U.S. patent number 3,856,649 [Application Number 05/341,999] was granted by the patent office on 1974-12-24 for solid state electrode.
This patent grant is currently assigned to Miles Laboratories, Inc.. Invention is credited to Marvin Alden Genshaw, Melvin Dee Smith.
United States Patent |
3,856,649 |
Genshaw , et al. |
December 24, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
SOLID STATE ELECTRODE
Abstract
A solid state electrode for use in determining ion concentration
in an aqueous solution. The electrode comprises an electrically
conductive inner element with a salt disposed on a surface portion
thereof having as a cation a cation form of the element and also
having an anion, a hydrophilic layer in intimate contact with the
salt and including a water soluble salt of said anion and a
hydrophobic layer in intimate contact with the hydrophilic layer
whereby the hydrophilic layer is shielded from contact with the
ion-containing aqueous solution. This electrode may function as a
reference electrode as well as an electrode for identifying
specific ions.
Inventors: |
Genshaw; Marvin Alden (Elkhart,
IN), Smith; Melvin Dee (Mishawaka, IN) |
Assignee: |
Miles Laboratories, Inc.
(Elkhart, IN)
|
Family
ID: |
23339911 |
Appl.
No.: |
05/341,999 |
Filed: |
March 16, 1973 |
Current U.S.
Class: |
204/418;
204/435 |
Current CPC
Class: |
G01N
27/3335 (20130101) |
Current International
Class: |
G01N
27/333 (20060101); G01n 027/30 () |
Field of
Search: |
;204/195M,195P,195F,1T
;128/2E ;324/29 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Schwalbach; Joseph C.
Claims
What is claimed is:
1. A solid state electrode for use in determination of ion
concentration in an aqueous solution comprising, an electrically
conductive inner element,
a salt having as a cation a cation form of at least a portion of
said inner electrode material and also having an anion, said salt
being disposed on a surface portion of said inner electrode,
a solid hydrophilic layer in intimate contact with said salt, said
solid hydrophilic layer including polyvinyl alcohol and a water
soluble salt of said anion, and
a solid hydrophobic layer in intimate contact with said solid
hydrophilic layer shielding said solid hydrophilic layer from
direct contact with the ion-containing aqueous solution when said
electrode is immersed therein.
2. An electrode as described in claim 1 wherein said salt is a
layer in intimate contact with said inner element.
3. An electrode as described in claim 1 wherein said anion is a
halogen.
4. An electrode as described in claim 1 wherein said hydrophilic
layer includes water and a water soluble salt.
5. An electrode as described in claim 1 wherein said hydrophobic
layer includes at least one polymer selected from the group
consisting of polyvinyl chloride, polymethylmethacrylate and
polyvinylidene chloride.
6. An electrode as described in claim 1 wherein said hydrophobic
layer consists essentially of a combination of polyvinyl chloride
and glycerol triacetate.
7. An electrode as described in claim 1 wherein an ion selective
material is included in said hydrophobic layer.
8. An electrode as described in claim 1 wherein said hydrophobic
layer consists essentially of a combination of polyvinyl chloride,
dipentyl phthalate and valinomycin.
9. An electrode as described in claim 1 wherein said hydrophobic
layer consists essentially of a combination of polyvinyl chloride,
1-bromonaphthalene and valinomycin.
Description
BACKGROUND OF THE INVENTION
This invention relates to an electrode for use in measuring ion
concentration. More specifically, this invention relates to a
totally solid state electrode which may be used as a reference
electrode or as an ion specific electrode for use in measuring
unknown ion concentrations in a solution.
It is known that variations in electrode potential may be used to
determine ion concentration in an aqueous solution. For the purpose
of such determination, one practice has been to immerse in the
solution containing the unknown ion concentration a reference
electrode and an ion specific or indicator electrode. The potential
of the reference electrode remains substantially constant
regardless of the concentration of the specific ion in the unknown
solution. The indicator electrode, on the other hand, is sensitive
to variations in the concentration of the specific ion, yielding a
change in EMF which may be measured with known electrical
devices.
Electrodes for use in determining ion concentrations have many
forms, from the well known glass electrodes to the more recent ion
selective membrane electrodes. Although the electrode art has
advanced in recent years, electrodes still require special
handling, particularly when assembling membrane electrodes, and
caution in use. Also, these electrodes are expensive and are
generally too large to use with micro quantities of solutions.
Further, these electrodes share the common structural feature of a
liquid inner electrolyte.
SUMMARY OF THE INVENTION
This invention is embodied in a totally solid state electrode for
use in determining ion concentration in an aqueous solution. This
electrode comprises an electrically conductive inner element having
disposed thereon a salt having as a cation a cation form of at
least a portion of the inner element and also having an anion. In
intimate contact with the salt is a solid hydrophilic layer
including a water soluble salt of said anion. In intimate contact
with the hydrophilic layer is a solid hydrophobic layer which
shields the hydrophilic layer from direct contact with the
ion-containing aqueous solution.
Accordingly, it is an object of this invention to provide a totally
solid state electrode requiring substantially no special handling
during its use.
Another object of this invention is to provide a totally solid
state electrode having a simple structure which may be
inexpensively manufactured.
A further object of this invention is to provide a miniaturized
solid state electrode suitable for use in measuring ion
concentrations in micro quantities of sample solutions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The electrically conductive inner element of the electrode of this
invention may be selected from metals that are commonly used for
this purpose. This metal is preferably selected from one which
readily forms an insoluble salt and has good electrical properties.
Such metals include silver, amalgams and the like. Although the
shape of the electrode is not critical, a symmetrical shape, such
as a wire, is advantageous in that its size may be very small and
it is readily available without additional fabrication. Other
configurations such as metalized films on nonconducting substrates,
sheets of conducting material, etc., may be used in this
invention.
The insoluble salt is in the form of a layer disposed on a surface
portion of the inner element and has, as a cation, the cation form
of the metal of the element. It also has an anion such as a
halogen. The salt layer may be formed by anodizing the element in a
suitable solution, by a physical application of a dispersion of the
salt in a suitable carrier that will adhere to the element or by
other suitable methods. The salt may be formed about an end portion
of the inner element or its position may be varied according to the
desired structural features of the electrode.
The hydrophilic layer is in intimate contact with the salt disposed
on the inner element. The thickness of this layer is not considered
critical and may be adjusted in accordance with desired
manufacturing techniques. The formation of this layer will be
discussed hereinafter and will not, therefore, be set forth at this
time. The salt included in this layer is a water soluble salt
having a cation selected from alkali metals or alkaline earth
metals such as sodium, potassium, magnesium, calcium, and barium;
and as anions halogens. Since there is a transfer of charge through
ion transfer across this layer the particular salt selected is
critical and must be compatible with the insoluble salt.
Representative of such salts are NaCl, KCl, KBr, MgCl.sub.2,
BaCl.sub.2 and other such halides that may be used with the
insoluble halide covering the inner element.
Overlaying the hydrophilic layer is the hydrophobic layer which
shields the hydrophilic layer from direct contact with the
ion-containing solution. This layer may be formed from well known
hydrophobic polymeric materials such as polyvinyl chloride (PVC), a
polymethylmethacrylate, polyvinylidene chloride, polystyrene and
the like. Prior to application these materials may be dissolved in
well known solvents therefore, such as cyclohexanone, xylene,
methylene chloride, ethylene chloride, etc. An increase in the
thickness of the hydrophobic layer results in a longer response
time for the electrode while also resulting in a longer storage
life (wet or dry) and longer useful life. It has been found
advantageous to combine with this material additives such as
glycerol triacetate, dipentyl phthalate, 1-bromonaphthalene and the
like or combinations thereof.
Although the hydrophobic layer shields the hydrophilic layer from
direct contact with the aqueous solution, the hydrophobic layer
appears to be analogous to the membrane of membrane electrodes or
the glass of glass electrodes. It is believed that an osmotic
equilibrium is established across the hydrophobic layer similar to
that established across semipermeable membranes.
The solid state electrode of this invention may be made ion
selective by incorporating with the hydrophobic layer an ion
selective material such as valinomycin; crown ethers; magnesium or
zinc uranyl acetate; monensin; 6,8-dichlorobenzoylene urea;
didecylphosphoric acid-dioctyl phenylphosphonate; monactin;
tetraphenylboron; tridodecylhexadecylammonium nitrate in
n-octyl-o-nitrophenyl ether;
4-amino-4'-chlorodiphenylhydrochloride, barium salt and other
similar ion complexing and selective materials. By incorporating
one of the above-mentioned materials in this layer, an ion
selective electrode for ions, such as K.sup.+, Ca.sup.+.sup.+,
NO.sub.3 .sup.- or SO.sub.4 .sup.-.sup.-, is provided which has the
advantageous features of the electrode of this invention.
The solid state electrodes of this invention are prepared by
disposing on a surface portion of the inner element a salt layer
having as a cation the cation form of the inner element.
Preferably, the salt layer is disposed on a small portion of the
inner element, such as on a tip portion when it is a wire, so that
it may be totally immersed in the solution to be tested. The
hydrophilic layer is placed in intimate contact with at least a
portion of the salt layer and includes a water soluble salt having
the same anion as the salt layer. The hydrophilic layer is readily
applied by momentarily dipping the inner electrode into a suitable
solution of the components of the hydrophilic layer. Promptly
following this dipping, the partially fabricated electrode is
momentarily dipped into a suitable solution of the components of
the hydrophobic layer such that the hydrophobic layer will totally
encompass the hydrophilic layer. The dipping into the hydrophobic
layer-forming solution is beneficially repeated from 2 to 6 or more
times as required to provide the desired thickness of hydrophobic
layer. Throughout the application of the hydrophobic and
hydrophilic layers, the environment around the electrode is
supported at a predetermined temperature and relative humidity so
that a hydrated state of the hydrophilic layer is maintained. This
hydrated state is considered important to the proper functioning of
the electrode of this invention.
The structure of and the preparation of the solid state electrode
of this invention will be further described in the following
examples which set forth specific embodiments of this invention
which are only representative thereof and do not limit the scope or
use of this invention in any way.
EXAMPLE 1
A reference electrode was prepared using as the inner element
thereof a straight length of 18 gage silver wire which was first
cleaned in isopropyl alcohol to remove organic residue thereon.
This wire was further cleaned with deionized water, and then a 2 mm
end portion thereof was anodized for one minute at 0.8-1.0 ma. in
0.1N HCl. The silver inner element with the salt layer disposed
thereon was dipped momentarily into a polyvinyl alcohol (ELVANOL
grade 72-60) -sodium chloride aqueous solution (10% PVA solution in
0.5M NaCl) to form thereon the hydrophilic layer. The element was
then promptly dipped momentarily into a glycerol
triacetate-polyvinyl chloride (PVC) solution, consisting of 14%
glycerol triacetate and 6% PVC dissolved in cyclohexanone, to form
the hydrophobic layer. The thus coated element was thereafter
similarly dipped into this glycerol triacetate-PVC solution at half
hour intervals five more times. The electrode was cured at
37.degree.C and 73% relative humidity during the application of the
hydrophobic layer and for at least 18 hours thereafter. The
hydrophobic layer totally covered the hydrophilic layer. The
balance of the silver wire, with the exception of a portion for its
connection to an external circuit, was covered with a wax
sealant.
The resulting electrode was about 2 mm in length and 2.5 mm in
diameter. The silver wire extended from the electrode an additional
1.5 cm of which about 5 mm adjacent to the electrode was covered
with the wax sealant. This electrode maintained a substantially
constant potential for normal testing periods when evaluated in
solutions of varying sodium and potassium ion concentration.
EXAMPLE 2
The procedure of this Example was the same as Example 1 with the
exception that KCl was substituted for NaCl in the hydrophilic
layer.
The resulting electrode had an appearance and performance
substantially identical with the electrode of Example 1.
EXAMPLE 3
The procedure of this Example was the same as Example 2 with the
exception that the KCl concentration was reduced to 0.005 M and the
solution used to form the hydrophobic layer consisted of 6% PVC,
14% dipentyl phthalate and 0.1% valinomycin in cyclohexanone.
The resulting electrode had an appearance substantially the same as
the electrodes of Examples 1 and 2. This electrode was observed to
have a high selectivity for potassium ions as set forth in the
following Example 4.
EXAMPLE 4
An electrode prepared according to Example 3 was evaluated in
aqueous solutions of different concentrations of mixtures of
potassium and sodium chloride as set forth in Table 1. Replicate
determinations were made in each solution in a random manner with
the six solutions consisting of two KCl concentrations of 3
meq/liter and 6 meq/liter in combination respectively with NaCl
concentrations of 120, 140 and 160 meq/liter. All electrode
measurements (.DELTA.E.sub.mv) were made versus a Standard Calomel
Electrode (SCE) (K401, Radiometer, Denmark) through a saturated
lithium trichloracetate salt bridge. The electrodes were dry
blotted between measurements. Measurements were made with a
Hewlett-Packard (3440A) Digital Voltmeter and an Analog Device 311
J follower as a preamplifier.
TABLE 1 ______________________________________ Electrode Potassium
Response in Mixed Salt Solutions NaCl .DELTA.E.sub.mv vs SCE
.DELTA.E.sub.mv vs SCE (meq/liter) KCl (3 meq/liter) KCl (6
meq/liter) ______________________________________ 120 0.4, 0.4
17.8, 17.7 140 0.7, 0.6 17.5, 17.5 160 0.5, 0.0 18.4, 17.7
______________________________________
It was observed that the differences between the EMF measurements
did not exceed 0.7 mv. for a given potassium ion concentration
regardless of the sodium ion concentration. Such a difference was
not considered significant and accordingly demonstrated the
selectivity of this electrode for K.sup.+ over Na.sup.+. It was
also observed that there was a greater than 25 fold difference in
.DELTA.E.sub.mv between the 3 meq/liter solution and the 6
meq/liter solution. Although electrode response was completed after
30 seconds, readings were taken after 2 minutes to insure that
equilibrium was reached.
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