JPS593345A - Dissolved oxygen meter equipped with electrode for removing interfering component - Google Patents
Dissolved oxygen meter equipped with electrode for removing interfering componentInfo
- Publication number
- JPS593345A JPS593345A JP57111695A JP11169582A JPS593345A JP S593345 A JPS593345 A JP S593345A JP 57111695 A JP57111695 A JP 57111695A JP 11169582 A JP11169582 A JP 11169582A JP S593345 A JPS593345 A JP S593345A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- dissolved oxygen
- porous metal
- interfering components
- interfering
- 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.)
- Pending
Links
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
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
Abstract
Description
【発明の詳細な説明】
本発明は内部に電解液および電極を封入し、酸素透過膜
の背後に多孔質金属陰極を装備した溶存酸素側において
、電解液中の妨害成分を除去する装置に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a device for removing interfering components in the electrolyte on the dissolved oxygen side, which includes an electrolyte and an electrode sealed inside and a porous metal cathode behind an oxygen permeable membrane. It is.
従来、内部に電解液および電極を封入し、酸素透過膜の
背後に多孔質金属陰極を装備した溶存酸素計においては
、多孔質金属陰極背面が電解液に接触するため、電解液
中溶存酸素、イオン等の干渉ケ受は易いという問題があ
った。特に、電解液中の溶存酸素による電流は、試料水
内溶存酸素による電流の５〜１０倍の値となるため、あ
らかじめ測定前に電解液中の溶存酸素濃度を還元によシ
減少させておく必要があシ、この操作に十数時間を要し
、測定の能率が悪かった。また、商温試料水を測定した
場合、−極反応に伴ない、生成する塩の溶解度が上昇し
てイオンを生じ、このイオンによる妨害電流のため、試
料水内溶存酸素濃度が出来ないという問題があった。Conventionally, in dissolved oxygen meters that have an electrolyte and an electrode sealed inside and a porous metal cathode behind an oxygen permeable membrane, the back surface of the porous metal cathode comes into contact with the electrolyte, so dissolved oxygen in the electrolyte, There was a problem in that it was easy to receive interference from ions and the like. In particular, the current due to dissolved oxygen in the electrolyte is 5 to 10 times the value of the current due to dissolved oxygen in the sample water, so the dissolved oxygen concentration in the electrolyte should be reduced by reduction before measurement. Unfortunately, this operation took more than ten hours, and the measurement efficiency was poor. In addition, when measuring sample water at commercial temperature, the solubility of the salt produced increases due to the -polar reaction, producing ions, and the interference current caused by these ions makes it impossible to measure the dissolved oxygen concentration in the sample water. was there.
本発明の目的は、内部に電解液および電極を封入し、酸
素透過膜の背後に多孔質金属陰極を装備した溶存酸素計
において、電解液から多孔質金属陰極表面に拡散し、還
元される妨害成分を除去する装置を提供するにある。The object of the present invention is to solve the problem of interference that is diffused from the electrolyte to the surface of the porous metal cathode and reduced in a dissolved oxygen meter that has an electrolyte and an electrode sealed inside and is equipped with a porous metal cathode behind an oxygen permeable membrane. The present invention provides an apparatus for removing components.
本発明の喘徴は、内部に電解液を刺入し、酸素透過膜の
背後に多孔質金属陰極を装備した溶存酸素計において、
前記、多孔質陰極の背後に、妨害成分を還元し、この妨
害成分が多孔質金属表面に拡散することを防止すること
を目的とした、妨害除去用電極を装備することにある。The wheezing symptoms of the present invention are realized in a dissolved oxygen meter that has an electrolyte inserted inside and is equipped with a porous metal cathode behind an oxygen permeable membrane.
Behind the porous cathode, an interference removal electrode is provided for the purpose of reducing interference components and preventing the interference components from diffusing to the porous metal surface.
以下、本発明の好適な実施例を第１図、第２図に基づき
説明する。第１図は本発明の妨害成分除去用電極を装置
し陰極として多孔質金属を用いた溶存酸素計の概略であ
る。多孔質金属陰極１はＡｕ、Ａｇ、Ｐｉ＠’ｉ用い一
’（Ｈ作すレ、マタ、陽極Ａ４．陽極Ｂ５はＡｇ′ｆｃ
用いて製作される。寛ｙｙｆ液３にはＫＣ１溶液が用い
られる。試料水中の溶存酸素透過膜６を透過して、多孔
質金属陰極１に設けられた孔内に拡散し、孔内表面で下
記反応（１）に従いＯＨ−に還元される。一方、陽極Ｂ
５でＯｘ ＋２ Ｈｔ Ｏ＋ ４ ｅ−→４０Ｈ−”・
（１）は、下記反応（２）に従い、陽極Ｂ５の材質であ
るＭがＡｇＣｔＫ酸化され、この結果、多孔質金属陰極
Ａｇ ＋ Ｃｔ−−＋ Ａｇ Ｃ１＋ ｅ−−−−（２
）１と陽極Ｂ５の間に電流が生じる。この電流は試料水
内溶存酸素濃度に比例するので、この電流を電流計７を
用いて測定することによシ、溶存酸素濃度を定量する。Hereinafter, preferred embodiments of the present invention will be described based on FIGS. 1 and 2. FIG. 1 is a schematic diagram of a dissolved oxygen meter using a porous metal as a cathode and equipped with an electrode for removing interfering components according to the present invention. The porous metal cathode 1 is made of Au, Ag, or Pi@'i'.
It is manufactured using The KC1 solution is used as the Kanyyf solution 3. The dissolved oxygen in the sample water permeates through the membrane 6, diffuses into the pores provided in the porous metal cathode 1, and is reduced to OH- on the inner surface of the pores according to reaction (1) below. On the other hand, anode B
5 Ox +2 Ht O+ 4 e-→40H-”・
In (1), according to the following reaction (2), M, which is the material of the anode B5, is oxidized with AgCtK, and as a result, the porous metal cathode Ag + Ct--+ Ag C1+ e----(2
)1 and anode B5. Since this current is proportional to the dissolved oxygen concentration in the sample water, by measuring this current using the ammeter 7, the dissolved oxygen concentration is quantified.
この多孔質金属陰極を用いた溶存酸素計においては、多
孔質金属陰惨１の背面が、電解液３に接触しているため
、電解液３の中に含まれる溶存酸素、イオン等妨害成分
が多孔質金属陰極１で還元され、妨害電流を生じ、試料
水内溶存酸素濃度測定の妨害となる。特に、高温で測定
する場合、昇温することによシ、陽極で生じるＡｇＣｔ
の溶解度が上昇し、生ずるＡｇ＋の妨害が顕著になる。In this dissolved oxygen meter using a porous metal cathode, since the back side of the porous metal cathode 1 is in contact with the electrolyte 3, interfering components such as dissolved oxygen and ions contained in the electrolyte 3 are absorbed through the porous metal cathode. It is reduced at the solid metal cathode 1 and generates an interfering current, which interferes with the measurement of the dissolved oxygen concentration in the sample water. In particular, when measuring at high temperatures, AgCt generated at the anode due to temperature increase.
The solubility of Ag+ increases and the resulting interference with Ag+ becomes more pronounced.
本発明の妨害成分除去用電極２は、これらを還元し、多
孔質金属陰極ｌにこれらが拡散し、妨害を生ずることを
防ぐ機能を有する。The interfering component removing electrode 2 of the present invention has the function of reducing these and preventing them from diffusing into the porous metal cathode 1 and causing interference.
本発明の妨害成分除去用電極２は％ Ａｕ＋ Ａｇ＊ｐ
ｔ等の導電体に、貫通孔を設け、この貫通孔を通しての
み電解液の連絡が可能である構造を有し、多孔質金属陰
極１の近傍に配置される。この妨害成分除去用電極２と
陽極Ａ４を結線し、妨害成分除去用電極２と陽極Ａ４の
間の電位差を、多孔質金属陰極１と陽極Ｂ５の間の電位
差と同一に保つ。The interfering component removing electrode 2 of the present invention has %Au+Ag*p
A through hole is provided in the conductor such as t, and the electrolyte can communicate with the electrolyte only through the through hole, and is placed near the porous metal cathode 1. This interfering component removing electrode 2 and anode A4 are connected, and the potential difference between the interfering component removing electrode 2 and anode A4 is kept the same as the potential difference between the porous metal cathode 1 and anode B5.
電解液３内の浜存酸素、イオン等妨害成分は、妨害成分
除去用電極２の貫通孔を拡散し、通過する際、還元され
るため、妨害成分が多孔負金属陰極１に到達して還元さ
れ、妨害電流を生ずる事を未然に防止することができる
。この時陽極Ａ４では、反応式（２）に基づく反応が進
行する。この妨害成分除去用′電極２の貫通孔内におけ
る、妨害成分の還元収率は、妨害成分除去用電極２の厚
さと貫通孔半径の比に依存する。この比に対する妨害成
分の還元除去収率の変化を第２図に示す。妨害成分除去
用電極２の厚さと貫通孔半径の比を２以上にすることに
より、貫通孔内還元収率は１．００％となシ、貫通孔内
を拡散し、通過する妨害成分を完全に除去することが可
能となる。貫通孔内還元収率は、妨害成分除去用電極厚
さと貫通孔半径の此のみに依存し、妨害成分の拡散係数
、温度には依存しない。このため、本発明の妨害成分除
去用電極は、妨害成分の種類、Ｓ度に依らず、一般に使
用できる。The interfering components such as oxygen and ions present in the electrolytic solution 3 diffuse through the through holes of the interfering component removal electrode 2 and are reduced when passing through, so the interfering components reach the porous negative metal cathode 1 and are reduced. It is possible to prevent interference current from occurring. At this time, a reaction based on reaction formula (2) proceeds at the anode A4. The reduction yield of the interfering component within the through hole of the interfering component removing electrode 2 depends on the ratio of the thickness of the interfering component removing electrode 2 to the radius of the through hole. FIG. 2 shows the change in the reduction removal yield of interfering components with respect to this ratio. By setting the ratio of the thickness of the interfering component removal electrode 2 to the radius of the through hole to be 2 or more, the reduction yield within the through hole is 1.00%, and the interfering components that diffuse and pass through the through hole are completely removed. It becomes possible to remove it. The reduction yield within the through-hole depends only on the thickness of the electrode for removing interfering components and the radius of the through-hole, and does not depend on the diffusion coefficient of interfering components or the temperature. Therefore, the interfering component removing electrode of the present invention can be used in general, regardless of the type of interfering component or S degree.
以上、本実施例によれば、多孔質金属を陰極として使用
する溶存酸素計において不可避的に生ずる、電解液内の
妨害成分による妨害電流を除去できる効果がある。特に
高温で試料水内溶存酸素濃度を測定する場合には、陽極
で生成するＡｇＣｔの溶解度が増大し、生ずるＡｇ”の
還元による、妨害電流が顕著となり、バックグラウンド
が上昇、変動して測定が出来なくなることを実験により
確認している。これに対し本発明の妨害成分除去用電極
を適用することによりこの妨害電流を除去できることを
実証した。本発明は高温試料水測定には不可欠のものと
考えられる。また、妨害成分除去用電極を用いない溶存
酸素計では、電解液の各社が大きく、測定に先立ちこの
中に含まれる溶存酸素をあらかじめ還元し、妨害電流を
必要なまで減少させるのに、多大の時間を費やしていた
。妨害成分除去用電極を多孔質金属陰極近傍に配置すれ
ば、妨害成分除去用陰極背後の大容量の電解液から多孔
質金属陰極表面に拡散する酸素を除去し、かつ、この二
電極間に含まれる電解液の容量を小さくすることができ
るので多孔質金属陰極背後の電解液中に含まれる溶存酸
素を速やかに還元し、測定を行なうまでに要する時間な
短縮できる効果がある。As described above, according to this embodiment, it is possible to eliminate the interfering current due to interfering components in the electrolytic solution, which inevitably occurs in a dissolved oxygen meter using a porous metal as a cathode. Particularly when measuring the dissolved oxygen concentration in sample water at high temperatures, the solubility of AgCt produced at the anode increases and the reduction of the resulting Ag" causes a noticeable interference current, which increases and fluctuates the background, making the measurement difficult. We have confirmed through experiments that this interference current cannot be removed.In contrast, we have demonstrated that this interference current can be removed by applying the interfering component removal electrode of the present invention.The present invention is indispensable for high-temperature sample water measurements. In addition, in dissolved oxygen meters that do not use an electrode for removing interfering components, various manufacturers of electrolyte solutions are large, and it is necessary to reduce the dissolved oxygen contained in the electrolyte before measurement and reduce the interfering current to the necessary level. If the electrode for removing interfering components is placed near the porous metal cathode, oxygen that diffuses to the surface of the porous metal cathode can be removed from the large volume of electrolyte behind the cathode for removing interfering components. In addition, since the capacity of the electrolyte contained between these two electrodes can be reduced, dissolved oxygen contained in the electrolyte behind the porous metal cathode can be quickly reduced, reducing the time required to perform measurements. There is an effect that can be achieved.
本発明によれば、多孔質金属ヲ除極として使用し、この
多孔質金属背面が電解液と接触している溶存酸素計にお
いて、’ａｍ液から多孔質金属に拡散する、！解液内溶
存酸素、イオン等、妨害成分を除去できるので、これら
の成分の還元電流が原因である、溶存酸素計出力電流の
バックグラウンドの増大、変動などを除き、出力電流の
安定化。According to the present invention, in a dissolved oxygen meter in which a porous metal is used as a depolarizer and the back surface of the porous metal is in contact with an electrolyte, diffusion from the am liquid into the porous metal. Since interfering components such as dissolved oxygen and ions in the solution can be removed, the output current can be stabilized by eliminating background increases and fluctuations in the dissolved oxygen meter output current caused by the reduction current of these components.
検出感度の向上をはかることが可能である。特に、？ｔ
％ 濡試料水測定時、陽極で生成するｈｇｃ：ｔの溶解
度が増大することにより生ずるＡｇ”の還元が原因とな
る妨害電流を除去することが出来るので、高温試料水測
定には不可欠である。また、妨害成分除去用電極を多孔
質金属陰極の近傍に配置することによシ、妨害成分除去
用電極背後の大容量の電解液から、多孔質金属陰極背面
に拡散する電解液中溶存酸素を除去しつつ、多孔質金属
陰極背面と妨害成分除去用電極の間の小容量の電解液中
の溶存酸素を速やかに還元して、多孔質金属陰極背後の
酸素を除去することができるので、電Ｍｔ封人後測定開
始までに要する時間を大幅に短縮できる効果がある。It is possible to improve detection sensitivity. especially,? t
% When measuring wet sample water, it is possible to remove the interfering current caused by the reduction of Ag'' caused by the increased solubility of hgc:t produced at the anode, so it is essential for measuring high temperature sample water. In addition, by placing the interfering component removal electrode near the porous metal cathode, dissolved oxygen in the electrolyte that diffuses to the back surface of the porous metal cathode can be removed from the large volume of electrolyte behind the interfering component removal electrode. While removing oxygen, dissolved oxygen in a small volume of electrolyte between the back surface of the porous metal cathode and the interfering component removal electrode can be quickly reduced, and the oxygen behind the porous metal cathode can be removed. This has the effect of significantly shortening the time required to start measurement after Mt closure.
第１図は本＠明の基本を示す断面概略図、第２図は妨害
成分除去用電極の厚さと貫通孔中径の変化に伴う妨害成
分除去用電極貫通孔内における還元収率の変化を示した
図である。Figure 1 is a cross-sectional schematic diagram showing the basics of this @Ming. Figure 2 shows the change in reduction yield within the through-hole of the electrode for removing interfering components due to changes in the thickness of the interfering component-removing electrode and the diameter of the through-hole. FIG.
Claims (1)
後に多孔質金属陰極を装備した溶存酸素計において、前
記、多孔質陰極の背後に、多孔質金属陰極の電位より正
の電位で還元される電解液中の成分（以下、妨害成分と
記す）を還元し、前記妨害成分が多孔質金属陰榛表面に
拡散するのを防止するため、妨害成分除去用電極を多孔
質金属陰極の背後に設けることを特徴とする妨害成分除
去用電極を装備した溶存酸素計。 ２、特許請求の範囲第１項において、導電体に小孔を複
数個員き、この孔内部で妨害成分を還元することを％徴
とする妨害成分除去用電極を装備しｆｃ溶存酸素針。 ３、特許請求の範囲第２項において、導電体の板厚と小
孔の半径の比を２以上にとることを特徴とする妨害成分
除去用電極を装備した溶存酸素計。[Claims] 1. In a dissolved oxygen meter that includes an electrolyte and an electrode sealed inside and is equipped with a porous metal cathode behind an oxygen permeable membrane, a porous metal cathode is provided behind the porous cathode. In order to reduce components in the electrolytic solution that are reduced at a more positive potential (hereinafter referred to as interfering components) and to prevent the interfering components from diffusing onto the surface of the porous metal shade, an electrode for removing interfering components is used. Dissolved oxygen meter equipped with an electrode for removing interfering components, which is characterized by being provided behind a porous metal cathode. 2. An FC dissolved oxygen needle according to claim 1, which is equipped with an electrode for removing interfering components, the conductor having a plurality of small holes and reducing the interfering components inside the holes. 3. A dissolved oxygen meter equipped with an electrode for removing interfering components, characterized in that the ratio of the thickness of the conductor to the radius of the small hole is 2 or more, as set forth in claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57111695A JPS593345A (en) | 1982-06-30 | 1982-06-30 | Dissolved oxygen meter equipped with electrode for removing interfering component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57111695A JPS593345A (en) | 1982-06-30 | 1982-06-30 | Dissolved oxygen meter equipped with electrode for removing interfering component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS593345A true JPS593345A (en) | 1984-01-10 |
Family
ID=14567816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57111695A Pending JPS593345A (en) | 1982-06-30 | 1982-06-30 | Dissolved oxygen meter equipped with electrode for removing interfering component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS593345A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0212126A2 (en) * | 1985-06-18 | 1987-03-04 | Radiometer A/S | Polarographic measuring electrode device |
| JPS63256833A (en) * | 1987-03-31 | 1988-10-24 | ライボルト・アクチエンゲゼルシヤフト | Method and device for inspecting leakage of system filled with steam or liquid or both steam and liquid |
| JPH04215897A (en) * | 1990-12-17 | 1992-08-06 | Tokyo Electric Power Co Inc:The | Method for controlling operation of anaerobic treatment tank |
| US5186798A (en) * | 1987-12-11 | 1993-02-16 | Hitachi, Ltd. | Solution quantitative analysis apparatus, quantitative analysis methods, and nuclear reactor water quality control system |
| JPH07125768A (en) * | 1993-10-25 | 1995-05-16 | Kureha Chem Ind Co Ltd | Package for moisture-curing caulking agent and packing device for moisture-curing caulking agent |
| AU697214B2 (en) * | 1994-04-14 | 1998-10-01 | Lifescan, Inc. | Electrochemical cells |
| FR2764985A1 (en) * | 1997-06-21 | 1998-12-24 | Draegerwerk Ag | ELECTROCHEMICAL OXYGEN DETECTOR |
| US6193865B1 (en) | 1997-09-11 | 2001-02-27 | Usf Filtration And Separations Group, Inc. | Analytic cell |
| US6284125B1 (en) | 1995-06-19 | 2001-09-04 | Usf Filtration And Separations Group, Inc. | Electrochemical cell |
| EP1494022A2 (en) * | 1993-04-09 | 2005-01-05 | Novartis AG | Extended use planar sensors |
| US7664607B2 (en) | 2005-10-04 | 2010-02-16 | Teledyne Technologies Incorporated | Pre-calibrated gas sensor |
| USRE42567E1 (en) | 1995-11-16 | 2011-07-26 | Lifescan, Inc. | Electrochemical cell |
| USRE44330E1 (en) | 1995-06-19 | 2013-07-02 | Lifescan Inc. | Electrochemical cell |
| JP2015501185A (en) * | 2011-10-28 | 2015-01-15 | コーニンクレッカ フィリップス エヌ ヴェ | Fluid soluble gas sensor |
| WO2021039392A1 (en) * | 2019-08-28 | 2021-03-04 | 株式会社堀場アドバンスドテクノ | Peracetic acid concentration meter |
-
1982
- 1982-06-30 JP JP57111695A patent/JPS593345A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0212126A2 (en) * | 1985-06-18 | 1987-03-04 | Radiometer A/S | Polarographic measuring electrode device |
| US4874501A (en) * | 1985-06-18 | 1989-10-17 | Radiometer A/S | Membrane for an electrochemical measuring electrode device |
| JPS63256833A (en) * | 1987-03-31 | 1988-10-24 | ライボルト・アクチエンゲゼルシヤフト | Method and device for inspecting leakage of system filled with steam or liquid or both steam and liquid |
| US5186798A (en) * | 1987-12-11 | 1993-02-16 | Hitachi, Ltd. | Solution quantitative analysis apparatus, quantitative analysis methods, and nuclear reactor water quality control system |
| JPH04215897A (en) * | 1990-12-17 | 1992-08-06 | Tokyo Electric Power Co Inc:The | Method for controlling operation of anaerobic treatment tank |
| EP1494022A3 (en) * | 1993-04-09 | 2009-09-02 | Novartis AG | Extended use planar sensors |
| EP1494022A2 (en) * | 1993-04-09 | 2005-01-05 | Novartis AG | Extended use planar sensors |
| JPH07125768A (en) * | 1993-10-25 | 1995-05-16 | Kureha Chem Ind Co Ltd | Package for moisture-curing caulking agent and packing device for moisture-curing caulking agent |
| AU697214B2 (en) * | 1994-04-14 | 1998-10-01 | Lifescan, Inc. | Electrochemical cells |
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