e n t s have been studied using a n e w l y d e -
signed m e m b r a n e test cell. A r a d i o t r a c e r - w e i g h t m e t h o d was used to m e a s u r e
sodium ion a n d w a t e r t r a n s p o r t n u m b e r s for two Nation| perfluorosulfonate
m e m b r a n e s . A homogeneous film shows r a p i d l y decreasing sodium ion t r a n s -
p o r t n u m b e r s w i t h increasing NaOH catholyte concentration, reaching a value
of 0.56 mol F -1 w i t h 12.5M solution at 80~ A f a b r i c - b a c k e d m a t e r i a l w i t h a
sulfonamide exchange site l a y e r yields c o n s i d e r a b l y higher values with a more
complicated concentration dependence. W a t e r t r a n s p o r t n u m b e r s for the l a t t e r
m e m b r a n e a r e also higher; a value of about 3 mol F -1 is found for typical e x -
p e r i m e n t s in w h i c h the a n o l y t e solution is 5M NaC1. Results are discussed in
t e r m s of the m e c h a n i s m of ionic m e m b r a n e t r a n s p o r t in relation to p o l y m e r
w a t e r a n d e l e c t r o l y t e sorption.

R e c e n t l y we have r e p o r t e d self-diffusion coefficients in 2-10M potassium h y d r o x i d e solutions at room t e m -

for s o d i u m ion in s e v e r a l NafionR perfluorosulfonate
ion e x c h a n g e m e m b r a n e s in c o n c e n t r a t e d sodium h y -
d r o x i d e solutions at e l e v a t e d t e m p e r a t u r e s (1). The
d e t e r m i n a t i o n of m e m b r a n e diffusion coefficients is
p a r t of an e x p e r i m e n t a l p r o g r a m to p r o v i d e p a r a m -
eters for a m u l t i c o m p o n e n t t r a n s p o r t model of m e m -
b r a n e c h l o r - a l k a l i cells (2-4). In a d d i t i o n to m e a s u r e -
m e n t s of ionic diffusion and m e m b r a n e w a t e r and
e l e c t r o l y t e contents (1), it is also necessary to d e -
t e r m i n e the d y n a m i c p r o p e r t i e s of the m e m b r a n e
u n d e r conditions t y p i c a l of a n o p e r a t i n g cell. These
conditions include c o n c e n t r a t e d solution environments,
e l e v a t e d t e m p e r a t u r e s , and high c u r r e n t densities.
Here we r e p o r t a n e w cell design for m e a s u r e m e n t
of the sodium ion a n d w a t e r t r a n s p o r t n u m b e r s in
ion exchange m e m b r a n e s u n d e r these conditions.
A r a t h e r extensive l i t e r a t u r e exists on the d e t e r -
m i n a t i o n of ionic and w a t e r t r a n s p o r t n u m b e r s in ion
e x c h a n g e m e m b r a n e s . The m a j o r i t y of this w o r k has
been r e v i e w e d b y L a k s h m i n a r a y a n a i a h (5, 6). Two
methods for ionic t r a n s p o r t m e a s u r e m e n t s are H i t t o r f -
t y p e electrolysis e x p e r i m e n t s and i n d i r e c t emf m e t h -
ods. In similar fashion, m e m b r a n e w a t e r t r a n s p o r t
n u m b e r s can b e m e a s u r e d b y electrolysis techniques
or b y s t r e a m i n g potential measurements. Aside from
the systematic discrepancies which have been o b -
s e r v e d b e t w e e n emf and the true electrolysis results
(5), the f o r m e r techniques a r e i n a p p r o p r i a t e for this
w o r k because w e wish to m e a s u r e m e m b r a n e p r o p -
erties u n d e r conditions of high c u r r e n t density. Elec-
trolysis methods based on m e a s u r i n g changes in either
solution v o l u m e o r w e i g h t can be employed. Volume
m e t h o d s a r e g e n e r a l l y m o r e convenient, b u t a r e sus-
ceptible to errors due to m e m b r a n e m o v e m e n t and
are difficult to use at e l e v a t e d t e m u e r a t u r e s . Sinha
a n d Bennion (7) have d e t e r m i n e d potassium ion
t r a n s p o r t n u m b e r s for a cation e x c h a n g e m e m b r a n e
* Electrochemical Society Active Member.
Key words: current efficiency, ion exchange, electrolysis.
perature. Low c u r r e n t densities, 12 A m - 2 o r less,
w e r e used a n d results w e r e d e t e r m i n e d b y m e a s u r e -
m e n t of solution v o l u m e changes a n d t i t r i m e t r i c
analysis. The a v e r a g e r e l a t i v e s t a n d a r d deviation o b -
tained for the p o t a s s i u m ion t r a n s p o r t n u m b e r w a s
6% even for these c a r e f u l l y p e r f o r m e d measurements.
The need to create a m e a s u r a b l e concentration change
d u r i n g electrolysis with this a p p r o a c h presents a
p a r t i c u l a r p r o b l e m for ionic t r a n s p o r t n u m b e r m e a -
surements in c o n c e n t r a t e d solution environments. If
concentration changes a r e k e p t s m a l l it is difficult t o
obtain sufficient accuracy in solution analysis to ob-
tain a r e l i a b l e result. If l a r g e r concentration changes
are produced, such m e m b r a n e p r o p e r t i e s as w a t e r
a n d electrolyte content are altered. I n the l a t t e r case
i n t e r p r e t a t i o n of results becomes difficult. Meares and
Sutton (8) have described an e l a b o r a t e m e t h o d for
m e a s u r i n g m e m b r a n e ionic t r a n s p o r t n u m b e r s at con-
stant chemical composition using radiotracers. A l -
t h o u g h this a p p a r a t u s is not r e a d i l y a d a p t a b l e to the
e x p e r i m e n t a l conditions of i n t e r e s t here, it d e m o n -
strates that the use of r a d i o t r a c e r s can be effective in
l a r g e l y r e m o v i n g the p r o b l e m of concentration changes
in the m e a s u r e m e n t of m e m b r a n e t r a n s p o r t p a r a m -
eters. Thus t h e e x p e r i m e n t s which a r e described
here a r e based on the r a d i o t r a c e r d e t e r m i n a t i o n of
sodium ion t r a n s p o r t numbers, c o m b i n e d w i t h a
w e i g h t m e t h o d for the m e a s u r e m e n t of w a t e r t r a n s -
p o r t numbers. Results a r e discussed in terms of the
factors which influence the overall t r a n s p o r t c h a r a c -
teristics of an ion exchange m e m b r a n e in a c h l o r -
a l k a l i cell.
Experimental
A~paratus.--A d i a g r a m of the m e m b r a n e t r a n s p o r t
test cell is shown in Fig. 1 and 2. The c y l i n d r i c a l cell
is constructed e n t i r e l y of Teflon, w i t h an outside
d i a m e t e r of 15 cm. The Teflon stirring a s s e m b l y in
each h a l f - c e l l is held in place using a p r e s s - f t b e a r -
ing the threaded end cap. Teflon-coated m a g n e t i c
 86 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
CAP MAGNET BEARING STIRRER MEMBRANE
Fig. 1, Ion exchange membrane transport cell
s t i r r i n g b a r s p r o v i d e coupling to e x t e r n a l l y p l a c e d
magnets which are a t t a c h e d to constant speed motors.
Solutions a r e s t i r r e d at speeds of 600 r p m to avoid
concentration polarization at m e m b r a n e surfaces a n d
to hasten t e m p e r a t u r e equilibration. The ion exchange
m e m b r a n e is placed b e t w e e n the half-cells using sili-
cone r u b b e r gaskets, and the cell assembly is then
c l a m p e d t o g e t h e r w i t h brass end plates a n d t h r e a d e d
bolts (not shown). The i n t e r i o r c o m p a r t m e n t of
each h a l f - c e l l is conical in shape; this design allows
105 2 e x p e r i m e n t so t h a t w a t e r lost b y e v a p o r a t i o n can be
7~
Fig. 2. Top view of a half-cell, with dimensions in mm
January 1982
77'
- -t--i-+
-'-/T
/
STIRRER BEARING MAGNET CAP
for even distribution of c u r r e n t lines of flux t h r o u g h
the m e m b r a n e , o p t i m u m d r a i n a g e for solution r e -
covery, and gas b u b b l e d i s e n g a g e m e n t space above
the solution level.
Circular p l a t i n u m mesh electrodes of 6 cm d i a m
are used in the cell; p l a t i n u m w i r e leads are fitted
t h r o u g h t h r e a d e d Teflon fittings in openings B. The
electrodes have center holes to accommodate t h e
s t i r r e r shafts. Openings A are used for solution d e -
l i v e r y and sample w i t h d r a w a l . W e i g h e d d r y i n g tubes
filled w i t h m o l e c u l a r sieves a r e fitted here d u r i n g the
determined. Solutions are h e a t e d w i t h 80W c a r t r i d g e
h e a t e r s ( W a t l o w Electric M a n u f a c t u r i n g Company)
placed in each half-cell; t e m p e r a t u r e control ( • 1 7 6
is achieved using a p l a t i n u m t e m p e r a t u r e sensor and
p r o p o r t i o n a l t e m p e r a t u r e controller ( C o l e - P a r m e r
I n s t r u m e n t C o m p a n y ) . The h e a t e r s and t e m p e r a t u r e
sensor a r e i n s e r t e d into t i t a n i u m t u b u l a r holders
which are fitted into openings C a n d D (Fig. 2).
Procedure.--The m e m b r a n e is e q u i l i b r a t e d w i t h a p -
p r o p r i a t e solutions at e l e v a t e d t e m p e r a t u r e in t h e
cell for up to 24 hr. These solutions are t h e n c a r e f u l l y
r e m o v e d b y syphoning and r e p l a c e d with weighed
portions of identical solutions, about 330 ml for each
half-cell. A f t e r t e m p e r a t u r e e q u i l i b r a t i o n is achieved,
the anode c o m p a r t m e n t is doped w i t h sodium-22
radiotracer, an initial weighed s a m p l e of anode solu-
tion is removed, and constant c u r r e n t ( • is
initiated. The exposed m e m b r a n e a r e a is 8 cm2; a
c u r r e n t of 1.6A is used in all e x p e r i m e n t s to y i e l d a
c u r r e n t density of 2 k A m -2. Electrolysis is continued
for 1-2 h r u n t i l solution concentrations have changed
b y a b o u t 1%. Finally, anode and cathode solutions
are syphoned and weighed, and samples of cathode
solution a r e a n a l y z e d for r a d i o a c t i v i t y and composi-
tion b y titration. T y p i c a l l y 0.5% of the original r a d i o -
active sodium-22 is t r a n s f e r r e d d u r i n g an e x p e r i m e n t .
E x p e r i m e n t s w e r e conducted in which solutions
were i n i t i a l l y w e i g h e d into a d r y cell, and the cell
VoL 129, No. I TRANSPORT PROPERTIES 87

was disassembled to d e t e r m i n e last traces ( < l g ) of
solution left after syphoning. Both procedures yield
identical results, confirming the accuracy of the
simpler approach.
The sodium ion t r a n s p o r t n u m b e r , tNa+, is calcu-
lated from the weight concentration and radioactiv-
ity of the anode solution a n d the total a m o u n t of
transferred radioactivity. The true sodium ion t r a n s -
port n u m b e r describes the net a m o u n t of sodium
ion transported from the anode to the cathode com-
p a r t m e n t ; back-diffusion of sodium ion generates
a n error w h e n using radiochemical methods, p a r -
ticularly at low c u r r e n t densities (8). E x p e r i m e n t s
were therefore performed where the cathode solu-
tion was doped with radiotracer and its appearance
i n the anode solution was monitored. Corrections to
tNa+ were less t h a n 0.5%, as would be expected at a
c u r r e n t density of 2 kA m -2.
To calculate the transport n u m b e r of water, tH~o
(mol F - l ) , the weight of w a t e r i n the cathode solu-
tion before and after electrolysis is d e t e r m i n e d from
solution weight concentrations and weights. The t r a n s -
port n u m b e r is t h e n given by
(AWtH20) F
tH20 -- -~- 1
18.01 (i,A) (t,sec)
The second t e r m i n Eq. [1] corrects for the consump-
tion of water in the cathode reaction. Estimated s t a n -
dard deviation for tNa+ and tH20 are 0.015 and 0.5 mol
F - l , respectively.
Materials.--Two Nation m e m b r a n e s were studied:
1150 e q u i v a l e n t weight u n b a c k e d film and Nation 295.
The latter m a t e r i a l is a n 1150 EW m e m b r a n e which is
backed with a n open weave Teflon fabric (70% open
area), and the cathode surface of the m e m b r a n e has
been treated with e t h y l e n e d i a m i n e to produce w e a k l y
acidic sulfonamide exchange sites. Various properties
of these m e m b r a n e s in concentrated sodium hydroxide
solution have b e e n reported previously (1).
Results and Discussion
Sodium ion and water t r a n s p o r t n u m b e r s for 1150
EW are listed in Tables I and II. The values i n Table
I are those of experiments in which identical NaOH
solutions were used in anode and cathode compart-
ments. I n Table II all experiments utilized 5M NaC1 as
the anode solution while cathode solutions were either
Table I. Sodium ion and water transport numbers for 1150 EW
Nation, sodium hydroxide solution
5M NaC1 or various concentrations of NaOH. As seen in
the tables a n d Fig. 3, tNa+ decreases smoothly with i n -
creasing NaOH concentration for 1150 EW. This would
be expected due to increasing electrolyte sorption into
the m e m b r a n e phase. However, it has been observed
that although electrolyte invasion does occur for Nation
m e m b r a n e s i n concentrated NaOH solutions, the
a m o u n t of sorbed electrolyte r e m a i n s r e l a t i v e l y con-
stant over the concentration ranges used in this work
(1, 9). M e m b r a n e water contents for 1100 EW (9) and
Nation 295 (1) are seen to be greatly affected though,
and so the only m a j o r change in m e m b r a n e composi-
tion is the reduction in water content with increasing
electrolyte concentration. (This is reflected i n Table I
by the generally lower tH20 values for 1150 EW as
NaOH concentration increases.) Mauritz a n d co-work-
ers suggest that a t u n n e l i n g process of the form
H
N a + O - - H O H - ~ N a + O H - H20
5-8+
would enhance hydroxide ion t r a n s p o r t i n e n v i r o n -
ments of decreasing w a t e r content due to increased
[1] polarization of the O - - H bond (9). This explanation
appears reasonable in light of the measured transport
n u m b e r s and the rather u n u s u a l electrolyte sorption
characteristics of these m e m b r a n e s .
A n interesting aspect of the tSa+ values for 1150 EW
in concentrated solution is their relatively large m a g -
nitude. I n general the low concentration of exchange
sites (about 1.0 X 10 -3 m o l / g swollen polymer) in
1150 EW would not be expected to cause sufficient
D o n n a n exclusion of electrolyte to allow tNa+ to rise
much above 0.5. I n comparison, K r e s s m a n and co-
workers measured tNa+ for a heterogeneous sulfonate
ion exchange m e m b r a n e with m u c h larger ion ex-
change capacity and found that in concentrated NaOH
solution at 25~ tNa+ falls below 0.5 for solution con-
centrations larger t h a n 4M (10). We would a t t r i b u t e
the difference to the ion clustered morphology of
Nation. The ion clusters generate centers of high ex-
change site concentration r a t h e r t h a n a more even
distribution throughout the m e m b r a n e phase as for
conventional materials (11). The ion clustering phe-
n o m e n o n has been shown to produce a v a r i e t y of u n -
i.O ~-

Solution 0.(~-
concen-
Temper- ~ration t~a+ tH~o
ature (~ (tool 1-D (tool F-D (tool F-D

80 5,0" 0.78 2.4 0.8--

9.8 0.64 0.5 m

10.9 0.62 1.2 o

11.2 0.61 0.6 E
12.8 0,56 0.5
90 8.0 0.76 3.0 -0.7--
9,8 0.64 0.4
13.0 0.60 0.9 7
-F-
9 Molar concentrations wore determined at r o o m temperature.
0.(5--

Table II. Sodium ion and water transport numbers for 1150 EW
Nation, sodium chloride and sodium hydroxide solutions
0.5-
Anode Cathode I I I f I _ i
Temper- solution solution tN~+ t~2o 0 2 4 6 8 10 12 14
ature (~ (real 1-1) (tool 1-z) ( m o l F -1) ( m o l F -z )

NaOH Concentration, mol L -T

70 N a t 1 , 5.0 NaCl, 5.0 0.99 3.6
80 5.0 5.0 0.99 2.8
90 5.0 5.0 1.00 2.3
80 N a t 1 , 5.0 N a O H , 5.0 0.80 2.1 Fig. 3. Sodium ion transport number vs. NaOH catholyte concen-
80 5.0 9.5 0.69 1.9 tration. O , 0 : 1 1 5 0 EW membrane; [~, I1: Hafion 295. Anolyte
80 5.0 11.0 0.62 1.9
80 ,5.0 12.4 0.58 1.7 solution is NaOH far light symbols and 5M NaC| for dark symbols.
 88 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
usual t h e r m o d y n a m i c and transport properties for
Nation m e m b r a n e s i n dilute solution e n v i r o n m e n t s (12-
15). The tNa+ values of near u n i t y in NaC1/NaC1
systems i n T a b l e II are p a r t i c u l a r l y noteworthy. The
m e m b r a n e concentrations of sodium ion and chloride
ion i n 1150 EW e q u i l i b r a t e d with 5M NaC1 solution
at 80~ are 1.9 • 10 -8 a n d 0.4 X 10-3 mol cm -~,
respectively (16), indicating that while there is b r e a k -
down of D o n n a n exclusion a n d s u b s e q u e n t electrolyte
sorption, chloride does not participate i n conduction
of c u r r e n t at a high c u r r e n t density.
The transport n u m b e r s i n Table I for N a O H / N a O H
systems are seen to have little t e m p e r a t u r e depen-
dence. A similar result was obtained for the t e m p e r a -
t u r e dependence of self-diffusion of sodium ion i n
1150 EW for 9.5M NaOH solution, where the activation
energy of diffusion from 60 ~ to 90~ was o n l y 2.5 kcal
mo1-1 (1).
T r a n s p o r t n u m b e r s for Nation 295 are presented i n
Table III for experiments using identical NaOH solu-
tions a n d for those in which the anode solution was
fixed at 5M NaC1. These results m a y be compared to
other m e a s u r e m e n t s of the transport properties of
Nation 295. Hora and Maloney report a n average
caustic c u r r e n t efficiency of 88% for this m e m b r a n e
w h e n used i n a chlor-alkali cell (17). Maloney also
reports a c u r r e n t efficiency of 93% at 5M NaC1, 10M
NaOH concentrations and 2 k A m - a c u r r e n t density
(18) Berzins measured a water transport n u m b e r of
3.2 tool F -1 for 9M NaOH caustic strength with a m e m -
b r a n e of the 295 composition b u t without fabric b a c k -
ing (19). I n a recent report, Dotson and co-workers
(20, 21) measured tNa+ and tH20 for Nation 295 at 85 ~
a n d 1-3 kA m -2 c u r r e n t density. For experiments
where identical NaOH concentrations are used as ano-
lyre a n d catholyte, they report t~2o values from 4.0 to
1.5 over the concentration range studied in Table III,
i n excellent agreement with our results. However, their
tNa+ values are all about 0.1 mol F - 1 lower t h a n ours,
although they observe a peak in tNa+ at about l l M
NaOH as seen in Fig. 3. No e x p l a n a t i o n can be offered
here for this discrepancy. These workers have observed
that the transport properties of Nation 295 are inde-
p e n d e n t of c u r r e n t density i n the 1-3 kA m -2 range
(18, 20, 21). Thus we have not varied c u r r e n t density
here b u t have focused instead on the influence of other
parameters.
As seen in Table III and Fig. 3, the dependence of
tNa+ on NaOH concentration has change dramatically
with the introduction of the sulfonamide layer on
the cathode surface of the membrane. At i n t e r m e d i a t e
concentrations tNa+ actually increases with increasing
concentration followed b y a rapid decrease as the
NaOH cathode solution concentration is raised about
12M. The sulfonamide l a y e r is characterized by both
reduced w a t e r content and sorbed electrolyte a n d thus
serves as a b a r r i e r to hydroxide transport (I, I7). As
discussed b y iVfauritz et al., i n e n v i r o n m e n t s of ex-
t r e m e l y low w a t e r Ievels, as would be present i n the
sulfonamide layer, ion p a i r i n g would reduce the effect
Table III. Sodium ion and water transport numbers,
Haflon 295, 80~
Anode Cathode
solution solution tNa+
(tool 1-z) ( m o l 1-z ) ( m o l F -1 )
NaOH, 4.2 NaOH, 4.2 0.93
5.5 5.5 0.92
9.5 9.5 0.96
11.0 11.0 0.94
12.5 12.5 0.83
5.8 5.8 0.80"
NaCI, 5.0 NaOH, 5.0 0.91
5.0 9.5 0.94
5.0 11.4 0.96
5.0 12.8 0.88
* Treated m e m b r a n e s u r f a c e f a c i n g a n o d e solution.
January 1982
of a proton t u n n e l i n g mechanism of hydroxide t r a n s -
port (9). Similar b u t less pronounced i m p r o v e m e n t s
in c u r r e n t emciency are seen even with ~afion com-
posite m e m b r a n e s where the cathode surface of the
m e m b r a n e is simply a higher e q u i v a l e n t weight sul-
fonate form, yielding fewer exchange sites (19).
The presence of a m i n i m u m i n the tNa+ plots for
Nation 295 can be related to the effects of electro-
osmosis, in general t~zo is a function of tNa+ and other
m e m b r a n e parameters, b u t also strongly depends on
anolyte concentration for cation exchange m e m b r a n e s
(5, 21). Sodium ion, as the m a j o r c u r r e n t carrier, t r a n s -
ports net positive a m o u n t s of water across the m e m -
brane. The frictional interaction b e t w e e n this water
and hydroxide serves to increase tNa+. K r e s s m a n and
Tye provide a general discussion of the effects of elec-
troosmosis on cation transport n u m b e r for cation ex-
change m e m b r a n e s i n concentrated solution e n v i r o n -
ments (22). They predict a m i n i m u m can be obtained
in the concentration dependence of tNa+ for a suffi-
ciently large electroosmotic effect, even if anode and
cathode solutions are of the same concentration. With
fixed NaC1 concentration a n d increasing NaOH con-
centrations in the cathode compartment, a n osmotic
component to water transport might also be expected.
This would serve to increase w a t e r - h y d r o x i d e fric-
tional interaction. As seen in Fig. 3, the result for
Nation 295 is to shift the tNa+ curve to higher con-
centrations of NaOH for the mixed electrolyte experi-
ments. For the 1150 EW membrane, where $H20 values
are smaller, m u c h smaller differences in tNa+ are
seen b e t w e e n the two types of experiment.
Although w a t e r transport provides a positive con-
t r i b u t i o n to t~a+, the presence of large a m o u n t s of
water in a m e m b r a n e serves to favor hydroxide m i -
gration relative to that of sodium ion. These opposing
effects lead to c u r r e n t efficiencies generally lower t h a n
90% for homogeneous Nation materials in highly con-
centrated NaOH solution environments. Berzins m e a -
sured c u r r e n t efficiencies and water transport n u m b e r s
for three Nation m e m b r a n e s in NaC1/NaOH systems at
80~ and 8 kA m -2 c u r r e n t density: 0.1 m m thick 1100
EW, 0.05 m m 1500 EW, a n d a composite m e m b r a n e
composed of the two homogeneous films (19). The
1100 EW m e m b r a n e shows c u r r e n t efficiencies of 55%,
40%, and 70% at NaOH concentrations of 6M, 10M, and
14M, respectively. For the 1500 EW m e m b r a n e , c u r r e n t
efficiency steadily declines from 85% to 55% over this
concentration range. The water transport n u m b e r i n -
creases for 1100 EW from 2 to 3.5 mol F -1 while for
1500 EW it decreases from 3 to 2 mol F -1 with increas-
ing NaOH concentration. The performance of the com-
posite film is very s i m i l a r to that of the 1500 EW m e m -
brane, with the exception of slightly increased water
transport. As predicted b y K r e s s m a n and Tye, a m i n i -
m u m i n c u r r e n t efficiency is seen for the m e m b r a n e
with larger w a t e r content and, p r o b a b l y due to a n os-
motic contribution, the 1100 EW m e m b r a n e actually
has a superior c u r r e n t efficiency at highest NaOH con-
centrations. Thus the overall performance of a homo-
geneous m e m b r a n e is the net result of complicated
interactions among cation transport, eleetroosmosis,
osmosis, and the effect of m e m b r a n e water content on
the hydroxide transport mechanism. We would a t t r i b -
ute the higher c u r r e n t efficiency of Nation 295 over the
$H20 1100 EW/1500 EW composite m e m b r a n e to the lower
(tool F -1 ) acidity of sulfonamide exchange sites, which would re-
duce water content, enhance ion pairing, and thus
4.1 discourage hydroxide ion transport.
3.1
1.8 The water transport n u m b e r for Nation 295 in NaC1/
1.4 NaOH experiments is seen to r e m a i n at about 3, i n -
1.4
2.2* dependent of NaOH concentration. This value is similar
3,9 to that of 1150 EW in 5M NaCI solution. It is interesting
2.9
3.0 to note that the sulfonamide layer does not appear to
2.9 restrict water transport. A n increase in water concen-
tration in the 1150 EW portion of the 295 m e m b r a n e
due to electroosmosis might be responsible for this
 Vol. I29, No. I TRANSPORT P R O P E R T I E S
behavior, perhaps resulting in intramembrane pres-
sure gradients (2).
Krishtalik discusses the performance of a hypotheti-
cal two layer cation exchange membrane in chior-alkali
electrolysis (23). One layer would be highly conduct-
ing, but have low selectivity for transport of cations
over anions, and the second layer (such as the sulfon-
amide layer" in Nation 295) would have opposite prop-
,erties. His treatment yields the result that when the
selective layer faces the hydroxide solution, the cur-
rent efficiency of the composite membrane would be
the same or slightly higher than that of the layer when
used alone as a homogeneous film. If the placement of
the composite membrane is reversed in the cell, the
current efficiency should be somewhat better than us-
ing the nonselective film alone, but much lower than
that of the composite membrane in the opposite place-
ment. One experiment was performed here for Nation
295 in NaOH solutions, in which the sulfonamide layer
faced the anode compartment. As predicted, the tNa+
value of 0.80 is marginally higher than the 0.78 re-
sult for 1150 EW, but much smaller than the value of
0.92 when the membrane is used in the opposite con-
figuration.
In conclusion, the current efficiency of a chlor-
alkali membrane cell is seen to be a complicated func-
tion of several membrane and solution parameters.
These interactions become more complex in composite
membranes. General features which lead to high cur-
rent efficiencies are large ion exchange capacity to en-
hance cation diffusion and reject electrolyte sorption,
low water content to prevent hydroxide migration by
a tunneling effect, and osmotic or electroosmotic water
transport to increase the frictional interaction between
water and hydroxide ion. The optimization of mem-
brane performance therefore depends on the difficult
task of simultaneously improving each of these prop-
erties.
Acknowledgments
Dr. R. L. Dotson of Olin Chemicals provided valu-
able design assistance and Mr. Fred Jarvis supervised
construction of the membrane transport cell. N. Tyrer
and B. Kipling performed some experimental portions
of this work. The authors thank E. I. du Pont de
Nemours and Company for providing membrane
samples. Financial support for this research was pro-
vided by the Olin Corporation, Chemicals Division,
Southeast Process Technology, Electrochemical Tech-
nology Group.
Manuscript submitted March 6, 1981; revised manu-
script received ca. July 1, 1981. This was Paper 394 pre-
sented at the St. Louis, Missouri, Meeting of the So-
ciety, May 11-16, 1980.
Any discussion of this paper will appear in a Discus-
sion Section to be published in the December 1982
JOURNAL.All discussions for the December 1982 Discus-
sion Section should be submitted by Aug. 1, 1982.
View publication stats
89
Publication costs o] this article were assisted by The
University o] Calgary.
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