Journal of The Electrochemical

Society

You may also like

- Utility of an Empirical Method of Modeling
Sodium Ion Diffusion in Nafion® Ion Exchange Combined Zero Gap/Attached Electrode
Membrane ChlorAlkali Cells
Membranes Clifford W. Walton and Ralph E. White

- Report on the Electrolytic Industries for the

Year 2001
To cite this article: H. L. Yeager et al 1980 J. Electrochem. Soc. 127 303 Pankaj Arora and Venkat Srinivasan

- Current sources of carbon tetrachloride

(CCl4) in our atmosphere
David Sherry, Archie McCulloch, Qing
Liang et al.
View the article online for updates and enhancements.

This content was downloaded from IP address 58.137.45.65 on 01/02/2024 at 08:05

Vol. 127, No. 2 GAS-DIVERTING ELECTRODES 303

results in ohmic drop s a v i n g because the electrode can REFERENCES

be p l a c e d in a v e r y close p r o x i m i t y to the m e m b r a n e .
I n addition, a n increase in the c u r r e n t efficiency is
r e p o r t e d due to the i n d u c e d t u r b u l e n c e at the surface
of the m e m b r a n e facing the cathode. The g a s - d i v e r t i n g
electrode can e l i m i n a t e limitations on the electrode
height w i t h r e s u l t a n t capital i n v e s t m e n t savings.
Acknowledgment
T h e s u p p o r t of B A S F W y a n d o t t e C o r p o r a t i o n is
gratefully acknowledged.
M a n u s c r i p t s u b m i t t e d M a r c h 23, 1979; revised m a n u -
script received Aug. 1, 1979.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the D e c e m b e r 1980
JOURNAL. All discussions for the D e c e m b e r 1980 Dis-
cussion Section should be s u b m i t t e d b y Aug. I, 1979.
Publication costs o~ this article were assisted by
B A S F Wyandotte Corporation.
1. C. W. Tobias, This Journal, 186, 833 (1959).
2. Z. Nagy, J. Appl. Electrochem., 6, 171 (1976).
3. F. Hine, M. ~ a s u d a , R. N a k a m u r a , and T. Noda,
This Journal, 122, 1185 (1975).
4. R. E. De La Rue, and C. W. Tobias, ibid., 106, 827
(1959).
5. M. G. Fouad, G. H. Sedahmed, and H. A. E1-Abd,
Electrochim. Acta, 18, 55, 279 (1973).
6. M. G. F o u a d and G. H. Sedahmed, ibid., 19, 861
(1974).
7. M. G. F o u a d and G. H. Sedahmed, ibid., 20, 615
(1975).
8. L. J. J. J a n s s e n and J. G. Hoogland, ibid., 18, 543
(1973).
9. D. Jennings, A. T. Kuhn, J. B. Stepanek, a n d R.
Whitehead, ibid., 20, 903 (1975).
10. I. R o u s a r and V. Cezner, ibid., 20, 289 (1975).
11. F. Hine and T. Sugimoto, A b s t r a c t 459, p. 1143, The
Electrochemical Society E x t e n d e d Abstracts, Vol.
78-1, Seattle, Washington, M a y 21-26, 1978.
12. E. D. Creamer, M. K r u m p e l t , and J. Jorne, U.S.
Pat. 4,142,950 (1979).

Sodium Ion Diffusion in Nation |

Ion Exchange Membranes
H. L. Yeager and B. Kipling
Department of Chemistry, University of Calgary, Calgary, Alberta, Canada T2N 1N4
and R. L. Dotson*
Olin Corporation, Charleston, Tennessee 37310

ABSTRACT
D e v e l o p m e n t of m e m b r a n e c h l o r - a l k a l i cells d u r i n g this past decade r e p r e -
sents a m a j o r a d v a n c e m e n t for commercial electrochemical technology. Chemi-
cal engineering applications of s e p a r a t i o n processes such as this involve diffu-
sional mass t r a n s f e r t h a t can be t r e a t e d as a rate process. The c h l o r - a l k a l i
a p p l i c a t i o n includes sodium, chloride, and h y d r o x y l ions plus w a t e r as mobile
species in caustic soda and b r i n e solutions and also b e t w e e n i m m i s c i b l e m e m -
b r a n e and solution phases. These immiscible phases are b r o u g h t into contact
to allow selective t r a n s f e r of sodium and w a t e r from b r i n e to the caustic solu-
tions. P r e v i o u s d a t a r e p o r t e d on NaOH diffusion t h r o u g h Nation| m e m b r a n e s ,
D N a O H , a r e difficult to i n t e r p r e t because not only do t h e y involve h y d r o x i d e and
sodium ion fluxes to give average diffusion coefficients, but also u n k n o w n
g r a d i e n t s of e l e c t r o l y t e and w a t e r concentration are p r e s e n t in the m e m b r a n e
phase. This p r e s e n t w o r k g r e a t l y simplifies these p r o b l e m s encountered b y
isolating and m e a s u r i n g the precise sodium ion self-diffusion coefficient, D N a + ,
w i t h r a d i o - t r a c e r techniques in various du Pont Nation@ and E D A modified
m e m b r a n e s . It t h e n relates the D~'a + to e q u i v a l e n t weight, surface t r e a t m e n t ,
and fabric backing in these membranes. These data for D N a + a r e v e r y i m p o r t a n t
in c h l o r - a l k a l i cells because the sodium ion is the m a j o r c u r r e n t carrier; t h e r e -
fore, its value can be r e l a t e d to the r e l a t i v e activation e n e r g y and voltage
drop among similar m e m b r a n e s .

T h e d e v e l o p m e n t of c h l o r - a l k a l i cells which e m p l o y m e n t a l p r o p e r t i e s ( I - i 0 ) and its application to chlor-

p e r m s e l e c t i v e ion exchange m e m b r a n e s as s e p a r a t o r s
r e p r e s e n t s a m a j o r a d v a n c e m e n t in electrochemical
technology. Nation| 1 perfluorosulfonic acid ion e x -
change m e m b r a n e s have the necessary chemical sta-
b i l i t y and ionic t r a n s p o r t p r o p e r t i e s which are needed
for this a p p l i c a t i o n as well as for fuel cells of various
designs. In o r d e r to b r i n g these technologies to full
commercialization, it is i m p o r t a n t to develop a
thorough u n d e r s t a n d i n g of the physical and chemical
p r o p e r t i e s of the m e m b r a n e for solution e n v i r o n m e n t s
in which it is to be used. Recently, s e v e r a l studies of
Nation have been r e p o r t e d which r e l a t e to f u n d a -
* Electrochemical Society Active Member.
Key words: transport, polymer, chlor-alkali.
1 R e g i s t e r e d t r a d e m a r k of E. I. d u P o n t de N e m o u r s a n d Com-
pany.
alkali (11-16) or fuel cell systems (17-20). The
central morphological f e a t u r e of Nation is the a g g r e g a -
tion of exchange sites and counterions into clusters,
w i t h a Bragg spacing of about 50A (l, 13). G i e r k e
discusses the ion clustering p h e n o m e n o n w i t h r e g a r d
to ion t r a n s p o r t and h y d r o x i d e rejection in chlor-
a l k a l i cells (13). The t r a n s p o r t p r o p e r t i e s of Nation
have been found to v a r y c o n s i d e r a b l y with e x t e r n a l
solution concentration (12, 16-18), p r e s u m a b l y due to
changes in 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 content.
M e m b r a n e s which are p r o d u c e d b y du Pont for
c h l o r - a l k a l i applications a r e g e n e r a l l y composites of
two e q u i v a l e n t weights of p o l y m e r or of one e q u i v a l e n t
w e i g h t w h e r e one surface has been chemically modified
to change the n a t u r e of the ion exchange grouping
304 J. EZectrochem. 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
(12, 14-16). These modifications alter the m e m b r a n e ' s
dynamic properties; it has been found for e x p e r i m e n t s
in wh i ch NaC1 and NaOH solutions are separated by
such m e m b r a n e s t h a t the properties of the m e m b r a n e
side w h i c h is in contact with NaOH solution dominate
the o v e r - a l l m e m b r a n e p e r f o r m a n c e (16). A p p a r e n t
m e m b r a n e diffusion coefficients of N a O H have been
m e a s u r e d for such systems (12, 16). Diffusion in-
creases w i t h l o w e r e q u i v a l e n t weights and increasing
NaOH concentration. S u r f a c e modification to produce
sulfonamide e x c h a n g e sites lowers diffusion rates by
a factor of fifty w h il e doubling the activation e n e r g y
of diffusion (16).
A difficulty in the i n t e r p r e t a t i o n of these a p p a r e n t
NaOH diffusion coefficients is that not only are h y d r o x -
ide and sodium ion fluxes coupled to produce an a v e r -
aged diffusion coefficient, but u n k n o w n gradients of
e l ect ro l y t e and w a t e r concentration exist in the m e m -
brane phase. In o r d e r to r e m o v e these problems, we
have m e a s u r e d the self-diffusion coefficient of Na + in
various Nation samples using a tracer method u n d er
e q u i l i b r i u m conditions. We wish to d e t e r m i n e the influ-
ence of e q u i v a l e n t weight, surface treatment, and
fabric backing on the m e m b r a n e diffusion of Na +,
w h i ch is the m a j o r c u r r e n t - c a r r y i n g species in the
c h l o r - a l k a l i m e m b r a n e cell. M e m b r a n e w a t e r and
NaOH concentrations have been d e t e r m i n e d also as a
function of t e m p e r a t u r e and solution con2entration.
Finally, the m e m b r a n e voltages of two Nation m at er i al s
w h i ch are produced for c h l o r - a l k a l i applications h a v e
been m e a s u r e d in an o p e r a t in g cell.
Experimental
The properties of Nation m e m b r a n e s w h i c h w e r e
studied are presented in Table I. Nation 214 and 295 are
m a n u f a c t u r e d for c o m m e r c i a l c h l o r - a l k a l i use and
h a v e one surface c o n v e r t e d to sulfonamide exchange
sites (14). This is accomplished by t r e a t i n g one sur-
face of the p o l y m e r w i t h e t h y l e n e d i a m i n e (EDA)
while in the sulfonyl fluoride form. Open w e a v e
Teflon fabrics are used with these m e m b r a n e s to i m -
prove strength. The T-900 fabric, used in No. 295, pro-
vides a large open area because r a y o n threads present
in the fabric can be chemically r e m o v e d after l a m i n a -
tion to the m e m b r a n e . In practice the sulfonamide side
of the m e m b r a n e is exposed to NaOH solution in a
c h l o r - a l k a l i cell.
M e m b r a n e s w e r e p r e t r e a t e d by e q u il ib r a t io n of the
m a t e r i a l for several hours in NaOH solution of given
concentration and t e m p e r a t u r e to be used in the ex -
periment. E q u i l i b r a t i o n times w e r e 8 hr or longer.
Since Nation's properties are not completely r e v e r s i b l e
w i t h t e m p e r a t u r e cycling (6, 18), data w e r e taken
using m e m b r a n e samples which had not been heated to
t e m p e r a t u r e s above that of the experiment. W at er
sorption m e a s u r e m e n t s w e r e m a d e by a w e i g h t - d r y i n g
method. Samples w e r e dried at 150~ in v a c u u m before
weighing, and completeness of drying was checked by
m e a s u r i n g the i n f r a r e d spectra of the dried materials.
Corrections for sorbed electrolyte w e r e applied to
w e i g h t changes.
Table I. Properties of Nation membranes
EDA Thick-
Membrane Equiv. conver- hess,
designation wt. sion mm
1150 EW 1150 -- 0.25
1200 EW 1200 -- 0.25
1150 (EDA) 1150 --0.04 mm 0.18
EDA 1150 total 0.18
No. 214 1150 ~0.04 mm 0.18
No. 295 1150 ~0.04 mm 0.18
February I980
M e m b r a n e Na + concentrations w e r e d e t e r m i n e d
using a r a d i o t r a c e r method. M e m b r a n e samples w e r e
e q u i l i b r a t e d w i t h a N a O t t solution w h i ch had been
doped w i t h 22Na+. The m e m b r a n e was then removed,
carefully blotted, and counted using a w e l l - c o u n t e r
w i t h associated electronics. The r ad i o t r acer was ob-
tained as a c a r r i e r - f r e e aqueous solution from c o m m e r -
cial sources, and was used as received. Fo r m e m b r a n e s
w i t h o u t fabric backing, dimensional changes w i t h
t e m p e r a t u r e and concentration w e r e m e a s u r e d and
used to calculate m e m b r a n e Na + molarities. A w i d e
flange m i c r o m e t e r (L. S. S t a r r e t t Company, Athol,
Massachusetts) was used to m e a s u r e the thickness of
m e m b r a n e samples, w i t h a r e p e a t a b i l i t y of about 0.01
mm. Fabric backed m e m b r a n e s showed m i n i m a l di-
mensional changes ( < 3 % ) .
Sodium .ion self-diffusion coefficients w e r e also de-
t e r m i n e d using 22Na+ radiotracer. In this procedure,
the membrane separates NaOH solutions of identical
composition, and the radiotracer is added to one solu-
tion to initiate the experiment. At periodic intervals,
1 ml samples are withdrawn from the second solution.
Steady-state conditions prevail as long as a small frac-
tion of the total amount of tracer has been transferred
(<2%). A diagram of the diffusion cell is shown in
Fig. I. The cell is constructed of borosilicate glass,
with Teflon stirring paddles in each I00 ml compart-
ment. Constant speed motors are used to drive the
stirrers at 500 rpm. Silicone rubber gaskets hold the
membrane in place; the exposed membrane area is
I0 cm 2. Cold water condensers are mounted on the
ports to prevent evaporation, Asearite-filled drying
tubes are used to prevent CO2 uptake from the at-
mosphere, and the cell is thermostatted to ___0.1~ us-
ing a glass w a t e r jacket.
The s t e a d y - s t a t e flux of Na + is g i v en by
J- ---DC--/d(1 + 2DCS/DCd) [1]
w h e r e J is the flux in mole cm -2 sec -1, D is the diffu-
sion coefficient, C is m o l a r concentration, d is m e m -
brane thickness, 8 is the thickness of the u n s t i r r e d
liquid film at each m e m b r a n e surface, and b a r r e d
quantities r ef er to values w i t h i n the m e m b r a n e phase
(21). With reasonable stirring and the high solution
concentrations used here, the second t e r m in the de-
n o m i n a t o r is m u c h less than unity and the expression
simplifies to
J --__ --DC/d [2]
A f ew e x p e r i m e n t s w e r e p e r f o r m e d in dilute solution.
In these cases, 5 was estimated f r o m values which have
been d e t e r m i n e d in the same cell u n d e r similar solu-
tion conditions (3, 5). The change in D from that
neglecting film diffusion was about 20% in the most
extreme case.
The voltage drop across Nation 214 and 295 under
conditions which duplicate an operating chlor-alkali
cell was measured using a Teflon la0oratory-scale cell.
A steel cathode and a TiO2-RuO2 coated titanium anode
were the working electrodes. Membrane area was 60
cm 2, the NaCl solution concentration was fixed at 4.8M,
and the cell temperature was controlled at 85~ The
membrane voltage drop was measured using two probe
electrodes and Luggin capillaries which extended to
WATER JACKET GASKETS TEFLON STIRRER MAGNET
Fabric
( % open
area )
MOTOR ~ j
--
--
--
- -
"T-24" TEELON
STIR OAR
MEMBRANE GLASS STIRRER
SUPPORT
(32%)
"T-900" Fig. 1. Cell for membrane diffusion studies
(70%)
Vol. 127, No. 2 ION EXCHANGE MEMBRANES 305

each m e m b r a n e surface. C u r r e n t density was set at

2 kAm-2.
Results and Discussion
1.0 /
M e m b r a n e w a t e r sorption and Na + concentration at 019
s e v e r a l t e m p e r a t u r e s and N a O H solution c o n c e n t r a -
tions are g i v e n in Tables II and III. T h e h i g h e r e x -
change capacity of 1150 e q u i v a l e n t w e i g h t (EW)
produces h i g h e r sorption c o m p a r e d to 1200 EW, as
expected. A comparison of results for the two backed
0.8 ~
8 0.7
m e m b r a n e s r e v e a l s the influence of the fabric. The
m u c h l a r g e r Na + and w a t e r concentrations for No. 295 n~
p r o b a b l y r e s u l t f r o m void spaces w i t h i n the m e m b r a n e nO 0.6 -
w h i ch are p r o d u c e d w h e n r a y o n strands are chemically CD
Z
dissolved. It is also seen that m e m b r a n e w a t e r contents <~
a r e v e r y sensitive to e x t e r n a l solution concentration. QC 0.5 -
F-
Th e Na + m e m b r a n e concentrations a r e essentially
constant; this m a y be because the increasing t e n d e n c y z 0.4 -
f or N a O H sorption is balanced by l o w e r e d w a t e r con- cq

tents as solution c o n c e n t r a t io n increases.

Plots of typical t r a c e r flux data a r e s h o w n in Fig. z 0.3 -
2 for the No. 214 m e m b r a n e . A t l o w e r t e m p e r a t u r e s , w
cD
t r a n s p o r t is o ft e n e x t r e m e l y slow and only u p p e r r~
w
limits to Na + m e m b r a n e diffusion coefficients can be 8. 0.2 -
m a d e in some cases. Self-diffusion coefficients of Na +
in all m e m b r a n e samples are given in Table IV. V e r y
si m i l ar trends can be seen for these diffusion coeffi- 0.1 -
cients as c o m p a r e d to m e m b r a n e w a t e r concentrations,
w i t h h i g h e r w a t e r sorption producing enhanced diffu- 0 ' I I I
sion. Self-diffusion coefficients for the two fabric 0 10 20 30 40 50 60 70
backed m e m b r a n e s m u s t be c o m p a r e d to those of the TIME, HOURS
u n b a c k e d m a t e r i a l s w i t h caution, however. The
m e a s u r e d area and thickness of No. 214 and No. 295 Fig. 2. Na + tracer flux in Nafion 214, 9.4M NaOH external
are not the effective values for a diffusing sodium ion. solution. 25~ O ; 40~ /k; 55~ V; 70~ []; 85~ O.
Errors in C and J w h i c h are caused by area m e a s u r e -
men t s cancel in Eq. [2], b u t the e r r o r in d, and in backed m e m b r a n e s is m o r e restricted than in t h e i r u n -
w h i ch employs d, will multiply. The presence of fabric backed analogs, 1150 EW or 1150 (EDA).
a p p r o x i m a t e l y doubles the m e a s u r e d thickness; t h e r e - If ionic diffusion in Nation can be t r e a t e d as a simple
fore we estimate that the actual Na + self-diffusion kinetic process w i t h a characteristic activation energy,
coefficients for these fabric b a c k e d m e m b r a n e s are then
about a factor of four s m a l l e r than the values listed in DNa+ ~ exp (--EAcT/RT) [3]
T a b l e IV. This m e a n s that Na + diffusion in the fabric
and a plot of log D vs. 1/T should be linear. This is
found to be true for the u n b a c k e d m e m b r a n e s b e t w e e n
Table II. Water sorption, g H20/g dry membrane 60 ~ and 90~ as sh o w n in Fig. 3. A c t i v a t i o n energies of
diffusion w e r e calculated f r o m the slopes of these lines
Temperature and are g i v en in Table V. Values of 3-5 kcal mole -1
Concen- are typical of ionic activation energies in aqueous
Membrane tration 60~ 70~ 80~ 9 o~
solution, and t h e r e f o r e Na + diffusion m a y be solution-
like in 1150 and 1200 EW. Conversion of some sulfonate
1200 E W 9.5M 0.072 0.097 0.082 0.069 e x c h a n g e sites to w e a k l y acidic su l f o n am i d e groupings
1150 E W 9,5M 0.080 0,111 0.098 0.091
a p p r o x i m a t e l y doubles the activation energy. This is
1150 ( E D A ) 9.5M 0.079 0.096 0.087 0.081
No. 295 9.5M 0.151 0.200 0.175 0.161 p r o b a b l y due not only to the r ed u ced w a t e r content
ll.OM 0.101 0.113 0.108 0.157 w i t h 1150 (EDA) but m o r e i m p o r t a n t l y to the enhanced
12.5M 0.070 0.075 0.081 0.087 attraction of sulfonamide sites to counterions. This
25~ 4O~ 55~ 70~ 85~
No. 214 5.9M 0.075 0.074 0.031 0.085 0.091
m i g h t be expected because of the m u c h s t r o n g e r basic
9.4M 0.032 0.U31 0.041 0.055 0.065 properties e x h i b i t e d by i o n i z e d sulfonamides r e l a t i v e
ll.0M 0.023 0.024 0.026 0.030 0.046 to sulfonates in aqueous solution. F u l l conversion to
12.5M 0.024 0.u28 0.027 0.025 0.034
15.1M 0.020 0.020 0.018 0.024 0.025 the sulfonamide f o r m w i t h the (EDA) m e m b r a n e

Table III. Membrane Na + concentration, male liter -1 Table IV. Self-diffusion coefficient of Ha +, cm2 sec-1 ( • 10s)

Temperature Concen- Temperature

Concentration tration
Membrane of N a O H 60~ 70~ 80 ~ 90~ Membrane of N a O H 60~ 70~ 80~ 90~

1200 E W 9.5M 2.54 2.29 2.32 2.48 1200 E W 9.5M 19.1 26.3 30.9 34.5
1150 E W 9.5M 2.95 2.83 2.61 2.56 1150 E W 9.5M 29.6 31.5 35.2 39.8
1150 ( E D A ) 9.5M 2.61 2.62 2,57 2.35 1150 ( E D A ) 9.5M 17.2 24.7 30.6 40.8
EDA 9,5M 1,64 1.64 1.50 1.49 EDA 9.5M 4.4 7.6 12.5 19.9
No. 295 9.5M 2.99 3.04 2.80 2.72 No. 295 9.5M 28.6 42.7 59.5 83.0
ll.0M 220 2.52 2.70 2.83 ll.OM 18.5 30.7 38.3 46.0
12.5M 2.81 3.31 3.01 2.82 12.5M 6.2 9 9.9 13.5 18.5
25~ 4~~ 55~ 70~ 85~ 25oC 40oc 55oc 70oc 85oc
No. 214 5.9M 1.48 1.61 1.77 1.76 1.71 No. 214 5.9M 11.8 23.1 54.4 102 154
9.4M 1.98 1.~6 2.03 2.02 1.91 9.4M 0.1 4.7 10.8 21.9 44.9
ll.0M 2.02 2.26 2.37 2.41 2.25 ll.0M <0.06 1.12 5.7 10.5 19.2
12,5M 2,26 2.63 2.33 2.20 2.13 12.5M <0,03 <0.03 1.70 5.1 1O.0
15.1M 2.75 2,99 2.80 2.37 2.38 15.1M <0,06 <0.06 0.1 0.45 0,53
306

I 0 - 6 L-"
olk
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 February I980

go ~, 10"
(D
OJ
E
r

ad Io -7
la I0_8 \ _

I I I I 10-9 ~ " ~ ( ) ~ (~)_

90 ~ 80 ~ 70 ~ 60 ~ I I I I I
I I I I 85oC 70 ~ 55 ~ 40 ~ 25 ~
2.7 I I I I I I I
2.8 2 9' 3.0 2.8 2.9 3.0 3.1 3.2 3.3 3.4
IO00/T, ~ 10001T , ~ -I
Fig. 3. Arrhenius plots for Na + diffu4on in Nation membranes, Fig. 4. Arrhenius plots for Na + diffusion in Nation 214, NaOH
9.5M NaOH external solution. O, 1150 EW; i1, 1200 EW; A, external solution. O, 5.9M; ~, 9.4M; ~, 11.0M; I-1, 12.5M; O,
1150 (EDA); V, EDA. 15.]M.

yields greatly reduced diffusion coefficients and a very

high energy of activation.
A r r h e n i u s plots for Nation 214 and 295 are shown 10-6
i n Fig. 4 and 5. L i n e a r relationships are again seen
above 60~ Results which were obtained for No. 214 at
lower t e m p e r a t u r e s indicate that the activation energy
of diffusion increases abruptly, especially at higher
NaOH solution concentrations. This suggests that the
mechanism of diffusion changes below a given t e m p e r a -
ture and solution concentration. This is similar to the
results of ionic self-diffusion m e a s u r e m e n t s in dilute o,I
solutions for Nation 120 EW using w a t e r and other E
swelling solvents (5). Activation energies of diffusion
for Na + were 7 and 4 kcal mole -1 for w a t e r and id
m e t h a n o l systems, respectively. However for Na + in I0-7
acetonitrile or Cs + in all three solvent systems, activa-
tion energies were 15-20 kcal mole -1. These m u c h
higher values were a t t r i b u t e d to the i n a b i l i t y of
counterions to transport b e t w e e n ion clusters. This m a y
explain the changes i n slopes for the lines in Fig. 4 as I I I I
well. ~ 90 80 70 60
Activation energies calculated from the higher t e m -
p e r a t u r e data for No. 213 and No. 295 are larger t h a n I I I I
that of the analogous m e m b r a n e without fabric back- 2.7 2.8 2.9 3.0
ing, 1150 (EDA). Also, the two fabrics yield different
increments to the activation energy. This suggests that 1 0 0 0 / T , ~ -I
the p o l y m e r morphology m a y be altered in the fabric Fig. 5. Arrhenius plots for Na + diffusion in Nation 295, NaOH
l a m i n a t i o n step of m a n u f a c t u r i n g such membranes, external solution. O, 9.5M; D, 11.0M; A, 12.5M.
for i n the absence of such changes the activation energy
of diffusion should r e m a i n constant. The lowering of
Table V. Activation energy of Na + diffusion in Nation, kcal EACT n e a r I I M NaOH solution concentration for both
mole- 1 m e m b r a n e s is interesting. These values were r e m e a -
sured with the same result. This suggests that an
NaOH o p t i m u m NaOH concentration m a y be found with
eonc. Temperature regard to the transport properties of Nation m e m b r a n e s
Membrane (M) range (~ E.~cT
in chlor-alkali cells.
The dependence of the Na + self-diffusion coefficient
1150 E W 9.5 60-90 2.5
1200 E W 9.5 60-90 4.7
on solution pH for Nation 295 is shown i n Fig. 6. Also
1150 ( E D A ) 9.5 60-90 6.9 plotted here is the change in the molarity of water i n
EDA 9.5 60-90 12.1 NaOH solution as a function of NaOH concentration,
No. 295 9.5 60-90 8,5 using s t a n d a r d chemical h a n d b o o k data. The pro-
ll.O 60-90 7.2 nounced decrease of the diffusion coefficient in con-
12.5 60-90 8.7
NO. 214 5.9 25-70 9.7 centrated solution for No. 295 can be a t t r i b u t e d to the
9.4 40-85 10.9 d e h y d r a t i n g effect of the drop in solution water con-
ll.O 55-85 9,1
12.~ 70-85 10.2 tent, as illustrated i n Fig. 6. At i n t e r m e d i a t e solution
"CoL I27, No. 2 ION EXCHANGE MEMBRANES 307

S e v e r a l o t h e r factors w o u l d need to be considered for

I0 -5 " - ~ and O H - concentrations, c u r r e n t efficiencies, and
10-6
la"
lO--t
III I I lilI[ll i r r,,,.l , ,
o.01 0.10 1.0
NaOH CONC.,M
Fig. 6. Na + diffusion coefficient in Nation 295 at 60~ NaOH
external solution; and change in water molarity in NaOH solution.
concentrations, m e m b r a n e w a t e r contents increase and
the diffusion of Na + rises b y a factor of a b o u t 50. The
r e d u c t i o n in diffusion coefficient in m o r e dilute solu-
tions is a t t r i b u t a b l e to the s u l f o n a m i d e exchange site
l a y e r in the m e m b r a n e . These sites a r e w e a k l y acidic,
and if the i n t e r n a l m e m b r a n e pH is not sufficiently
high, the sites will p r o t o n a t e to r e m o v e the ion e x -
change c a p a b i l i t y of this l a y e r of m e m b r a n e . This
w o u l d g r e a t l y reduce Na + diffusion. This r e s u l t has
r e l e v a n c e to the c h l o r - a l k a l i cell. The p H g r a d i e n t
across the m e m b r a n e s e p a r a t o r will be affected b y the
a d j u s t a b l e b r i n e acidity; the results in Fig. 6 suggest
t h a t b r i n e p H m a y have a p r o n o u n c e d effect on m e m -
b r a n e t r a n s p o r t properties. We conclude t h a t the o p -
e r a t i n g p r o p e r t i e s of m e m b r a n e s such as Nation 214
a n d 295 m a y be v e r y sensitive to gradients in m e m -
b r a n e p H and w a t e r content.
M e m b r a n e voltage drops for these m e m b r a n e s in a
l a b o r a t o r y scale c h l o r - a l k a l i cell are shown in Fig. 7.
It is seen t h a t the m e m b r a n e voltage for No. 214 is
a b o u t double that of No. 295, as w o u l d have been p r e -
dicted from t h e i r respective Na + diffusion coefficients.
1.4
1.2
1.0
= 0.8
O m o r e d e t a i l e d comparisons of cell m e m b r a n e voltages,
however. These include the respective m e m b r a n e N a +
electro-osmotic w a t e r transport. A n o t h e r f e a t u r e of the
o p e r a t i n g p r o p e r t i e s of these m e m b r a n e s is shown in
Fig. 7, w h e r e the m e m b r a n e v o l t a g e of No. 295 has
d r o p p e d b y 0.15V a f t e r s e v e r a l weeks of operation.
H o w e v e r this is accompanied b y a decrease in c u r r e n t
efficiency f r o m 87 to 73%. P o l y m e r degradation, long
t e r m morphological changes, or the slow accumulation
of b r i n e i m p u r i t i e s a r e seen as possible c o n t r i b u t i n g
factors. F u t u r e w o r k will e x a m i n e the effect of g r a d i -
ents in m e m b r a n e p H and w a t e r content, a n d imposed
electrical c u r r e n t on the t r a n s p o r t p r o p e r t i e s of these
membranes.
Acknowledgment
Dr. N. Cyr, 1t. Huntrods, and H. C. Kuo p e r f o r m e d
e x p e r i m e n t a l portions of this work. The authors wish
~,,,.I to t h a n k E. I. du Pont de Nemours and C o m p a n y for
10.0 p r o v i d i n g m e m b r a n e samples. F i n a n c i a l s u p p o r t for
this r e s e a r c h was p r o v i d e d b y the Olin Corporation.
M a n u s c r i p t s u b m i t t e d June 12, 1979; r e v i s e d m a n u -
script received Aug. 29, 1979.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be published in the D e c e m b e r i980
JOURNAL. A l l discussions for the D e c e m b e r 1980 Dis-
cussion Section should be s u b m i t t e d b y Aug. 1, 1980.
Publication costs of this article were assisted by the
Olin Corporation.
REFERENCES
1. S. C. Yeo and A. Eisenberg, J. Appl. Polym. Sci.,
21, 875 (1977).
2. M. s B. Kipling, and H. L. Yeager, Anal.
Chem., 48, 1120 (19.76).
3. M. Lopez, B. Kipling, and H. L. Yeager, ibid., 49,
629 (1977).
4. H. L. Yeager and A. Steck, ibid., 51, 862 (1979).
5. H. L. u a n d B. Kipling, J. Phys. Chem., 83,
1836 (1979).
6. W. G. F. Grot, G. E. Munn, and P. N. Walmsley,
P a p e r 154 p r e s e n t e d at The Electrochemical S o -
ciety Meeting, Houston, Texas, M a y 7-11, 1972.
7. 11. A. K o m o r o s k i and K. A. Mauritz, J. Am. Chem.
Soc., 100, 7487 (1978).
8. K. A. Mauritz, C. J. Hora, and A. J. Hopfinger,
Polym. Prepr., Am. Chem. Soc. Div. Polym.
Chem., 19, 324 (1978).
9. K. A. M a u r i t z and S. R. Lowry, ibid., 19, 336 (1978).
10. R. A. Komoroski, ibid., 19, 341 (1978).
11. S. G. Cutler, ibid., 19, 330 (1978).
12. T. Berzins, P a p e r 437 p r e s e n t e d at The E l e c t r o -
chemical Society Meeting, Atlanta, Georgia, Oct.
9-14, 1977.
13. T. D. Gierke, P a p e r 438 p r e s e n t e d at The E l e c t r o -
chemical Society Meeting, Atlanta, Georgia, Oct.
9-14, 1977.
14. C. J. H o r a and D. E. Maloney, P a p e r 441 p r e s e n t e d
at The Electrochemical Society Meeting, A t -
lanta, Georgia, Oct. 9-14, 1977.

0.6

0.4
START-UP ./4

>-S 15. D. E. Maloney and C. J. Molnar, P a p e r p r e s e n t e d

at t h e 71st A n n u a l Meeting, A m e r i c a n Institute
of Chemical Engineers, Miami Beach, Florida,
Nov. 12-16, 1978.
16. T. Berzins, P a p e r p r e s e n t e d at the 71st A n n u a l
Meeting, A m e r i c a n Institute of Chemical E n g i -
neers, Miami Beach, Florida, Nov. 12-16, 1978.
0.2 I I I 17. F. G. Will, This Journal, 126, 36 (1979).
MNGOH 5 10 15 18. 11. S. Yeo and J. McBreen, ibid., 126, 1682 (1979).
I I I I 19. 1t. S. Yeo and D-T. Chin, P a p e r 249 p r e s e n t e d at
10 20 30 " 40 The Electrochemical Society Meeting, Boston,
Massachusetts, M a y 6-11, 1979.
WEIGHT % NaOH 20. F. G. Will and H. S. Spacil, P a p e r 14 p r e s e n t e d at
The Electrochemical Society Meeting, Pittsburgh,
Fig. 7. Membrane voltage drop in operating chlor-alkali cell; P e n n s y l v a n i a , Oct. 15-20, 1978.
4.8M NaCI, 2 kA m - 2 current density, 85~ O , Nation 214; O, 21. F. Helfferich, "Ion Exchange," Chap. 8, p. 348,
Nation 295; (~, Nation 295 after use. M c G r a w - H i l l , New Y o r k (1962).