United States Patent 0 cc 3,431,182

Patented Mar. 4, 1969

1 2
Yet another principal object of the invention is to pro
3,431,182 vide a sensing electrode sensitive to ?uoride ion activity
FLUORIDE SENSITIVE ELECTRODE AND in a stable and reproducible manner.
METHOD OF USING SAME
Martin S. Frant, Newton, Mass., assignor to Orion Re Still another object of the present invention is to pro
search, Inc., Cambridge, Mass., a corporation of Massa vide a ?uoride io ~sensitive electrode comprising means
chusetts supporting an imporous barrier or membrane of a sub
Filed Feb. 4, 1966, Ser. No. 525,197 stantially water insoluble, crystalline ionic ?uoride and
US. Cl. 204-1 12 Claims means in electrical contact with one side of the mem
Int. Cl. B01k 3/06 brane at a substantially ?xed reference potential.
10 Yet other objects of the invention will in part be obvi
ous and will in part appear hereinafter. The invention ac
ABSTRACT OF THE DISCLOSURE cordingly comprises the apparatus possessing the con
struction, combination of elements, and arrangement of
A potentiometric type electrode for and method of de parts and comprises the several steps and the relation of
tecting ?uoride ion activity in solution, the electrode hav 15 one or more of such steps with respect to each of the
ing, as its ion-sensitive element, a membrane of substan others of which are exempli?ed in the following detailed
tially imporous, solid, ionic ?uoride substantially insolu disclosure, and the scope of the application of which
ble in the solution. The membrane is contacted at one will be indicated in the claims.
surface by the solution and at the other surface by a refer For a fuller understanding of the nature and objects of
ence electrolyte providing a ?xed contact potential. Exem 20 the present invention, reference should be had to the
plary membranes are formed of ?uorides of the lan following detailed description taken in connection with
thanide series of selected rare earth metals, preferably as the accompanying drawing wherein:
single large crystals. FIG. 1 is a schematic, side-elevational, cross-sectional
diagram of an electrode embodying the principles of the
. 25 present invention and useful for ?uoride ion detection in
a solution.
' This invention relates to electrochemical detection and FIG. 2 is a schematic, side-elevational view, partly in
measurement and more particularly to methods for deter cross-section, of a cell employing an electrode similar to
mining and measuring the presence of ?uoride ions, and FIG. 1 for the detection of ?uoride ions;
novel apparatus for use in such methods. 30 FIG. 3 is a graph of the response of an electrode of the
Considerable interest exists in providing methods for present invention to ?uoride ions.
determining the concentration of dissolved ?uorides in The present invention is based upon the use of an
water, particularly since ?uoridation of municipal water imporous membrane of crystalline ?uoride substantially
supplies has now become quite common. A number of insoluble in water, as a ?uoride transducer. The term
gravimetric and volumetric methods are in use for deter membrane as used herein, consistent with its usage in
mining dissolved ?uoride, but all of these suffer from the potentiometric electrode technology, is intended to em
drawback that they are only applicable to relatively con brace a sheet-like structure, generally regardless of ?ex
centrated solutions, since they require that the ?uoride be ibility or curvature, which provides a pair of limiting sur
determined by the precipitation of calcium ?uoride, lead faces between which charge transfer is effected.
?uoride, lead ?uoride-chloride, or some other insoluble 40 Referring now to the drawing, there is shown in FIG.
?uoride salt. The same is true of indirect titrations such 1 electrode 20 embodying the principles of the present in
as that involving calcium and EDTA. Further, all of the vention and comprising an elongated, hollow tubular con
gravimetric and volumetric procedures require isolating of tainer or stem 22 open at both ends. The stem typically
a sample from the stream and subsequent analysis at a is formed of a liquid-impervious, substantially rigid, elec~
later point in time. 45 trically-insulating material, such as unplasticized poly
Some electrochemical techniques are known but have vinylchloride, polytetra?uoroethylene, or the like, substan
been quite unsatisfactory. For example, polarographic de tially chemically inert to salt solutions containing ?uoride
terminations of ?uoride can be made but require much ions and with which the stern might be placed in contact.
preliminary processing to remove interfering ions. Fur One end of stem 22 is capped or sealed with a barrier
ther, such methods are sensitive to electrode area and 50 disc or membrane 24 formed of a substantially imporous,
spacing, stirring rate and other variables. An ampero high-purity, crystalline ?uoride. Membrane 24 can be
metric method is known based on the etching of silicon quite thick, for example, 1A" although thinner structures
by ?uorides, but requires a highly acid test solution. An are preferred. Membrane 24 can be sealed across the
electrode has been reported [S. Megregian, Anal. Chem. one end of stem 22 with an appropriate sealing com
29, 106365 (1957)], which is based on the dissolution pound such as an epoxy or polyester resin. Alternatively,
of zirconium oxide from zirconium metal, but its response as shown, the membane is mounted by an O-ring 26
was only to concentrations of ?uoride greater than nor disposed about the periphery of the opening in the
mally found in drinking water, and was not Nernstian. stem, and held in pressed-?t against the O-ring by
The present invention, therefore, contemplates an im annular ?ange 27 of collar 28 threadedly mounted on
proved method and means for detecting electrochemically, 60 the stem. When collar 28 is rotated in the proper direc
the presence of ?uoride ions in solution.
tion, it advances axially, forcing membranes 24 in a
Further objects of the present invention are to provide tight ?t abainst the O-ring, thus sealing the one end
a method of detecting ?uoride ions which requires no re of stem 22. Both the O-ring and collar 28 are preferably
agent addition or sample pretreatment, and is insensitive made of plastic material such as polyvinylchloride.
to sample solution ?ow rate, thereby permitting direct-on 65 Disposed internally of stem 22 and in electrical and
stream monitoring; to provide means for carrying out the
physical contact with the inner surface of membrane 24
foregoing method which yields a continuous output signal is charge transfer means providing a ?xed concentration
voltage bearing a simple logarithmic relation to ?uoride
of ions. This means is shown as a reference electrolyte
ion activity with suf?ciently rapid response time to 30, for example, an aqueous saturated solution of KCl,
changes in the ?uoride ion activity to permit control in 70
substantially real-time. AgCl, and 1 molar in ?uoride from KF. Immersed in
electrolyte 30 is internal reference electrode 32, for
 3,431,182 4
3 solution, will develop a potential Em according to the
example the well-known Ag-AgCl element. This combin
ation of electrolyte 30 and reference electrode 32 provides well-known Nernst equation as follows:
means for electrically contacting the internal face (i.e.
the surface of the membrane contacting the reference (I) Em=constant+%T ln AF
electrolyte) at a substantially stable or ?xed potential. where AF- is the ?uoride ion activity in the sample
The other open end of stem 22 is ?tted with annular
cap 34 having an aperture in which is sealed the usual solution.
As shown in FIG. 2, sensing electrode 20 of the present
coaxial cable 36, the central conductor of which is invention in use is placed so that the outer surface of
connected to internal reference electrode 32 and the membrane 24 contacts solution 40 under test (i.e. which
peripheral conductor of which is intended to provide 10 contains the ?uoride ions sought to be detected). A
electrostatic shielding. standard reference electrode 42 is also placed in contact
The more important considerations in fabricating the
electrode of FIG. 1 lie in the material and structure with solution 40.
Electrode 42 typically is the usual assembly housed
of membrane 24 and the nature of the seal between in a conventional glass shell containing an Ag-AgCl
the electrode stem and the membrane as above described. 15
electrode in saturated aqueous KCl-AgCl separated by
The other elements and the shape and size of the an asbestos ?ber junction from a l M NaOH solution.
electrode are not particularly critical and can be selected The latter solution occupies the lower end of the shell
according to the anticipated use. and is coupled to solution 40 through the usual ?ber
The ?uoride salts used to form the membrane of the junction shown at 44. Both sensing electrode 20 and
present invention are those which are highly insoluble reference electrode 42 are connected electrically to re
in water and can be formed into a substantially imporous, spective inputs of electrometric device 46, the latter
solid ionic crystalline mass, i.e. membrane. Among such being preferably the usual high-input impedance volt
salts are particularly the tri?uorides of bismuth, scan
dium, yttrium and the lanthanide series of rare earth meter.
In operation of the assembly of FIG. 2, a potential,
metals, and the di?uoride of lead. The membrane can 25 Em, of substantially ?xed value (assuming constant tem
be formed as a compressed pellet of polycrystallite
powder or as a unitary monocrystal depending on a perature conditions) develops between reference elec
trode 42 and solution 40 independently of ?ouride
number of factors. concentration in the latter. Another potential, Em, will
For example, it is di?icult to grow large crystals of
BiF3. However, powdered BiFa can be compressed in 30 develop across membrane 24 between internal electrolyte
30 and solution 40, but Em is dependent or varies log
steel dies at elevated temperature to provide an imporous arithmically according to the activity or concentration of
pellet. Typically, one can employ a pressure of 50,000
p.s.i. at 500~550 C. Without heating at this pressure, ?ouride ions in solution 40. Because the potential, Em,"
the pellet produced is porous and unsuitable. Naturally, between reference electrode 32 and electrolyte 30 is also
higher pressures at lesser temperatures will prove adequate 35 ?xed, the total potential Et, appearing between electrodes
to provide the requisite pellet. The heating does produce 42 and 20 will be the sum of Em, EreL and Emt. and thus
some metallic bismuth inclusion in the pellet but this varies with Em only. E, can be readily measured on
impurity does not affect the performance of the mem electromethic device 46, thus indicating the presence
brane because it does not appear at any surface where it and activity of the ?uoride ions in solution 40.
will be susceptible to redox potentials. Powdered poly The electrode of FIG. 1 was tested in an assembly such
crystalline lead di?uoride and the other noted ?uorides as that of FIG. 2 in a number of experiments to demon
can be similarly compressed into the desired membrane. strate the nature of the response to ?uoride ions in aqueous
Alternatively, a number of rare earth metal ?uorides salt solutions as set forth in the following examples:
are commercially available as monocrystalline slabs Example I
quite suitable for use as a membrane of the present in The electrode of FIG. 1 was constructed as follows:
vention. For example, neodymium ?uoride is available a commercial grade of bismuth tri?uoride was com
in optical grade, solid, grown monocrystals purportedly pressed in a steel die approximately a quarter of an
99.99% pure. Similarly, lanthanum, cerium, praseodym inch in diameter, to a thickness of about 3 mm. at a
ium, and other rare earth metal ?uorides are commercial pressure in excess of 50,000 p.s.i. This tablet, still in the
ly available in monocrystalline form. 50
die, was then heated to 500-550 C. and then recom
The membranes, whether monocrystalline or poly
crystalline, can be of mixed ?uoride structures such as pressed while still hot.
The tablet was sealed over the end of a polyvinyl
a mixture of lanthanum and cerium ?uorides, provided, chloride tube and an internal contact was made by
of course, that the ?uorides are all highly water insoluble. placing a quantity of bismuth amalgam in contact with
The mixed-?uoride structures exhibit selectively to ?uor the tablet. A platinum wire was inserted into the amalgam
ide ions comparable to single-?uoride structures. as a lead. The electrode was tested in an assembly such
The term highly insoluble as used herein is intended as shown in FIG. 2 wherein reference electrode 42 was
to mean that the ?uoride crystals have a solubility an Ag-AgCl electrode.
product when in equilibrium with the aqueous solution This electrode of the invention was used to obtain
being examined by the electrode, such that the concentra a series of responses to a number of pure aqueous sodium
tion in that solution of ?uoride ions derived from the ?uoride solutions of different molarities, with the fol
crystals is less than the lowest ?uoride activity that lowing results:
one can reasonably expect or intend to measure.
From a practical standpoint, because it is usually 65 Concentration of F", m./l.: Reading in mv.
desired to measure P- concentrations at least as low 1><10~1 +87
1><102 ____________________________ __ +140
at 1 p.p.m., it is preferred that the solubility product
1><103 ____________________________ __ +194
of the ?uoride membrane be smaller than would yield 5><104 ____________________________ __ +212
a 1 p.p.m. F- concentration when placed into equilibrium 1><104 ___ +232
with distilled water. Thus, a number of insoluble ?uor s><105 _ ____ +254
ides, such as CaF-z and BaFz are unsuitable. 1><105 ____________________________ __ +281
It has now been discovered that a membrane of XP 0 _____ __ _,__ +307
separating two solutions (where XP is a ?uoride salt
of the invention) one of which contains ?uoride ions at To determine the effect of interfering anions on the
a ?xed concentration and the other of which is a sample electrode response, this electrode was tested in a number
 3,431,182
of aqueous solutions each containing a different anion
6
tri?uoride as the membrane. When tested as in Example
in a particular concentration. The responses found as IH, the following readings were obtained:
follows:
Reading in mv. Reading in mv.
Concentration of F-, m./l. ?uoride only 1X10-z MO1
Anion and concentration, m./l.: Mv. response present
Cl 1><105 ________________________ __ +309 +30 +30
Cl-, 1x104 _________________________ __ +282 +84 +85
+140 +143
Cl-, 1><10-3 ________________________ __ +267 +196 +201
H0031 1><10-5 _____________________ __ +296 +216 +219
+252 +254
SO4=, 1><10-4 _______________________ __ +264 +269 +265
+304 .................. __
I~, l><10-4 _________________________ .. +267
N03", 1x104 ______________________ __ +280
Ion at 1X10"3 m./ 1.: Reading in mv.
P04E ___ + 142
Example II CH +157
15
HPO4= __ + 194
A pellet of optical grade (99.99% pure), monocrystal HCO3_ _ __ +220
line lanthanum tri?uoride, about 10 mm. in diameter H2PO4- +317
and 4 mm. thick, was sealed over the end of a polystyrene SO4= ________________________________ _... +264
tube. The latter was ?lled with an aqueous solution 20 NO3- _______________________________ .. +314
saturated with respect to KC] and AgCl and 1 molar in
?uoride. An Ag-AgCl electrode was placed in the Example V
internal solution. An electrode was formed as in Example II using opti
This electrode was tested in a con?guration such as cal grade neodymium tri?uoride as the monocrystalline
is shown in FIG. 2 using a standard Ag-AgCl electrode 25 membrance, and when tested as in Example HI, the
as reference electrode 42. A number of aqueous solu following results were obtained:
tions of only sodium ?uoride at ditferent concentrations
were tested and the readings in millivolts vs. log con _ Readings in mv. Readings in mv.
centration are graphically shown in FIG. 3. A similar Concentration of F-, m./l. ?uoride only 1><10-2 MO1
present present
series of ?uoride solutions, each containing Cl- ions in
l><10-2 molarity, were also tested and the readings are 1X 101 M______________________ _ _ +29 +29
also_ shown in FIG. 3 indicating that the electrode re
sponded to P- ions in substantially the same manner re~
gardless of the presence of Cl ions.
The electrode was further tested in aqueous solution
of various ions, all at 10-3 M concentrations. The read
ings in millivolts are each shown and identi?ed by the Ions and concentrations, m./l.: Readings in mv.
ionic symbol in FIG. 3. OH-, 1><10-4 _______________________ __ +230
HPO4=, 5><l0~1 _____________________ __ +200
Example HI 40 HCOf, 1><1-0-2 _____________________ __ +200
HgPOf, 1 ><102 ________________ ____.._ +174
An electrode was formed as in Example II except SO4=, 5><10-2 _______________________ __ +270
that the membrane was optical grade monocrystalline N031 1x 10-2 _______________________ __ +280
praseodymium tri?uoride (10 mm. diameter, 2 mm.
thick). When similarly tested against similar aqueous 45 Example VI
solutions the following results were obtained: An electrode was formed as in Example II using a
monocrystalline slab of lanthanum tri?uoride containing
10 mol percent of neodymium tri?uoride.
Reading in mv. Reading in mv. When tested as hereinbefore described in a series of
Concentration of F-, 111.11. ?uoride only 1X102 MCI
present present 50 pure aqueous ?uoride solutions, the following results were
obtained:
+28 +28
+82 +82 Concentration of F, m./l. Response in mv.
+138 +141 1X10-2 ____ +98
+193 +199
+213 +216 1X 10-3 _____________________________ __ +149
+249 +251 5 X 10-4 .. __ +168
+265 __________________ __

2.5><l04 ____________________ ______.____ +184

1 X 10-4 _. +199
5 X 10-5 _ _ +210
When tested against other ions as in Example II, each 2.5><105 ________________________ __.____ +215
being in aqueous solution at a 1><103 M concentration 1X 10-5 _____________________________ _._ +239
the following results were obtained: Example VII
Ion: Reading in mv. The electrode of FIG. 1 was constructed by preparing
a membrane of lead ?uoride powder compressed at room
P04E _______________________________ __ +156
65 temperature under pressure in excess of 60,000 p.s.i. The
OH _______________________________ __ +161
HPO4= ____ _ +194
membrane was sealed, as shown, over the end of a rigid
H003 __________________________ __.___ +225
polyvinylchloride tube and internal aqueous ?lling solu
tion of saturated KCL-AgCl-KF was inserted into the
SO4=
H2P04_
_______________________________
____ _._ __ +270 tube. As reference electrode 42, an Ag-AgCl wire was
70 provided. '
N05,- ________________________________ __ +288
When tested in aqueous ?uoride solutions as herein
Example IV before described, it was found to respond to ?uoride ions
but only in concentrations greater than 1><l0-3 M. It
also showed approximately equal sensitivity and similar
An electrode was formed as in Example II using cerium slope for chloride ions as for ?uoride ions. It is thus
 3,481,182 8
7 believed due to the extreme insolubility of the ?uoride
limited to use where one of these ionic species is present salts used in the invention, which prevents interference
at relatively higher concentration than the other or where due to metathetical reactions with almost all ionic species
the sum of mixed ?uoride-chloride activity is desired. in aqueous solution.
Example VIII Obviously, other electrode con?gurations can be made.
Thus, for example, a ?ow-through type of ?uoride elec
The electrode of Example V was selected, as repre trode can be made by growing or compressing an appro
sentative of the others, for determining the elfect of pH priate ?uoride into cylindrical form and axially boring
on electrode response. Measurements were made on sam out the center to form a hollow tube with walls as thick
ples of aqueous NaF solution standardized at 1X102 M, as 1A". The exterior of the tube can then be electrically
having pH adjusted either with NaOH or HCl. 10 connected at a ?xed contact potential to a wire as by
It was found that between about pH 5 to pH 13 the coating the tube with an annular strip of an appropriate
electrode response was completely independent of the amalgam or otherwise electrically connecting a wire to
pH. Above pH 13, where the hydroxyl ion concentration the latter. The exterior is then sealed with insulation.
exceeds the ?uoride ion concentration, the electrode re If a solution with ?uoride ions is passed through the tube
sponded markedly to the hydroxyl ion. Below pH 5 on 15 interior, the desired potential will develop across the tube
the acid side, the electrode continued to indicate the true from the interface with the solution to the electrically
?uoride activity. This latter is known to diminish rapidly
as a function of pH because of the formation of undisso conductive wire.
Since certain changes may be made in the above ap
ciated HF; thus, the response curve no longer was ?at. paratus and processes without departing from the scope
20
Example 1X of the invention herein involved it is intended that all
matter contained in the above description or shown in
That the electrodes of the foregoing examples can be the accompanying drawing shall be interpreted in an illus
used for monitoring a wide range of drinking water is
trative and not in a limiting sense.
established by the following experiments.
Water samples were selected from the following com 25 What is claimed is:
1. An electrode for detecting ?uoride ion activity in
munities: solution, and comprising, in combination:
(l) Wayland, Mass. which does not ?uoridate its a substantially imporous membrane adapted to have
municipal supply and uses deep wells as the source. This one surface thereof contacted by said solution, said
water was relatively low in mineral content. surface comprising an ion-sensitive crystalline ?uo
(2) Cambridge, Mass. where the water from local open ride selected from the group consisting of lead
reservoirs does not contain added ?uorides, and at the ?uoride and the tri?uorides of bismuth, scandium,
time of testing was very high in dissolved solids because yttrium and the lanthanide series of rare earth metals
of a drought condition. The water contained 234 p.p.m. said surface being substantially free of the metal of
total dissolved solids, had a hardness of 132 p.p.m., and which said ?uoride is the salt; and
a chloride content of 60 p.p.m. 35
means forming an electrical contact with the opposite
(3) Newton, Mass. which add ?uorides to its water by surface of said membrane at a substantially ?xed
an indirectly controlled system. The water is obtained
from Quabbin reservoir, some sixty miles distant.
contact potential.
2. An electrode as de?ned in claim 1 wherein said
These waters were tested with the lanthanum ?uoride crystalline ?uoride is the tri?uoride of a metal of the
electrode of Example II with the following results: 40
lanthanide series.
Community: F- in p.p.m. 3. An electrode as de?ned in claim 1 wherein said
Wayland ______________________________ __ .12 crystalline ?uoride is the tri?uoride of cerium, lanthanum,
Cambridge _____________________________ __ .12 praesodymium, neodymium, or mixtures thereof.
Newton _______________________________ __ .72 4. An electrode as de?ned in claim 3 wherein said
As will be seen from the foregoing representative membrane is a monocrystal of said crystalline ?uoride.
5. An electrode as de?ned in claim 1 wherein said ?uo
examples, the bismuth and lead ?uorides show excellent ride in said membrane is in polycrystalline form.
responsiveness to ?uoride ions, but for some purposes, 6. Method of making an electrode sensitive to ions in
their response to other ions such as chloride, sulfate and
the like, is too high. For example, this level of response a ?uid, comprising the steps of:
forming an ion-sensitive portion of said electrode of a
to other ions would be a problem in testing the relatively substantially imporous membrane comprising an
hard waters found in some areas. ion-sensitive crystalline ?uoride, at least one surface
On the other hand, scandium, yttrium and the lantha of said membrane being substantially free of the
num group of rare earth ?uoride electrodes appear to metal of which said ?uoride is the salt, said ?uoride
have selectivity for the ?uoride ion over chloride by a being selected from the group consisting of lead
factor so much greater that the presence of quite high 55 ?uoride and the tri?uorides of bismuth, scandium,
(ca. 10'2 M or about 200 p.p.m.) concentrations of yttrium and the lanthanide series of rare earth metals;
chloride do not seem to affect the electrode response
except at levels of ?uoride of approximately 1><10~5 M and
forming an electrical contact to another surface of said
(i.e. about 0.2 ppm.) or less. The most seriously com membrane at a ?xed contact potential.
peting ions seem to be OH" and P045. The response to 60 7. Method as de?ned in claim 6 wherein said step of
hydroxyl ion, which is about 20 mv. or more below the forming comprises the step of compressing said ?uoride,
response to ?uoride ion, is not considered serious inas in powdered form, into said membrane at pressures above
much as the presence of hydroxyl ions is easy to meas about 30,000 p.s.i. referred to room temperature.
ure and, if necessary, the electronics associated with the 8. Potentiometric method of measuring the activity of
electrode can be duly compensated for hydroxyl re ?uoride ion in solution and comprising the steps of:
sponse. Further, this is necessary, if at all, only where contacting said solution with a reference electrode to
the water has a pH above 8. The effect of the phosphate
ion is not considered serious either unless in highly basic establish a ?xed contact potential;
contacting said solution with a surface of a substan
solutions (>pH 12) and in fact, may instead be due tially imporous, ionic crystalline membrane of a
to hydroxyl ion. Around pH 7 the phosphate is normally 70 ?uoride, said surface being substantially free of the
present in about 1:1 proportions of mono and dihydrogen metal of which said ?uoride is the salt, and said
phosphate ions, neither of which particularly interferes ?uoride being selected from the group consisting of
with the ?uoride determination. the ?uorides of the lanthanide series of rare earth
The electrodes of the present invention are generally metals from lanthanum to europium inclusive,
quite speci?c in their response to ?uoride ion and this is 75
 3,431,182
connecting the other membrane surface to electrically
conductive means at a ?xed contact potential; and
measuring the total poteniial between said reference
electrode and said electrically conductive means.
9. A potentiometric system for measuring ion activity
of a sample solution, comprising:
a reference electrode adapted to provide a reference
potential when in contact with said sample; '
a sensing electrode having an ion-sensitive portion
thereof comprising solid imporous, ionic, crystalline
?uoride and being substantially free at a surface 10
thereof from the metal of which said ?uoride is the
salt, said ?uoride being selected from the group
consisting of the ?uorides of the lanthanide series of
rare earth metals from lanthanum to europium in 15
clusive; and
an electrical circuit connecting said electrodes for
measuring the electrical potential of a contact be
tween said ion-sensitive portion and said sample at
said surface. 20 HOWARD S. WILLIAMS, Primary Examiner.
10. An ion-sensitive element of an electrode for poten
tiometric detection of ?uoride activity in solution and
comprising: -
a ?uoride-ion sensitive membrane including at least
10
one ?uoride of the lanthanide series of rare earth
metals.
11. An ion-sensitive element of an electrode for poten
tiometric detection of ?uoride activity in solution and
comprising: I
a ?uoride-ion sensitive membrane including at least
one ?uoride selected from the group consisting of
the ?uorides of the lanthanide series of rare earth
metals from lanthanum to europium inclusive.
12. An ion-sensitive element of an electrode for poten
tiometric detection of ?uoride activity in solution and
comprising:
a ?uoride-ion sensitive membrane including lanthanum
?uoride.
References Cited
UNITED STATES PATENTS
3,058,901 10/1962 Farrah ___________ __ 2041.1
3,129,148 4/1964 Steinbrecher et al. __._ 204-195
T. TUNG, Assistant Examiner.
US. Cl. X.R.
204195, 291, 295