JPH029304B2 - - Google Patents
Info
- Publication number
- JPH029304B2 JPH029304B2 JP56047897A JP4789781A JPH029304B2 JP H029304 B2 JPH029304 B2 JP H029304B2 JP 56047897 A JP56047897 A JP 56047897A JP 4789781 A JP4789781 A JP 4789781A JP H029304 B2 JPH029304 B2 JP H029304B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ion
- selective
- sensitive
- potential difference
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012528 membrane Substances 0.000 claims description 24
- 239000012488 sample solution Substances 0.000 claims description 11
- 239000011343 solid material Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 108010067973 Valinomycin Proteins 0.000 description 1
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Description
【発明の詳細な説明】
本発明はイオン選択性感応物質膜を用いたイオ
ン選択性電極に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ion-selective electrode using an ion-selective sensitive material membrane.
或る種の膜で２種の液を境しておくと両側の液
における特定イオンの濃度差に応じて膜の両面間
に電位差を発生する。このような膜がイオン選択
性感応膜（以後単に感応膜と云う）で、このよう
な膜は電示的分析においてイオン選択性電極を構
成するのに利用される。この種の膜は多くは有機
質で柔軟でありそれを薄膜にして用いるので取扱
い上大へん不便である。 When two types of liquids are separated by a certain type of membrane, a potential difference is generated between both sides of the membrane depending on the difference in the concentration of specific ions in the liquids on both sides. Such a membrane is an ion-selective sensitive membrane (hereinafter simply referred to as a sensitive membrane), and such a membrane is used to constitute an ion-selective electrode in electrochemical analysis. Most of these types of membranes are organic and flexible, and are very inconvenient to handle because they are used in thin films.
本発明は上述したような感応膜を用いたイオン
選択性電極で感応膜の柔軟性に基く取扱い上の不
便さを解消することを目的としてなされた。 The present invention was made with the purpose of solving the inconvenience in handling due to the flexibility of the sensitive membrane in an ion-selective electrode using the above-mentioned sensitive membrane.
上述したような目的に適するものとして従来か
ら金属電極棒の表面に上述した感応膜を塗布法に
より形成したものが提案されている。この型のイ
オン選択性電極は感応膜と金属電極棒との間に一
定の接触電位差があり、感応膜表面と試料液との
間に特定のイオンの活量に応じた電位差が発生し
て、この２つの電位差が加算されたものが試料液
の電極棒との間の電位差として現れるものと考え
られる。しかし具体的にこの電位差を測定するに
は試料液に参照電極を挿入し、上記した電極棒と
参照電極との間の電位差を測定することになる
が、電極棒と感応膜との間の接触電位差が不明で
あるから、実際の測定に当つては何等かの方法に
よる較正が必要であり、上記接触電位差は温度に
より変る可能性があるから、この型のイオン選択
性電極は測定操作が面倒になる。 As a device suitable for the above-mentioned purpose, one in which the above-mentioned sensitive film is formed on the surface of a metal electrode rod by a coating method has been proposed. This type of ion-selective electrode has a certain contact potential difference between the sensitive membrane and the metal electrode rod, and a potential difference depending on the activity of a specific ion is generated between the sensitive membrane surface and the sample liquid. It is thought that the sum of these two potential differences appears as a potential difference between the sample liquid and the electrode rod. However, to specifically measure this potential difference, a reference electrode must be inserted into the sample solution and the potential difference between the electrode rod and the reference electrode described above must be measured. Since the potential difference is unknown, calibration using some method is required for actual measurement, and since the contact potential difference mentioned above may change depending on temperature, measurement operations with this type of ion-selective electrode are troublesome. become.
本発明に係るイオン選択性電極は上述したよう
な測定操作上の面倒さも解消することができるも
のである。以下実施例によつて本発明を説明す
る。 The ion selective electrode according to the present invention can also eliminate the troublesome measurement operations as described above. The present invention will be explained below with reference to Examples.
第１図及び第２図は本発明の一実施例を示す。
１１は電極本体で容器を一本の管１２が貫通した
形になつている。この電極本体の材質は任意で、
このような形に成形できかつ丈夫なものであれ
ば、プラスチツク、ガラス、金属何れでもよい。
実際にイオン選択性電極として作用するのは管１
２の部分で、管１２に試料溶液を流すようになつ
ている。管１２の内面及び電極本体１１の内面
（管１２の外面も含む）全体に感応膜４が付着形
成してある。このような感応膜物質はイオン感応
物質とポリ塩化ビニルとの混合物をテトラヒドロ
フラン（THF）で溶解したもので、これを塗布
し溶媒のTHFを蒸発させ膜を乾固させて感応膜
を得る。イオン感応物質としてバリノマイシンを
用いるとK+イオンに対し選択的に応答する感応
膜が得られる。電極本体１１内には感応膜が応答
するイオンの既知濃度の電極液２が入れてあり、
その液中に内部電極１が挿入してある。感応膜４
が上述したK+イオン選択性感応膜であるときは
この電極は云うまでもなくK+イオンに選択性を
持つのであり、その場合電極液２としては濃度既
知のKCl溶液を用い内部電極１はKCl溶液中の
Cl-イオンに応答するAgCl膜を形成した銀線のよ
うなものを用いる。こゝで内部電極としてK+に
応答するものを用いても良いことは云うまでもな
い。 1 and 2 show an embodiment of the present invention.
Reference numeral 11 denotes the electrode body, which has a shape in which a single tube 12 passes through the container. The material of this electrode body is optional.
It may be made of plastic, glass, or metal as long as it can be molded into this shape and is durable.
Tube 1 actually acts as an ion-selective electrode.
2, the sample solution is allowed to flow into the tube 12. A sensitive film 4 is attached to the entire inner surface of the tube 12 and the inner surface of the electrode body 11 (including the outer surface of the tube 12). Such a sensitive film material is a mixture of an ion-sensitive material and polyvinyl chloride dissolved in tetrahydrofuran (THF), and a sensitive film is obtained by applying this, evaporating the solvent THF, and drying the film. When valinomycin is used as an ion-sensitive substance, a sensitive membrane that responds selectively to K + ions can be obtained. The electrode body 11 contains an electrode solution 2 with a known concentration of ions to which the sensitive membrane responds.
An internal electrode 1 is inserted into the liquid. Sensitive membrane 4
When is the above-mentioned K + ion-selective sensitive membrane, this electrode is, of course, selective to K + ions, and in that case, the electrode solution 2 is a KCl solution with a known concentration, and the internal electrode 1 is in KCl solution
A silver wire-like material with an AgCl film that responds to Cl - ions is used. It goes without saying that an internal electrode that responds to K + may be used here.
以上の構成で管１２に試料溶液を流すと、試料
溶液中の目的イオンの活量に応じた電位差が試料
溶液と管１２内面の感応膜４との間に発生し、電
極本体１１内面の感応膜４と電極液２との間には
一定の電位差が生じており、電極液２と電極１と
の間にも一定の電位差が発生しているので、電極
１と試料溶液との間には上述した３つの電位差を
加算した電位差が発生している。 When a sample solution is flowed through the tube 12 with the above configuration, a potential difference corresponding to the activity of the target ion in the sample solution is generated between the sample solution and the sensitive membrane 4 on the inner surface of the tube 12, and the sensitive membrane 4 on the inner surface of the electrode body 11 is generated. A certain potential difference occurs between the membrane 4 and the electrode solution 2, and a certain potential difference also occurs between the electrode solution 2 and the electrode 1, so there is a difference between the electrode 1 and the sample solution. A potential difference is generated that is the sum of the three potential differences described above.
電極本体１１の材質は前述したように任意であ
るが、ガラスとかプラスチツクのような絶縁性材
質を用いたときは電極抵抗を低下させるためイオ
ン選択性電極として機能する管１２の本体１１内
に在る部分はなるべく薄肉であることが望まし
い。電極本体１１を金属にするときは管１２は特
に薄肉であることは必要ではないが、感応膜にピ
ンホールがないように特に注意する必要がある。
これは試料液とか電極液がピンホールを通して金
属に接触すると金属と溶液間に一定の起電力が生
じ、金属全体がその電位になるから内部電極と試
料溶液との間の電位差はピンホールが無い場合と
かなり異つた値になる。 The material of the electrode body 11 is arbitrary as described above, but when an insulating material such as glass or plastic is used, it may be present in the body 11 of the tube 12 that functions as an ion-selective electrode in order to reduce the electrode resistance. It is desirable that the part that is exposed is as thin as possible. When the electrode body 11 is made of metal, the tube 12 does not need to be particularly thin, but special care must be taken to ensure that there are no pinholes in the sensitive membrane.
This is because when the sample solution or electrode solution contacts the metal through a pinhole, a certain electromotive force is generated between the metal and the solution, and the entire metal becomes at that potential, so there is no pinhole in the potential difference between the internal electrode and the sample solution. The value will be quite different in this case.
第１図，第２図に示した電極は単独ではもちろ
ん電極電位を測定できない。試料溶液には他方で
参照電極を接触させる必要がある。この参照電極
として電極の内部構造即ち電極本体内面のイオン
感応性，電極液，内部電極のイオン感応性を上述
イオン選択性電極の内部構造と同じにしておくこ
とにより電極内部に発生している電位差を相殺で
きるから２つの電極間の電位差はイオン選択性電
極の目的イオン活量に応答した電位差となる。始
めに述べた金属棒電極に直接感応膜を形成したも
のでは上述した電極内部構造において発生してい
る電位差を相殺するようにできないから測定操作
が面倒になるのである。 Of course, the electrodes shown in FIGS. 1 and 2 cannot measure electrode potentials alone. On the other hand, it is necessary to contact the sample solution with a reference electrode. As this reference electrode, the internal structure of the electrode, i.e., the ion sensitivity of the inner surface of the electrode body, the electrode liquid, and the ion sensitivity of the internal electrode are kept the same as the internal structure of the ion-selective electrode described above, thereby generating a potential difference inside the electrode. can be canceled out, so the potential difference between the two electrodes is a potential difference that responds to the target ion activity of the ion-selective electrode. In the case where a sensitive film is directly formed on the metal rod electrode mentioned above, the measurement operation becomes troublesome because it is not possible to cancel out the potential difference generated in the internal structure of the electrode.
なお上述第１図の実施例は容器に管を貫通させ
た形に意味があるのではないから中に内部電極液
を入れ、その中に内部電極を挿入した中空電極本
体を被検液中に挿入する形で中空電極本体の内外
面に感応膜を形成してもよい。電極本体材料は任
意であるがポリ塩化ビニルを用い、イオン感応物
質とテトラヒドロフラン（PVCの溶媒）との混
合物を表面に塗布してTHFを蒸発させると電極
本体表面が溶かされてイオン感応物質と混合して
固まるから電極本体表面に強固な感応膜面を形成
することができる。また上述した塗布と云つた方
法に限らずスパツタリング，CVD或はプラズマ
による感応膜の付着のさせ方も可能である。 Note that in the embodiment shown in Figure 1 above, there is no meaning in having the tube penetrate the container, so the internal electrode liquid is placed inside the container, and the hollow electrode body with the internal electrode inserted therein is immersed in the test liquid. A sensitive film may be formed on the inner and outer surfaces of the hollow electrode body in an inserted manner. The electrode body material can be any material, but polyvinyl chloride is used, and when a mixture of an ion-sensitive substance and tetrahydrofuran (PVC solvent) is applied to the surface and THF is evaporated, the electrode body surface is dissolved and mixed with the ion-sensitive substance. Since it hardens, a strong sensitive membrane surface can be formed on the surface of the electrode body. In addition to the coating method described above, it is also possible to apply the sensitive film by sputtering, CVD, or plasma.
本発明イオン選択性電極は上述したような構成
で、感応膜が丈夫な物体表面に形成されているの
で構造的に強く取扱いが楽となり、電極形状が任
意にできる（電極本体の造型可能な範囲で任意）
ので、流通試料の連続測定用とか試料を容器に採
つては測定するバツチ式の精密測定用とか目的に
応じた形の電極を得ることができる。 The ion-selective electrode of the present invention has the above-described structure, and the sensitive membrane is formed on the surface of a durable object, making it structurally strong and easy to handle. (optional)
Therefore, it is possible to obtain electrodes of a shape suitable for the purpose, such as for continuous measurement of circulating samples or batch-type precision measurement in which samples are collected in a container and measured.
第１図は本発明の一実施例における縦断側面
図、第２図は上記のＡ―Ａ水平断面図である。
１……内部電極、２……電極内部液、４……感
応膜、５……試料溶液、１１……電極本体。
FIG. 1 is a longitudinal sectional side view of one embodiment of the present invention, and FIG. 2 is a horizontal sectional view taken along the line AA mentioned above. DESCRIPTION OF SYMBOLS 1... Internal electrode, 2... Electrode internal liquid, 4... Sensitive membrane, 5... Sample solution, 11... Electrode body.
Claims (1)
電極本体の試料溶液との接液面及び電極本体内面
にイオン選択性感応膜を形成し、電極本体内に電
極内部液を入れ、同液内に内部電極を挿入してな
ることを特徴とするイオン選択性電極。1. An ion-selective sensitive membrane is formed on the surface of the electrode body formed in an arbitrary hollow shape from an appropriate solid material in contact with the sample solution and on the inner surface of the electrode body, and the electrode internal solution is placed inside the electrode body. An ion-selective electrode characterized by inserting an internal electrode into the ion-selective electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56047897A JPS57161543A (en) | 1981-03-30 | 1981-03-30 | Ion selective electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56047897A JPS57161543A (en) | 1981-03-30 | 1981-03-30 | Ion selective electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57161543A JPS57161543A (en) | 1982-10-05 |
| JPH029304B2 true JPH029304B2 (en) | 1990-03-01 |
Family
ID=12788186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56047897A Granted JPS57161543A (en) | 1981-03-30 | 1981-03-30 | Ion selective electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57161543A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558451A (en) * | 1978-05-10 | 1980-05-01 | Fresenius Eduard Dr | Ion selecting sensor and method of producing same |
-
1981
- 1981-03-30 JP JP56047897A patent/JPS57161543A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558451A (en) * | 1978-05-10 | 1980-05-01 | Fresenius Eduard Dr | Ion selecting sensor and method of producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57161543A (en) | 1982-10-05 |
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