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Thomas A. Zawodzinski, Jr.,* Michal Neeman, Laurel 0. Sillerud, and Shimshon Cottesfeld
Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (Received: September 17, 1990;
In Final Form: March 18, 1991)
Pulsed field gradient spin-echo 'HNMR measurements of 'Hintradiffusioncoefficients at 30 "C in hydrated Nafion membranes
are reported. The dependence of the 'Hself-diffusion coefficient on membrane water content was a central part of this
investigation. 'Hdiffusion coefficients ranged from 0.6 X 10-6 to 5.8 X IOd cmz/s for the range of membrane water content
2-14 water molecules per sulfonate. The membrane water content was controlled by isopiestic equilibration of the membrane
sample with water vapor above aqueous LiCl solutions of well-defined water activities. The dependence of membrane water
content on water activity enables us to estimate "chemical diffusion coefficients" from the intradiffusion coefficients measured
by NMR.
-
ELECTRO-OSMOTICDRAG
1
-
BACK DIFFUSION
ANODE
H2(g)+2H*+2e
t
MEMBRANE
CATHODE
02+4H*++2H20
0.8 -
-
* 0.4 -
0.3 -
0.2 -
0.1 -
0' I I I
I I I I 1 I
0 1 2 3 4 5 6 7 8 9
GRADIENT STRENGTH ( G k m ) MOLES OF WATER PER EQUIVALENT
Figure 5. Fit of PGSE data to cq I . Figure 6. Specific conductivityof Nafion 117 as a function of hydration
state.
TABLE I: 'H Intndiffusion Coefficients, 30 O C
water content D, water content D, 0 DH+(cond)
(HzO/SO,H) IO6 cm2/s (HzO/S03H) IO6 cm2/s D i H( N W
2
3
0.6 f 0.06' (SDEb)
1.2 0.08 (SDE)
6
9
*
3.7 0.15
4.4 & 0.07
1
0
-
m'
10 20
MOLES OF WATER PER EQUIVALENT
I
30
TABLE III: Chemical Diffusion Coefficients and C is the concentration of the diffusing species (Le. the
membrane water content). The "chemical" diffusion coefficients
water content Dh, water content D-, are obtained by use of eq 3 and the isopiestic data shown above.
(H,O/SOIH) 106 cm2/s (H20/S03H) lo6 cm2/s
The curve shown in Figure 3 is transformed into a plot of In "a
2 1.3 6 2.0 vs In C,,,,,. This curve is next fit to a third-order polynomial,
3 4.2 9 1.7
4 2.3 14 1.5 and the derivative term in eq 3 is then directly obtained. The
calculated values of Dchcmshow a much smaller range of variation
indicates no immobile water at low membrane water contents since with water content than do the self-diffusion coefficients (Table
no very broad components are observed in the spectrum. Thus, 111). This is caused mainly by the much stronger variation of
we conclude that, in the extreme of low water content, H20and water activity with water content a t the lower water contents
H+probably diffuse by an identical mechanism, i.e. that the mobile studied, as can be seen in Figure 3. The large variations of the
species under an electric field is solvated H+, of mobility identical activity coefficient of water at low water contents provide an
with that of H20.At such low water levels in the membrane, all additional "drive" for water transport, compensating for the large
'Hnuclei would thus diffuse together and the measured diffusion drop in the value of the intradiffusion coefficients.
coefficient of 'His, again, a good estimate of the water diffusion This report demonstrates the capability of the NMR technique
coefficient in the membrane. Thus, on the basis of the above to provide the desirable information of diffusion coefficients of
arguments for high and for low water contents, we tentatively water ('H) in PEFC membranes maintained at a well-defined state
identify the 'Hdiffusion coefficient measured here as the intra- of partial hydration. More extensive work is currently in progress
diffusion coefficient of H20in the membrane over the entire range in our laboratory to determine diffusion coefficients of water in
of membrane water contents. We are, however, planning ex- Nafion and other ionomeric membrane systems under a variety
periments employing H2I7Oto provide definitive water diffusion of conditions, most importantly, elevated temperatures. PGSE
coefficients in order to further substantiate this point. measurements on hydrated Nafion membranes employing "0as
In a real membrane in which a water concentration gradient the probe nucleus will be carried out to directly ascertain the
exists, such as in an operating fuel cell, diffusion of water through diffusion coefficient of water in the membrane. As suggested
the membrane takes place in a chemical potential gradient. Flux above, the results described in this communication are currently
as described by Fick's law is generally relative to a concentration being applied in the development of a water transport model for
gradient, Le. polymer electrolyte fuel cell systems.17
flux = Dc,,,(dC/dx) (2) Acknowledgment. This work was supported by the U S . De-
partment of Energy, Office of Conservation and Renewable En-
Conversion of a measured intradiffusion coefficient to a "chemical"
diffusion coefficient is carried out using the equation ergy.
Registry NO. H20,7732-18-5.
Dchem = KC)^*
d In a
(3)
(17) (a) Springer, T. E.; Gottesfeld, S.;Radzinski, S.;Zawodzinski, T. A.
Book of Abstracts, 178th Meeting of the ElectrochemicalSociety, Seattle,
where Dchcmis the "chemical" diffusion coefficient, D* is the WA, Oct 1990; Abstract No. 118. (b) Springer, T. E.; Zawodzinski, T. A,;
intradiffusion coefficient, a is the activity of the diffusing species, Gottcsfeld, S . J . Electrochem. Soc., in press.
Iodide and bromide solutions are sonolyzed under pH conditions, where reactions of the products, i.e. hydrogen peroxide
and iodine (or bromine), do not occur. The total yield of the products as well as the hydrogen yield is independent of solute
+
concentration. The results are understood in terms of the competition of the OH OH and the OH solute reactions.+
A local concentration of 4 X M of the OH radicals in an interfacial region between the cavitation bubbles and the liquid
is derived from the data obtained. The sonolysis of azide solutions is also investigated. The main product is nitrogen, which
is formed in the reaction of N3- with OH radicals in the millimolar concentration range. At higher azide concentrations,
additional nitrogen is formed as hydrogen atoms are also scavenged. Ammonia and hydrazine are minor products of the
N3- sonolysis.
( I ) (a) Henglein, A. Ulrrasonlcs W87, 25, 6 . (b) Aduances in Sone (3) Suslick, K. S . ulrrasound, I r s Chemical, Physical, and Biological
chemistry; Mason, T.,Ed.;Jai Press: Vol. 3, in press. Eflects; VCH: Weinheim, 1988.
(2) Mason, 7. J.; Lorimer, J. P. Sonochemistry, T W ,Applicarions and (4) Carmichael. A. J.; Mossoba, M.; Riesz, P.; Christman, C. L. IEEE
Uses of Ulrrusound In Chemistry; Ellis Honvood Ltd.: Chichwter, 1988. Trans. 1986, UFFC-33, 148.