Luminescence Probe Studies of Nafion Polyelectrolytes

N. E. Prieto and C. R. Martin*

Department of Chemistry, Texas A&M University, College Station, Texas 77843

ABSTRACT
Results of luminescence probe studies of solutions of the polyelectrolytes obtained upon dissolving Nafion are re-
p o r t e d . The p r i m a r y o b j e c t i v e of this work was to s t u d y the n a t u r e of the i n t e r a c t i o n s b e t w e e n t h e s e a n i o n i c
polyelectrolytes and their counterions. Both 1100 and 12"00 equivalent weight Nation were studie~l; solutions of these
Nations were prepared using a procedure developed in this laboratory. These luminescence probe studies have shown that
strong b i n d i n g to the Nation polyelectrolytes occurs when both hydrophobic and electrostatic interactions are possible.
Hence, Nation preferentially binds hydrophobic cations such as Ru(bpy)~2+ (bpy = 2,2'-bipyridine), methylviologen, and
auramine O over simple inorganic cations such as H +, Na +, and Mg 2+. The implications of this u n u s u a l ion exchange selectiv-
ity to transport properties of Nation films and membranes are discussed.

Perfluorinated ionomers (1) have been used in a 2 spectrofluorometer. Ru(bpy)32+, AO +, and 6 - I n - l l +

v a r i e t y of electrochemical applications, including use
in chlor-alkali cells (2, 3), water electrolyzers (4),
z i n c - b r o m i n e cells (5), h y d r o g e n - h a l o g e n cells (6),
h y d r o g e n - o x y g e n fuel cells (7), and as agents for the
p r e p a r a t i o n of chemically modified electrodes (8).
These ionomers also have a n u m b e r of n o n e l e c t r o c h e m -
ical uses (9, 10). Because of their r e m a r k a b l e versatility,
much c u r r e n t research effort is being devoted to study-
ing the morphological a n d chemical properties of these
ionomers (1). We have recently described a procedure
for dissolving perfluorinated ionomer m e m b r a n e s (11).
This allows, for the first time, for a s t u d y of the i n -
trinsic chemical properties of the poly(perfluorosul-
fonate) ( P F S ) molecule itself. Such studies should
allow for a more thorough u n d e r s t a n d i n g of the chemi-
cal features, and perhaps of the morphological features,
of ionomer membranes. We report at this time results
of various luminescence probe studies of the polyelec-
trolytes obtained b y dissolving the 1100 and 1200 equi-
valent weight versions of du Pont's Nation (1). The
p r i m a r y objective of this work is to s t u d y the i n t e r -
action.s b e t w e e n these anionic polyelectrolytes and
their counterions.
Experimental
Materials.--Samples of 1100 and 1200 equivalent
weight Nation were k i n d l y donated b y E. I. du Pont
de Nemours and Company. These were dissolved using
the procedure of Martin et al. (11), which uses 50:50
e t h a n o l - w a t e r as the solvent. The alcohol was removed
from these solutions, i m m e d i a t e l y before use, by heat-
ing. The Na + form of the polyelectrolytes ( N a - P F S ' s )
were obtained b y adding carefully measured quantities
of NaOH to the polymer solutions. Ru(bpy)sC12
6H~O (bpy = 2,2'-bipyridine) (G. F. S m i t h ) , 1,1'-
d i m e t h y l - 4 , 4 ' - b i p y r i d i n i u m dichloride h y d r a t e (meth-
ylviologen) (Aldrich), and 1,1'-diheptyl-4,4'-bipyri-
d i n i u m dibromide (heptylviologen) (Aldrich) were
used without f u r t h e r purification. T r i s ( 2 , 4 - p e n t a n e d i -
o n e ) c o b a l t (III), Co (acac)8, (Alfa) was recrystallized
from benzene, washed with diethyl ether, and dried at
60~ (12). A u r a m i n e O [ 4 , 4 ' - ( i m i d o c a r b o n y l ) b i s (N,N'-
d i m e t h y l a n i l i n e ) monohydrochloride] (the cation is ab-
breviated AO + (Sigma) was recrystallized from NaC1
(13). 11- (3-hexyl- 1-indolyl) u n d e c y l t r i m e t h y l a m m o -
n i u m bromide [the cation is abbreviated ( 6 - I n - l l +)
(14) ] was donated b y N. J. Turro. All other reagents
were ACS reagent grade and were used without fur-
ther purification. Triply distilled water was used
t h r o u g h o u t this work. The I100 and 1200 e q u i v a l e n t
weight versions of Nation gave essentially identical
results. Only the 1100 data are reported.
Emission intensity and absorbance measurements.--
Emission spectra were obtained using a Spex Fluorolog
* Electrochemical Society A c t i v e Member.
were excited at 455, 435, and 290 nm, respectively.
Emission i n t e n s i t y was monitored at 600 n m for the
Ru(bpy)32+* quenching studies. Absorption spectra
were t a k e n using a B e c k m a n Model 26 photometer.
The solutions for the luminescence intensity m e a -
surements were prepared b y adding aliquots of stock
solutions of the p o l y m e r (1% weight volnme [ w / v ] ) to
R u ( b p y ) 8 ~'~+ (2 • 10-~M), AO + (5 • 10-~M), or
6 - I n - l l + (2 • 10-ZM) solutions in quartz cuvettes.
H a m i l t o n microliter syringes were used. The cuvette
solution was mixed thoroughly after each addition of
polymer solution, and intensities were corrected for
dilution. The addition of salt solution or q u e n c h e r to
a P F S / R u ( b p y ) 3 u+ or P F S / A O + solution followed a
similar procedure.
Lifetime measurements.--Ru (bpy) 33+ * lifetime m e a -
surements were done at the Center for Fast Kinetics
Research at the U n i v e r s i t y of Texas at Austin. Life-
times for Ru(bpy).~ 2+* in pure water, in a solution
0.01% in H - P F S (proton form of the polyelectrolyte)
and in a solution of 0.01% N a - P F S were obtained [all
solutions were 2 • 10-5M in R u ( b p y ) 3 2 + ] . Solutions
were degassed with prepurified nitrogen. A Quantrel
YG 481 N d : Y A G Q-switched dye laser (535 rim, ca.
10 ns pulse) was used as the excitation source. L u m i -
nescence emission was monitored at 650 n m with an
RCA R928 photomultiplier tube and processed with a
Biomation (Gould) m u l t i c h a n n e l analyzer and a P D P -
11/70 minicomputer. Metal screens were used to at-
tenuate the incident laser intensity.
Results and Discussion
The luminescence probe studies.--As noted above,
the p r i m a r y objective of this work is to study the
n a t u r e of the interactions between the Nailon poly-
electrolytes a n d their counterions. Clearly, an electro-
static interaction (15a) will be present, b u t because
hydrophobie interactions (15b) have been implicated
in various studies of Nation m e m b r a n e s (8, 16, 17), it
was of interest to see if evidence for such interactions
could be observed in solutions of the polyelectrolytes.
Luminescence probe studies have been shown to be
quite effective at characterizing p o l y i o n - c o u n t e r i o n
interactions in other polyelectrolyte systems (18-24).
Two types of luminescence probe experiments were
used here. The first involved studies of the effect of
addition of the PFS's on the luminescence emission i n -
tensities of various cationic probes in aqueous solution.
Three s t r u c t u r a l l y diverse probes, 6-In-11 + (14, 22, 23),
R u ( b p y ) a 2+, and AO + (24) were chosen for these
studies. 8 - I n - l l + was chosen because the effect of
solvent polarity on its e m i s s i o n characteristics are
dramatic and well characterized (14, 22, 23), and be-
cause it has been used to study p o l y i o n - c o u n t e r i o n
interactions in p o l y ( s t y r e n e - s u l f o n a t e ) ( P S S ) (23).
R u ( b p y ) a 2+ was chosen because Lee and Meisel have

751
 752 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 April 1984

suggested that hydrophobic interactions b e t w e e n this 9 . 5 9 E ~5

ion and the fluorocarbon chain material occur in 1200

equivalent weight Nation m e m b r a n e s (16). AO + was
chosen because it has proved to be ideally suited for
s t u d y i n g p o l y m e r - p r o b e interactions (24).
=D
The second set of luminescence probe experiments
involved studies of the effect of the PFS's on the rates
of q u e n c h i n g of Ru(bpy)82+* by various electron c
transfer q u e n c h i n g agents. R u ( b p y ) 3 e+ was chosen CJ

for these studies because it strongly binds to the v-

PFS's (vide infra) and because its luminescence i n

aqueous solution has been well characterized (25).
Luminescence intensity studies.--Figure 1 shows the
effect of addition of a n aqueous solution of N a - P F S
(1 w / v ) on the emission spectra of 6-In-11 +. A pro-
O.I]E OS
nounced blueshift in the position of the emission spec- ~so. o~ 2~s. ~ 34o. oo
t r u m is observed (wavelength of m a x i m u m emission
Position (nm]
intensity, kmax, in water is 374 nm, 1max in Nation
solution is 356 n m ) . A blueshift in the emission of a Fig. 2. Excitation spectra of 6-1n-ll + (2 X 10-hM, monitored
probe (relative to water) is often indicative of a more at 374 nm). A: no Nafion added. B: after addition of Na-PFS
hydrophobic e n v i r o n m e n t for the probe (26). [The solution, 7.26 X 10 - 8 mols of - - S O 3 - sites added. C: after addi-
photochemical mechanism for such a shift is discussed tion of more Na-PFS solution, 1.99 • 10 - 7 mols of - - S O ~ - sites
by Brand and Gohlke (26).] The observed blueshift, added.
then, suggests that Nation is engaging in hydrophobic
interactions with 6 - I n - l l +. I n this type of luminescence
n m increases as N a - P F S is added to a solution of
probe study, however, it is desirable to compare the
6 - I n - l l +. Turro has shown that the absorbance for
emission of the probe from the u n k n o w n e n v i r o n m e n t
this probe increases as the polarity of the e n v i r o n m e n t
with its emission spectrum from some w e l l - c h a r a c t e r -
a r o u n d the probe decreases (22, 23); furthermore, a
ized e n v i r o n m e n t . It is k n o w n that PSS can engage in
similar increase in absorbance was observed with
strong hydrophobic interactions with its counterions
PSS (23). Figure 2 shows excitation spectra obtained
(18, 23). Turro and Okubo observed a pronounced with the fluorometer, b u t true absorbance spectra (ob-
blueshift in the emission of 6 - I n - l l + from aqueous
tained with the spectrophotometer) gave identical re-
solutions of PSS, which they attributed to hydrophobic
sults. Finally, it is i m p o r t a n t to note that while the
b i n d i n g of this probe by PSS (23). The similarity in
data shown in Fig. 1 and 2 refer specifically to the
the responses of this probe to the u n k n o w n (Nation)
Na + form of PFS, essentially identical results were ob-
and standard (PSS) e n v i r o n m e n t s adds f u r t h e r evi-
tained with the proton form. These studies clearly
dence for hydrophobic interactions between 6 - I n - l l +
show that 6 - I n - l l + engages in strong hydrophobic
and Nation.
interactions with the PFS's.
In addition to the shift in 1max, a de,crease in emis-
Figure 3 shows the effect of concentration of N a - P F S
sion intensity, with the initial additions of Na-PFS,
(expressed as the molarity o f - - S O 3 - sites) on the
is observed (Fig. l b ) , followed by a gradual increase
intensity of emizsion by Ru(bpy)82+*. Emission i n -
in intensity with f u r t h e r additions (Fig. lc). Similar
tensity is expressed as the ratio I/I ~ where I ~ is the
results were obtained by Turro and Okubo in their
i n t e n s i t y in pure water, and I is the i n t e n s i t y after
investigations of N a - P S S (23). They suggest that
addition of an i n c r e m e n t of the N a - P F S solution (21).
quenching by trace impurities present in the polymer
Emission intensity increases with increasing concen-
solution may account for the initial decrease in emis-
sion i n t e n s i t y (23). tration of PFS u n t i l a stoichiometrically e q u i v a l e n t
a m o u n t of - - S O 3 - sites have been added to the solu-
F u r t h e r evidence for a strong hydrophobic compo-
tion (i.e., u n t i l 2 • [---SO~-] : [ R u ( b p y ) 8 2 + ] ) . This
n e n t to the interaction between 6 - I n - l l + and P F S
increase in intensity is not due to some p o l y m e r - i n -
is obtained from studies of 6 - I n - l l + absorption
duced change in b u l k concentration of the Ru (bpy)8 ~+,
spectra. As shown in Fig. 2, the absorbance at 290
because the absorption spectrum (corrected for dilu-
tion) is unaffected b y the presence of PFS, n o r is it
6,72E 05 due m e r e l y to a change i n the shape of the emission

1.S

1,4

1.3

C._ I/[.

1.2

1.1
8. t ~ E 05 , I
300. gO 4~(~, C0 500.00

Pos i -t: t o n [nm] 1.0

2 4 8 8 10 12 14
Fig. 1. Effect of addition of Na-PFS on fluorescence spectra for
[ so3 sites ] ! 1o-5
6-1n-11 + (2 X 10-5M). A: no Nation added. B: after addition of
Na-PFS solution, 3.79 X 10 - s mols of - - S O ~ - sites added. C: Fig. 3. Dependence of Ru(bpy)a 2+* luminescence emission in-
after addition of more Na-PFS solution, 5.05 X 10 - 7 mols of tensity on concentration of Na-PFS. [Ra(bpy)~2+] ~ 2 X IO-SM.
- - S O 3 - sites added. k E X ~ 455 nm, ,~,EI~I~ 610 nm.
VoL 131, No. 4 NAFION POLYELECTROLYTES 753

band, because an analogous plot of the areas u n d e r its contact w i t h water. Therefore, a q u a n t u m yield
the emission bands gives an identical curve. W h e n increase would be expected.
g r e a t e r than stoichiometric amounts of P F S are added, The final luminescence p r o b e used was AO +. In
a leveling in emission i n t e n s i t y is o b s e r v e d (Fig. 3). nonviscous solvents, electronic excitation e n e r g y in
The leveling of the emission i n t e n s i t y at the stoi- AO + is dissipated as heat via rotation of its p h e n y l
chiometric equivalence point impiicates a role for rings (24). F o r this reason, AO + does not fluoresce in
electrostatic interactions in the o b s e r v e d increase in w a t e r (Fig. 5) or o t h e r nonviscous solvents (24).
emission intensity. However, if a hydrophilic, d i v a l e n t B i n d i n g of AO + to polyanions hinders p h e n y l r i n g
m e t a l ion (e.g., Mg 2+) is a d d e d to a R u ( b p y ) 3 2 + / P F S rotation, and fluorescence can be observed (24). F i g u r e
solution, a huge excess of the h y d r o p h i l i c ion is r e - 5 shows t h a t N a - P F S can induce fluorescence in AO +.
quired to r e t u r n I / I ~ b a c k to 1 (Fig. 4, the ratio As was the case w i t h Ru(bpy)82+, fluorescence in-
(mols Mg2+/mols R u ( b p y ) 3 a+) to m a k e I / I ~ 1 is ca. tensity is p r o p o r t i o n a l to [ - - S ( ) 3 - ] until a stoichio-
1000). If the increase in emission i n t e n s i t y (Fig. 3) m e t r i c a l l y e q u i v a l e n t q u a n t i t y of p o l y m e r is added.
resulted from p u r e l y electrostatic interactions, t h e F u r t h e r m o r e , h u g e excesses (ca. 1000-fold) of N a + a r e
a b i l i t y of Mg 2+ to replace Ru (bpy)32+ as the c o u n t e r - r e q u i r e d to r e t u r n the emission i n t e n s i t y to b a c k g r o u n d
ion of the p o l y e l e c t r o l y t e would not be so s e v e r e l y levels, indicating that AO + also binds via a concerted
retarded, t h a t is, one m i g h t expect the ratio (mols h y d r o p h o b i c / e l e c t r o s t a t i c interaction.
Mg2+/mols R u ( b p y ) a 2 + ) r e q u i r e d to m a k e I / I ~ ca. 1 Q u e n c h i n g s t u d i e s . - - I t is well k n o w n that quenching
to be close to unity. Given the h y d r o p h o b i c n a t u r e of reactions b e t w e e n an electronically excited cation and
Ru(bpy)82+, the results in Fig. 4 indicate that t h e r e a cationic quencher are accelerated in the presence of
is also a strong h y d r o p h o b i c interaction b e t w e e n this a po]yanion (19, 27, 29). This acceleration is due to
counterion a n d the PFS's. The b i n d i n g of Ru(bpy)32+ the concentration of the cations in the d o m a i n a r o u n d
to t h e P F S ' s is via a concerted h y d r o p h o b i c / e l e c t r o -
static interaction.
W h e n R u ( b p y ) ~ 2+ is used as a luminescence probe 5
of h y d r o p h i l i c polyions, w h e r e only electrostatic i n t e r - 1.0-
actions are extant, emission i n t e n s i t y does not change
w i t h the c o n c e n t r a t i o n of the polyion (27). This s u g -
gests t h a t the increase in emission i n t e n s i t y in Fig. 3
is caused b y the h y d r o p h o b i c p a r t of the interaction.
K u r i m u r a e~ al. s a w a s i m i l a r increase in emission
i n t e n s i t y w h e n P S S was a d d e d to a R u ( b p y ) s 2+ solu-
tion and also concluded t h a t this increase was due to
h y d r o p h o b i c interactions (21). A consideration of the
effect of w a t e r on the n o n r a d i a t i v e rate constant p r o -
vides a possible e x p l a n a t i o n for the observed increases
in Ru (bpy) 82+* emission intensity. As r e c e n t l y noted
b y Casper and M e y e r (28), w a t e r is p a r t i c u l a r l y ef-
fective at p r o m o t i n g n o n r a d i a t i v e decay in Ru(bpv)~ 2+*.
It seems likely, then, that a n y interaction which shields
Ru(bpy)82+* from w a t e r will increase its q u a n t u m
yield [the r a d i a t i v e rate constant is r e ] a t i v e l y i n s e n -
sitive to solvent (28)]. Since it is the i n c o m p a t i b i l i t y
of w a t e r and the h y d r o p h o b i c solute which p r o m o t e s
h y d r o p h o b i c b o n d i n g (15b), it is reasonable to as- hl
s u m e t h a t when b o u n d to PFS, R u ( b p y ) ~ 2+ minimizes
o.B
N

1.4

1.3

!/Io
1.2

i
I.I " 9 ~ -J

{D 5 I0 15 20 450 500 550 600 650

wavelength, nm
[Mg2+] (mM)
Fig. 5. Fluorescence spectra of AO + as a function of concen-
Fig. 4. Effect of addition of MgSO4 on emission intensify of tration of Na-PFS ( [ A O + ] ~ 5 • 10-5M, ~EX = 435 rim). 1:
Ru(bpy)32+* from a Ru(bpy)32+/Na-PFS solution. 2 X 10 - s n~ Na-PFS. 2 : 9 X 10 - 9 mols of - - S O 3 - sites, 3 : 1 . 8 X 10 - 8
mols Ru(bpy)32+, 6 X 10 - 8 mols Nafion - - 5 0 3 - sites (see Fig. mols --SO3 sites. 4 : 2 . 7 X 10 - s mols - - S O 3 - sites. 5:
3). 3.6 X 10 - 8 mols - - S O 3 - sites.
754 J. ElecSrochem. 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
the polyion chains (i.e, the local concentrations of
both emitter a n d quencher are higher than the b u l k
concentrations) (19, 27, 29). It was of interest to see
if acceleration of quenching reactions between cationic
quenchers and R u ( b p y ) ~ ~+* could be observed in the
presence of the P F S s . F u r t h e r m o r e , given the strongly
hydrophobic n a t u r e of the PFS's (vide supra), it was
of p a r t i c u l a r interest to see if a c o n t r i b u t i o n from
hydrophobie interactions (18) could be discerned in
a n y acceleration observed.
Quenching rate constants were d e t e r m i n e d using the
emission i n t e n s i t y form of the S t e r n - V o l m e r equation
(30). Typical S t e r n - V o l m e r plots are shown in Fig. 6.
We have obtained a p p a r e n t quenching rate constants
from such plots for hydrophilic cation, hydrophobic
cation, and n e u t r a l quenchers in the presence of both
N'a-PFS a n d H - P F S ' s (Table I). Measured Ru(bpy)~~+*
lifetimes of 640 _+ 10 ns ( N a - P F S ) and 590 _+ 10 ns
( H - P F S ) were used for calculation of these rate con-
stants. They are called a p p a r e n t quenching rate con-
stants because they have been calculated assuming the
b u l k quencher concentrations. To obtain real q u e n c h -
ing rate constants, the values shown in Table I would
have to be normalized, as described by Meisel et al.
(19). Since it is the m a g n i t u d e of the rate constant
e n h a n c e m e n t which is of interest here, normalization
was not attempted.
Table I shows that quenching rate constants are
enhanced for all of the cationic quenchers. The a m o u n t
of enhancern:ent can be described q u a n t i t a t i v e l y by
the e n h a n c e m e n t factor (~), which is the ratio of the
a p p a r e n t rate constant in the presence of the polymer
to the rate constant observed in pure water. E n h a n c e -
m e n t factors (Table II) for the hydrophobic cations
(methylviologen and heptylviologen) are seven to
ten times larger t h a n the e n h a n c e m e n t factors for the
hydrophilic cations. As in the previous set of experi-
ments, these data show that hydrophobie interactions
can play a n i m p o r t a n t role in the b i n d i n g of counter-
ions to the PFS's. Again, however, the importance of
the electrostatic component of the interaction is d e m o n -
strafed because q u e n c h i n g b y n e u t r a l Co (acac)~ is not
changed appreciably b y the presence of the polyanion.
[Co(acac)3~ x IO-4M
0 8 I0 12
-17
o.o F I 0
5
[Cu2+] x 10"4M
[MV2+3 x IO-4M
Fig. 6. Typical Stern-Volmer plots for quenching of PFS-bound
Ru(bpy)~ ~+* by various quenchers. I-Ru(bpy)32+] = 2 X 10-5M,
[Na-PFS] = 0.05%.
April 1984
Table I. Apparent second-order.rate constants (M-1S -1) for
quenching of Ru(bpy)~ +* emission by various quenchers. Effect
of the PFS's on the rate constants
Quenchers
Medium Cu~+ Fea~ MV2+9 HV~+b CO(acac) .e
Water 7.7 x 10~a 2.1 x l0se 4.5 x 10~ 4.2 • 10s~ 1.1 x 109h
H-PFSI 2.4 • 109 2.2 x 10~ 1.5 x 10n 9.7 • 10~o 1.5 x 10~
Na-PFS1 3.9 x 10.8 4.5 x 10~t
a Methylviologen.
b Heptylviologen.
eacac = a c e t y l a c e t o n e .
Ref. (33).
e Ref. (19).
f Ref. (16).
Ref. (54).
1~Ref. (12).
i Solution was 2 • 10-~Min Ru(bpy)8~§and 0.05% in p o l y m e r .
Table II. H-PFS induced enhancement factors, c~ (.---- apparent
rate constant in the presence of polymer divided by pure water
rate constant) for various quenchers*
Quencher Cu 2+ Fe ~ MV~+ HV=+ Co(acac) s
a 31 10 330 230 1.4
* S e e Table I.
As was indicated by the data obtained in the i n t e n s i t y
studies, a concerted hydrophobic/electrostatic i n t e r -
action is required to produce strong binding.
Conclusions
This work has shown that strong b i n d i n g to the
Nation polyelectrolytes occurs w h e n both electrostatic
and hydrophobic inter'actions are possible. This helps
to e x p l a i n w h y a Nation film on an electrode surface
retains hydrophobic counterions (e.g., Ru(bpy)32+,
MV 2+) (8) w h e n the film is immersed in a solution
containing high (e.g., 0.1M) salt concentrations and
none of the hydrophobic ion. Nation shows v e r y dif-
ferent selectivity t h a n the polyelectrolytes investigated
b y A n s o n (31), which a p p a r e n t l y bind only via elec-
trostatic interactions. We are c u r r e n t l y investigating
ion exchange selectivity in cationic analogs of Nation
to see if hydrophobically d r i v e n ion exchange is a
general phenomenon.
This work raises i m p o r t a n t points concerning t h e
transport properties of Nation. The p e r m e a b i l i t y of a
material to a solute species is proportional to the prod-
uct of the partition constant and the diffusion coeffi-
cient for that species in the material. I n most of the
electrochemical applications of Nation, high p e r m e a -
bility to" cations is desired. Because of the affinity of
the p o l y m e r for hydrophobic cations (i.e., high p a r t i -
tion constant), these ions could show higher p e r m e -
abilities t h a n s m a l l e r alkali metal ions, if the m e m b r a n e
is in contact with a solution containing both types of
cations. Finally, these data corroborate results obtained
previously in this laboratory, which showed that rates
of ionic diffusion through Nation films can be affected
b y hydrophobic interactions (32).
Acknowledgments
This work was supported in part b y the Office o f
Naval Research and the Robert A. Welch Foundation.
The authors would like to t h a n k M. A. J. Rodgers and
S. A t h e r t o n of the Center for Fast Kinetics Research,
U n i v e r s i t y of Texas at Austin, for assisting with the
lifetime m e a s u r e m e n t s and for valuable discussions.
Manuscript submitted March 11, 1983; revised m a n u -
script received Oct. 26, 1983. This was P a p e r 566 p r e -
sented at the San Francisco, California, Meeting of the
Society, May 8-13, 1983.
Vol. I31, No. 4 N A F I O N POLYELECTROLYTES 755

The O]~ce of Naval Research assisted in meeting the "Ion E x c h a n g e and Solvent Extraction," Vol. 2,
publication costs oi this article. J. A. M a r i n s k y and Y. Marcus, Editors, Marcel
Dekker, N e w Y o r k (1969).
REFERENCES 16. P. C. Lee and D. Meisel, J. Am. Chem. Soc., 102,
1. A. E i s e n b e r g and H. L. Yeager, Editors, "Perfluori- 5477 (1980).
hated Ionomer Membranes," ACS Symposium 17. C. R. M a r t i n and H. Freiser, Anal. Chem., 53, 902
Series No. 180, ACS, Washington, DC (1982), and (1981).
references therein. 18. N. J. Turro and T. Okubo, J. Phys. Chem., 86, 1535
2. W. Grot, Chem.-Ing.-Tech., 50, 299 (1978). (1982).
3. W. Grot, G. E. Munn, and P. M. Walmsley, P a p e r 19. D. Meisel J. Rabani, D. Meyerstein, and M. S.
154 p r e s e n t e d at the Meeting of the E l e c t r o c h e m - Matheson, ibid., 82, 985 (1978).
ical Society, Houston, TX, M a y 7-11, 1972. 20. T. Okubo and N. J. Turro, J. Phys. Chem. Soc., 85,
4. R. S. Yeo, J. McBreen G. Kissel, F. Kulesa, and S. 4'034 (1981).
Srinivasan, J. Appl. Electrochem., 1O, 741 (1980). 21. Y. K u r i m u r a , H. Yokota, K. Shigehara, and E.
5. F. G. Will, This Journal, 126, 36 (1979). Tsuchida, Bull. Chem. Soc. Jpn., 55, 55 (1982).
6. R. S. Yeo and D.-T. Chin, ibid., 127, 549 (1980). 22. N. J. Turro, Y. Tanimoto, and G. Gabor, Photo-
7. A. B. LaConti, A. R. Yragala, and J. R. Boyack, in chem. Photobiol., 31, 527 (1980).
"Electrode M a t e r i a l s and Processes for E n e r g y 23. N. J. Turro and T. Okubo, J. Am. Chem. Soc., 104,
Conversion and Storage," J. D. E. McIntyre, S. 2985 (1982).
Srinivasan, and F. G. Will, Editors, p. 354, The 24. G. Oster and Y. Nishijima Fortschr. Hochpolym.
E l e c t r o c h e m i c a l Society Softbound Proceedings Forsch., 3, 313 (1964).
Series, Princeton, NJ (1977). 25. K. K a l y a n a s u n d a r a m , Coord. Chem. Rev., 46, 159
8. C. R. Martin, I. Rubinstein, and A. J. Bard, J. Am. (1982).
Chem. Soc., 104, 4817 (1982), and references 26. L. B r a n d and J. R. Gohlke, Ann. Rev. Biochem., 41,
therein. 843 (1972).
9. G. A. Olah, G. K. S. P r a k a s h , and J. Sommer, Sci- 27. D. Meisel and M. S. Matheson, J. Am. Chem. Soc.,
ence, 206, 13 (1979). 99, 6577 (1977).
10. H. L. Yeager and A. Steck, Anal. Chem., 51, 862 28. J. V. Casper and T. J. Meyer, ibid., 105, 5583 (1983).
(1979). 29. H. Morawetz, Acc. Chem. Res., 3, 354 (1970).
11. C. R. Martin, T. A. Rhoades, and J. A. Ferguson, 30. C. A. P a r k e r , "Photoluminescence of Solutions,"
ibid., 54, 1639 (1982). pp. 71-74, Elsevier P u b l i s h i n g Co., A m s t e r d a m
12. D. Meyerstein, J. Rabani, M. S. Matheson, and D. (1968).
Meisel, J. Phys. Chem., 82, 1879 (1978). 31. N. O y a m a and F. C. Anson, This Journal, 127, 247
13. R. H. Conrad, J. Heitz, and L. Brand, Biochem., 9, (1980).
1540 (1970). 32. C. R. M a r t i n and K. A. Dollard, J. Electroanal.
14. N. E. Schore and N. J. Turro, J. Am. Chem. Soc. 97, Chem., 159, 127 (1983).
2488 (1975).
15. a. A r e v i e w of p o l y e l e c t r o l y t e / c o u n t e r i o n i n t e r a c - 33. D. Meisel, M. Matheson, and J. Robin, J. Am. Chem.
tions is given in G. S. Manning, Ann. Rev. Phys. Soc., 100, 117 (1978).
Chem., 23, 117 (1972); b. A b r i e f r e v i e w of h y - 34. M. A. J. Rodgers a n d J. C. Becker, J. Phys. Chem.,
drophobic interactions is g i v e n b y J. F i e t e l s o n in 84, 2762 (1980).

The Effect of Reactive Gases on Oxygen Sensor Responses

J. I. Federer
Oak Ridge National Laboratory, Metals and Ceramics Division, Oak Ridge, Tennessee 37830

ABSTRACT
Ceramic electrolyte oxygen sensors consisting of stabilized zirconia with platinum electrodes were compared in
flowing gases in a laboratory apparatus. The oxygen partial pressures indicated by these sensors in reactive gases were
substantially different. Gases containing CO p r o d u c e d a greater difference than gases containing H2. The responses of these
sensors were attributed to their relative catalytic behavior.

C o m m e r c i a l l y a v a i l a b l e oxygen m e a s u r i n g devices
include those based on ceramic electrolytes, p a r a m a g -
netism, a n d electrometry. A n i m p o r t a n t use of o x y g e n
sensors i's m e a s u r e m e n t of o x y g e n concentrations in
the combustion e n v i r o n m e n t s of i n d u s t r i a l furnaces and
a u t o m o b i l e exhausts. In these applications, the sensors
m e a s u r e the o x y g e n concentration and, if coupled with
a u x i l i a r y i n s t r u m e n t a t i o n , control the a i r / f u e l ratio
b e i n g burned. A p o t e n t i a l a p p l i c a t i o n for o x y g e n sen-
sors is in fluidized bed combustors (FBC's) b u r n i n g
coal. The n e e d for an o x y g e n sensor was d e m o n s t r a t e d
d u r i n g corrosion testing of candidate s t e a m - t u b e m a -
terials in a test bed. S e v e r e oxidation-sulfidation cor-
rosion of t y p e 316 stainless steel occurred in one
location of t h e bed, b u t the same alloy corroded little
at s i m i l a r t e m p e r a t u r e s in other locations (1, 2). This
b e h a v i o r suggested t h a t t h e corrosiveness of the e n -
v i r o n m e n t v a r i e d significantly w i t h i n the bed. Corro-
sion of stainless steels b y an oxidation-sulfidation
m e c h a n i s m is g o v e r n e d b y the t h e r m o d y n a m i c s t a b i l i t y
Key words: ceramics, electrolyte, cell, catalysis.
of the oxides and sulfides of the elements involved (3,
4). F l u c t u a t i o n s in o x y g e n and s u l f u r concentrations
t h a t result in combinations of low oxygen and high
sulfur might increase corrosion. A n o x y g e n m e a s u r i n g
s y s t e m (OMS) was needed, therefore, to s t u d y and
control corrosion b e h a v i o r in fluidized beds. S e v e r a l
m o v a b l e devices might s y s t e m a t i c a l l y r e v e a l o x y g e n
concentrations within the bed, t h e r e b y aiding i n t e r -
p r e t a t i o n of corrosion results. Subsequently, s t a t i o n -
a r y devices at strategic locations could m o n i t o r and
control o x y g e n concentrations at levels consistent with
efficient combustion and acceptable corrosion.
C o m m e r c i a l l y a v a i l a b l e o x y g e n sensors were i n v e s t i -
gated to d e t e r m i n e the t y p e most suitable for FBC use.
This investigation focused on the mode of operation,
t e m p e r a t u r e capability, and m e a s u r i n g r a n g e of ce-
r a m i c electrolyte, p a r a m a g n e t i c , and electrometric d e -
vices. P a r a m a g n e t i c devices use the p a r a m a g n e t i c
p r o p e r t y of oxygen (most other gases are d i a m a g n e t i c )
to p r o d u c e a flow of oxygen, a constituent of a gas
m i x t u r e , o v e r a t h e r m i s t o r in .contact with the gas.