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rate limitation by internal electron transfer would interrupt an of the sulfite-reduced fragment to reduce ferricyanide was con-
expected increase in kl2 at low ionic strength, provided the internal firmed both electrochemically and spectrophotometrically, thus
reaction is less affected by variations in ionic strength. demonstrating that the Mo fragment sample was active. From
Elucidation of Site of Reactivity with Electron Acceptors. The this we infer that the reaction site of these mediators (except
preceding analysis demands evidence that the measured kn values [Fe(CN)6]4~/3~) is the enzymic Fe(II) site, as is the case for the
correspond to reaction exclusively at the SO heme site on our physiological acceptor, cytochrome c.13 It should also be noted
experimental time scale. Sulfite oxidase is a dimer of two identical that no evidence was found for direct electron transfer between
subunits, each of which contains a Mo atom present as a mol- the EPG electrode and the Mo fragment, either in the presence
ybdopterin cofactor,13,31 the site at which oxidation of sulfite or in the absence of sulfite.
occurs.13 Each subunit also contains the above mentioned cyt
65-like center where reduction of the physiological electron ac- Acknowledgment. This research was supported in part by
ceptor, cytochrome c, occurs subsequent to an internal charge grants from the National Science Foundation and the North
transfer.13 Cleavage of the holoenzyme into Mo- and Fe-con- Carolina Biotechnology Center.
taining domains by trypsin and isolation of the Mo fragment yields Registry No. [Co(3,4,7,8-Me4-phen)3]2+, 47889-06-5; [Co(3,4,7,8-
a sulfite-reducible molybdoprotein which has lost the ability to Me4-phen)3]3+, 86176-94-5; [Co(4,7-Me2-phen)3]2+, 47872-45-7; [Co-
reduce cytochrome c, but which retains a level of ferricyanide (4,7-Me2-phen)3]3+, 62791-75-7; [Co(5,6-Me2-phen)3]2+, 47872-55-9;
reductase activity which is virtually unchanged compared to that [Co(5,6-Me2-phen)3]3+, 62869-82-3; [Co(4-Me-phen)3]2+, 80711-11-1;
observed for the holoenzyme.13,14* [Co(4-Me-phen)3]3+, 80711-14-4; [Co(5-Me-phen)3]2+, 47860-25-3;
Against this established background, we tested whether various [Co(5-Me-phen)3]2+, 96504-30-2; [Co(phen)3]2+, 16788-34-4; [Co-
metal complex electron acceptors catalytically oxidize sulfite in (phen)3]3+, 18581-79-8; [Ru(NH3)6]2+, 19052-44-9; [Ru(NH3)6]3+,
18943-33-4; [Co(5-NH2-phen)3]2+, 113442-71-0; [Co(5-NH2-phen)3]3+,
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
or the anionic complex [Co(dps)3]4~/3_ (vide supra). The ability sulfite, 14265-45-3.
Thomas A. Zawodzinski, Jr.,* Michal Neeman, Laurel O. Sillerud, and Shimshon Gottesfeld
Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (Received: September 17, 1990;
In Final Form: March 18, 1991)
Pulsed field gradient spin-echo'H NMR measurements of 'H intradiffusion coefficients at 30 °C in hydrated Nafion membranes
are reported. The dependence of the 'H self-diffusion coefficient on membrane water content was a central part of this
investigation. ’H diffusion coefficients ranged from 0.6 X 10"6 to 5.8 X 10"* cm1 2/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.
reported activation energy of 4.5 kcal/mol. The method used to indicated by constant sample weight, was reached under these
estimate the diffusion coefficients by Yeo and Eisenberg, taking conditions after 4 days. All membrane weighing steps were carried
advantage of the /'/2 dependence of the uptake in the initial portion out by rapidly transferring the membrane to a weighing bottle
of the uptake curve, is not necessarily appropriate. The sorption and weighing by difference. The water content of a given mem-
of water takes place in a membrane with varying water content, brane was determined by weighing the equilibrated membrane
whereas the diffusion coefficient is not known a priori to be followed by completely drying the same membrane sample by
independent of the state of membrane hydration. As Crank has suspending it over P205 in a sealed jar for several days and re-
pointed out for the case of variable diffusion coefficients,4 sorption weighing it. This last treatment leads to a membrane water
will depend on t'l* no matter what the relationship is between the content of (practically) zero based on the following argument.
diffusion coefficient and the concentration of water in the film.
Drying the membrane under vacuum at room temperature for long
Yeager and Steck5 reported diffusion coefficients of water in periods leads to a water content of X
=
(X = the number of water
1
Nafion 120 membranes containing various alkali-metal cations molecules per sulfonate), as demonstrated by Bunce et al.8 We
determined by radiotracer measurements. In these studies, the find that further drying at 105 °C under vacuum of a membrane
diffusion coefficient of water was measured only for fully hydrated dried in the latter fashion results in a weight loss corresponding
membranes. The water diffusion coefficient is dependent on the to loss of one water per sulfonate. That all water is lost at 105
cation present in the membrane, with the value of the diffusion °C is consistent with the results reported by LaConti and co-
coefficient of water in Na+ form (fully hydrated) Nafion equal workers.9 This is slightly at odds with data presented by Yeo
to 2.65 X 10"6 cm2/s at 25 °C and the values for K+ and Cs4 forms and Eisenberg,3 which suggests a small amount (roughly 0.2 wt
slightly smaller. %) of residual water present after drying at 105 °C under vacuum.
More recently, Verbrugge and co-workers have published studies
Drying by suspending the membrane over P2Os leads to weight
of the transport of methanol and of protons (referred to throughout losses equivalent to those obtained via the 105 °C vacuum
this manuscript as H+ with no intent to imply specifics of spec- treatment. Furthermore, both our vapor-phase isotherms (see
iation) and other ions through Nafion membranes by radiotracer below) and maximum uptake data upon immersion in liquid water
techniques.6 These experiments were carried out with the are in quantitative agreement with those reported by others using
membrane exposed to a bulk aqueous acid solution. This situation other extreme drying protocols. We believe that our low-tem-
is not identical with that found in a PEFC in terms of either the
perature drying method is to be preferred since exposure of
hydration state of the membrane or the presence of co-ions in the polymer samples in the acid form to elevated temperatures gen-
membrane.
erally leads to some charring of the polymer, with unknown effects
We report here some results obtained by pulsed field gradient on, for example, the ion-exchange capacity of the polymer.
spin-echo (PGSE) NMR measurements of 'H intradiffusion Membrane conductivity was determined by using the cell
coefficients in Nafion membranes of various, well-controlled states sketched in Figure 2. The “window" structure was employed to
of hydration. allow membrane equilibration in situ. The resistivity of the
membrane was measured by using a pair of pressure-attached high
Experimental Section surface area Pt electrodes at 5 kHz. Both real and imaginary
Nafion 117 membranes were pretreated by boiling in dilute components of the impedance were measured and compared to
H202 solution, rinsing in boiling water, boiling in dilute sulfuric ensure that the real Z-axis intercept was closely approximated
acid solution, and rinsing in boiling water. Establishment and and that the measurement was free of the effects of lead induc-
maintenance of a well-defined water content are prerequisites for tance. For determinations of conductivity of partially hydrated
measurement of transport properties in membranes of different membranes, the cell was suspended in a closed vessel above the
states of hydration. To control the membrane hydration state, equilibration solution. Conductivity measurements on fully hy-
we have employed isopiestic equilibration of membrane samples drated membrane samples were carried out with the cell immersed
in liquid water. Temperature was controlled in both cases by
(3) Yeo, S. C.; Eisenberg, A. J. Appl. Polym. Scl. 1977, 21, 875.
(4) Crank, J. The Mathematics of Diffusion, 2nd ed.; Clarendon: Oxford, (7) Pushpa, K. K.; Nandan, D.; Iyer, R. M. J. Chem. Soc., Faraday Trans.
1975: Chapter 9. 1 1988. 84, 2047.
(5) Yeager, H.; Steck, A. J. Electrochem. Soc. 1981, 128, 1880. (8) Bunce, N.; Sondheimer, S.; Fyfe, C. Macromolecules 1986, 19, 333.
(6) (a) Verbrugge, M.; Hill, R. J. Phys. Chem. 1988, 92, 6778. (b) (9) LaConti, A.; Fragala, A.; Boyack, J. In Electrode Materials and
Verbrugge, M. J. Electrochem. Soc. 1989,136, 417. (c) Hill, R.; Verbrugge, Processes for Energy Conversion and Storage; McIntyre, J. D. E., Srinivasan,
M. J. Electrochem. Soc. 1990, 137, 886, 893. S., Will, F., Eds.; The Electrochemical Society: Pennington, NJ, 1977; p 354.
6042 The Journal of Physical Chemistry, Vol. 95, No. 15. 1991 Zawodzinski et al.
12
r *
&
| 6
2 RF Pulses 0- U_ A
gr gd gd gr
0
0 0.1 02 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
WATER ACTIVITY
Figure 4. (a) Pulsed field gradient spin-echo (PGSE) sequence, (b) Slow
immersing the entire vessel in a water bath. The cell constant diffusion enhanced modification of PGSE sequence (SDE-PGSE).
was calculated from the spacing of the electrodes and the thickness
of the membrane sample. (The latter was measured with a
micrometer in each case.)
a gradient-encoded magnetization. Experimentally, a pair of
NMR experiments were carried out using a Bruker AM-400 symmetrically spaced field gradient pulses is placed onto a normal
NMR spectrometer using a Bruker microimaging probe equipped spin-echo sequence, as illustrated in Figure 4a. The predicted
with 50-mm gradient coils and a 5-mm Helmholtz coil insert. dependence of signal attenuation on gradient strength is
Gradient pulses were shaped through a preemphasis network to
minimize the effect of eddy currents. The effect of any remaining
eddy currents was checked by measuring the signal intensity of
a sample of water as a function of time between the end of an
where A(g) is the signal intensity observed with applied gradient
applied gradient pulse and the onset of acquisition. For times of
20 ms or longer, the signal intensity was constant. Experiments g, A(0) is the signal intensity observed in the absence of an applied
were carried out with delays between gradient pulses and rf pulses gradient, y is the nuclear gyromagnetic ratio, D is the intradif-
fusion coefficient, and 5 and A are as shown in Figure 4a. The
or acquisition of 20 ms or more. Samples were prepared by
pulse spacing and duration can be altered to obtain information
equilibration and then placed in a homemade multicompartment on any restrictions to diffusion (e.g. pore walls) on the distance
NMR tube within which equilibration could be maintained. A
scale determined by the experimental time scale and the diffusion
small Kel-F container with the equilibration solution was screwed
coefficient.12
onto the bottom of a chamber containing the membrane which
A fundamental requirement of the PGSE technique is that
was then screwed into a positioning rod. Small bits of threaded
diffusional attenuation be significant relative to relaxation of the
rod were used to join the various compartments. A hole drilled
observed nuclei. If relaxation is too rapid, determination of
through the center of the threaded connector between the cham- diffusion coefficients via the PGSE experiment is difficult or
bers containing membrane and solution allowed vapor phase
contact. The sample temperature was controlled by means of the impossible to carry out. Boyle et al.n have indicated, based on
their relaxation study of water in Nafion, that PGSE experiments
Bruker VT1000 probe temperature controller and calibrated by
would be impractical for this system. However, the Nafion
a Luxtron 1000B fiber optic temperature probe.
The gradient was calibrated by observing the profile of a samples used by Boyle et al. were, as they demonstrated, con-
taminated with iron, causing significantly shortened relaxation
calibrated water phantom in the presence of gradients covering
times (7, on the order of 10 ms for 1100 EW Nafion). Other
the range used experimentally. To extract the diffusion coefficient
workers have measured proton 7,s and 72s which are significantly
from the raw experimental data, the observed signal intensity for
16 incremented field gradient strengths was fit to the predicted longer at room temperature (roughly 100 and 50 ms, respec-
tively).14 We find in our experiments on well-purified, protonic
decay curve using a nonlinear least-squares procedure from SAS forms of Nafion that proton longitudinal relaxation times vary
software (SAS Institute Inc.) on a micro VAX computer.
over the approximate range 80-200 ms for water at various
Results and Discussion concentrations in Nafion 117 membranes (less water in the
membrane leads to shorter relaxation times), while transverse
Equilibration of Nafion membranes with aqueous LiCl solutions relaxation times are generally about half as long at 25 °C. There
at 30 °C leads to the water sorption curve shown in Figure 3. The
is thus an ample time window in which to perform PGSE mea-
shape of this curve is similar to that obtained by Pushpa et al.
surements.
at 25 °C. However, a somewhat lower water uptake was observed
'H diffusion coefficients in pieces of hydrated Nafion 117
by us over most of the water activity range. A particularly in- membrane were determined for samples with various water con-
teresting feature of this curve is the relatively small change in water
content over the range of water activity 0.15-0.75. At water tents, as established by the isopiestic technique described above.
activities above 0.75, the water content of the membrane changes A typical plot of the observed signal attenuation versus gradient
much more rapidly with water activity. strength (for a sample containing 9 waters per sulfonate) is shown
in Figure 5 together with the best-fit curve predicted from eq 1.
Though measurements of diffusion coefficients by the PGSE
The measured intradiffusion coefficients are summarized in Table
technique have been reported for polymer/penetrant systems,10 I as a function of water content. 'H diffusion coefficients in Nafion
to our knowledge none at all have been reported for ion-exchange
decrease with decreasing water content. No systematic difference
polymers. In the pulsed field gradient spin-echo (PGSE) NMR
experiment," an intradiffusion coefficient for species bearing the
detected nucleus is determined from the diffusions! dephasing of (12) Tanner, J. E.; Stejskal. E. O. J. Chem. Phys. 1968, 49, 1768.
(13) Boyle, N. G.; McBrierty, V. J.; Douglass, D. C. Macromolecules
1983, 16, 75.
(10) Stilbs, P. Prog. Nucl. Magn. Resort. Speclrosc. 1987, 19, 1 and ref- (14) (a) Slade, R. C. T.; Hardwick, A.; Dickens, P. G. Solid Slate Ionics
erences therein. 1983, 9/10, 1093. (b) Sivashinsky, N.; Tanny, G. B. J. Appl. Polym. Scl.
(11) Stejskal, E. O.; Tanner, J. E. J. Chem. Phys. 1965, 42, 288. 1981, 26, 2625.
Perfluorosulfonate Ionomeric Membranes The Journal of Physical Chemistry, Vol. 95, No. 15, 1991 6043
0.12
Jj 0.10
5
0.08
|
5 0.06
D
Q
Z
8 0.04
O
E
0
0 10 20 30
MOLES OF WATER PER EQUIVALENT
TABLE III: Chemical Diffusion Coefficients and C is the concentration of the diffusing species (i.e. the
membrane water content). The “chemical” diffusion coefficients
water content Adwn> water content
are obtained by use of eq 3 and the isopiestic data shown above.
(H20/S03H) 106 cm2/s (H20/S03H) 106 cm2/s
The curve shown in Figure 3 is transformed into a plot of In amur
2 1.3 6 2.0
vs In Cwater. This curve is next fit to a third-order polynomial,
3 4.2 9 1.7
and the derivative term in eq 3 is then directly obtained. The
4 2.3 14 1.5
calculated values of Z>chem show 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, III). This is caused mainly by the much stronger variation of
we conclude that, in the extreme of low water content, H20 and water activity with water content at 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
‘H nuclei would thus diffuse together and the measured diffusion drop in the value of the intradiffusion coefficients.
coefficient of 'H is, 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
water (*H) in PEFC membranes maintained at a well-defined state
arguments for high and for low water contents, we tentatively
identify the 'H diffusion coefficient measured here as the intra-
of partial hydration. More extensive work is currently in progress
diffusion coefficient of H20 in 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 H2170 to 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 170 as
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, i.e. polymer electrolyte fuel cell systems.17
flux =
Z)chem(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”
ergy.
diffusion coefficient is carried out using the equation
Registry No. H20, 7732-18-5.
Radical Scavenging In the Sonolysis of Aqueous Solutions of I-, Br, and N3~
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 -I- solute reactions.
A local concentration of 4 X 10'3 4M 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.
(1) (a) Henglein, A. Ultrasonics 1987, 25, 6. (b) Advances in Sono- (3) Suslick, K. S. Ultrasound, Its Chemical, Physical, and Biological
chemistry. Mason, T, Ed.; Jai Press; Vol. 3, in press. Effects-, VCH: Weinheim, 1988.
(2) Mason, T. J.; Lorimer, J. P. Sonochemistry, Theory, Applications and (4) Carmichael, A. J.; Mossoba, M.; Riesz, P.; Christman, C. L. IEEE
Uses of Ultrasound in Chemistry, Ellis Horwood Ltd.; Chichester, 1988. Trans. 1986, UFFC-33, 148.