JP3188772B2 - Coulometric detector - Google Patents
Coulometric detectorInfo
- Publication number
- JP3188772B2 JP3188772B2 JP27992792A JP27992792A JP3188772B2 JP 3188772 B2 JP3188772 B2 JP 3188772B2 JP 27992792 A JP27992792 A JP 27992792A JP 27992792 A JP27992792 A JP 27992792A JP 3188772 B2 JP3188772 B2 JP 3188772B2
- Authority
- JP
- Japan
- Prior art keywords
- sample
- tube
- electrode chamber
- working electrode
- detector
- 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 - Fee Related
Links
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明はクーロメトリー検出器に
関し、さらに詳しくは流動性試料中の被定量物質を定電
位電量分析法により絶対定量することができる、自然環
境用、汚染監視用、生産ライン監視用の連続計測に適し
たクーロメトリー検出器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coulometric detector, and more particularly to a natural environment, contamination monitoring, and production line capable of absolutely quantifying a substance to be determined in a fluid sample by potentiostatic coulometry. The present invention relates to a coulometric detector suitable for continuous measurement for monitoring.
【0002】[0002]
【従来の技術】近年、電解槽で被定量物質を電解したと
きの電気的な変化量を測定し、被定量物質を迅速かつ高
精度に定量する方法が提案されており、その一つの方法
として、作用極室内の導電性多孔質体からなる電極に電
解液を含浸させ、この作用極室と隔膜を介して設けられ
た試料室から試料中の被定量物質を作用極室内に拡散せ
しめ、電解、定量する方法が挙げられる(特開平3−1
81850号公報)。この方法によれば、気体または液
体試料中の被定量物質を短時間でかつ高精度に定量する
ことができる。しかし、試料室に供給される試料の流れ
が不均一となりやすく、また電極室での被定量物質の拡
散方向が一方向であることから拡散効率が悪く、そのた
めに応答性が充分でなく、また試料室の設置が必要であ
り、検出器のコンパクトが図りにくく、さらに試料室、
作用極室および対極室の3室積層型検出器となるため、
構成が複雑化し、電解液の流入構造や漏液対策等に特別
の考慮が必要であり、取扱性に劣るものであった。2. Description of the Related Art In recent years, there has been proposed a method of measuring an electric change amount when a substance to be determined is electrolyzed in an electrolytic cell and quantifying the substance to be determined quickly and with high accuracy. Electrolyte is impregnated into the electrode made of a conductive porous body in the working electrode chamber, and a substance to be determined in the sample is diffused into the working electrode chamber from the working electrode chamber and a sample chamber provided through a diaphragm. And a method for quantification (JP-A-3-13-1).
No. 81850). According to this method, the substance to be determined in the gas or liquid sample can be quantified in a short time and with high accuracy. However, the flow of the sample supplied to the sample chamber is likely to be non-uniform, and the diffusion efficiency of the substance to be determined in the electrode chamber is unidirectional, so that the diffusion efficiency is poor, and therefore the response is not sufficient. It is necessary to set up a sample chamber, and it is difficult to make the detector compact.
Since it is a three-chamber stacked detector of the working electrode chamber and the counter electrode chamber,
The configuration is complicated, and special considerations are required for the inflow structure of the electrolyte and measures against liquid leakage, and the handling is inferior.
【0003】[0003]
【発明が解決しようとする課題】本発明の目的は、前記
従来技術の問題を解決し、流動性試料中の被定量物質の
透過、拡散性に優れ、応答性が高く、かつ構造が簡単で
取扱いの容易な試料流通型クーロメトリー検出器を提供
することにある。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the prior art, and to provide excellent permeation and diffusion of a substance to be determined in a fluid sample, high responsiveness, and a simple structure. An object of the present invention is to provide a sample flow type coulometric detector which is easy to handle.
【0004】[0004]
【課題を解決するための手段】本発明は、電解液が含浸
された多孔質電極を有する作用極室と対極室が隔膜を挟
んで対向配置されたクーロメトリー検出器において、前
記作用極室内にイオン交換膜、半透膜および微多孔膜の
少なくとも1種からなるチューブを装填し、該チューブ
内に流動性試料を通過させて該試料中の被定量物質を前
記作用極室内に透過、拡散させるようにしたことを特徴
とするクーロメトリー検出器に関する。According to the present invention, there is provided a coulometric detector in which a working electrode chamber having a porous electrode impregnated with an electrolyte and a counter electrode chamber are opposed to each other with a diaphragm interposed therebetween. A tube composed of at least one of an exchange membrane, a semipermeable membrane, and a microporous membrane is loaded, and a fluid sample is passed through the tube to detect a substance to be determined in the sample.
The present invention relates to a coulometric detector characterized by being transmitted and diffused into a working electrode chamber .
【0005】本発明に用いられるチューブとしては、例
えば、デュポン社製商品名ナフィオン117チューブ等
のイオン交換膜チューブ、セルロース膜等の半透膜チュ
ーブ、ポリエチレン、ポリプロピレン、テフロン製等の
微多孔膜チューブ、多孔性セラミック膜等の微多孔膜チ
ューブなどが挙げられる。これらは被定量物質の種類に
応じて適宜選定され、またこれらのチューブを併用する
こともできる。Examples of the tube used in the present invention include ion-exchange membrane tubes such as Nafion 117 tube (trade name, manufactured by DuPont), semipermeable membrane tubes such as cellulose membrane, and microporous membrane tubes made of polyethylene, polypropylene, Teflon, etc. And a microporous membrane tube such as a porous ceramic membrane. These are appropriately selected according to the type of the substance to be determined, and these tubes may be used in combination.
【0006】チューブの断面形状には特に限定されない
が、被定量物質の拡散性、絶対定量性および流通性(流
動抵抗)などの点から、チューブの内径は0.2mm〜3
mmの範囲が好ましく、また作用極室内に装填されるチュ
ーブの長さは、チューブ径等にもよるが10mm〜500
mmの範囲が好ましい。[0006] The cross-sectional shape of the tube is not particularly limited.
The length of the tube loaded in the working electrode chamber is preferably 10 mm to 500 mm, depending on the tube diameter and the like.
A range of mm is preferred.
【0007】本発明において、作用極または対極には、
導電性繊維の集合体であるクロスやフェルトなど、具体
的にはカーボンクロスやカーボンフェルトなどが用いら
れる。また電解液には、支持電解質または支持電解質と
反応試薬を含む水溶液または非水系溶液が用いられる。
非水系溶液を用いた場合には100℃以上の高温試料の
測定に対応することができる。隔膜としては、ポリスチ
レンスルホン酸膜やイオン交換膜などが用いられる。In the present invention, the working electrode or the counter electrode includes:
A cloth or a felt, which is an aggregate of conductive fibers, specifically, a carbon cloth or a carbon felt is used. As the electrolytic solution, an aqueous solution or a non-aqueous solution containing a supporting electrolyte or a supporting electrolyte and a reaction reagent is used.
When a non-aqueous solution is used, it can be used to measure a high-temperature sample of 100 ° C. or higher. As the diaphragm, a polystyrene sulfonic acid membrane, an ion exchange membrane, or the like is used.
【0008】図1は、本発明の一実施例におけるクーロ
メトリー検出器の説明図である。図において、クーロメ
トリー検出器1には、隔膜5を介して作用極室3と対極
室4が対向配置されている。作用極室3には電解液が含
浸されたカーボンクロス等からなる多孔質電極が充填さ
れ、試料透過チューブ2が装填されている。該試料透過
チューブ2の両端は集電板10を連通してそれぞれ試料
供給口6と試料流出口7に接続する。一方、多孔質電極
を有する対極室4には対極液が対極液供給口8から供給
され、対極流出口7から系外に排出される。FIG. 1 is an explanatory diagram of a coulometric detector according to one embodiment of the present invention. In the figure, a working electrode chamber 3 and a counter electrode chamber 4 are opposed to each other on a coulometric detector 1 with a diaphragm 5 interposed therebetween. The working electrode chamber 3 is filled with a porous electrode made of a carbon cloth or the like impregnated with an electrolytic solution, and the sample transmission tube 2 is loaded therein. Both ends of the sample transmission tube 2 are connected to a sample supply port 6 and a sample outlet 7 through a current collector 10. On the other hand, a counter electrode solution is supplied to a counter electrode chamber 4 having a porous electrode from a counter electrode liquid supply port 8 and discharged from the counter electrode outlet 7 to the outside of the system.
【0009】このようなクーロメトリー検出器におい
て、流動性試料は、試料供給口6から一定流量で連続的
に試料透過チューブ2に導入されて該チューブ2内を通
過して試料流出口7から系外に排出される。試料が試料
透過チューブ2を通過する間に該試料中の被定量物質が
チューブの全周囲から作用極室3内に透過、拡散し、電
気分解を受ける。チューブ内を通過する間に全被定量物
質が透過できるため、絶対定量が可能である。また作用
極室に被定量物質のみが供給されるため、電解に際して
は試料に含まれる他の成分の影響を受けることがなく、
測定精度が向上する。[0009] In such a coulometric detector, flowable sample is introduced from the sample-supplying port 6 to continuously transmit a specimen tube 2 at a constant flow rate out of the system from the sample flow outlet 7 through the inside the tube 2 Is discharged. While the sample passes through the sample permeation tube 2, the substance to be determined in the sample permeates and diffuses from the entire periphery of the tube into the working electrode chamber 3, and undergoes electrolysis. Absolute quantification is possible because all substances to be quantified can pass through the tube. Also, since only the substance to be determined is supplied to the working electrode chamber, the electrolysis is not affected by other components contained in the sample,
Measurement accuracy is improved.
【0010】[0010]
【実施例】以下、本発明を実施例により詳しく説明す
る。 実施例1〜5 図1に示すクーロメトリー検出器の構成を〔カーボンク
ロス対極(対極液含浸)/隔膜/カーボンクロス作用極
(作用極液含浸)/試料透過チューブ〕とし、水道水
中の残留塩素の定量、水中の溶性COD成分の定量、
メタノール中の水分の定量、燃焼排ガス中のSO2
の定量、ガス中のオゾンの定量を行い、その結果を表
1に示した。なお、各試料の測定に際し、使用した対極
液、隔膜、作用極液および試料透過チューブ材質は表1
に示した通りであり、作用極室に装填したチューブの長
さは150mmであった。表1から、本発明の検出器によ
れば、高精度の絶対定量を容易に行うことができること
がわかる。The present invention will be described below in more detail with reference to examples. Examples 1 to 5 The configuration of the coulometric detector shown in FIG. Determination, determination of soluble COD components in water,
Determination of water in methanol, SO 2 in flue gas
And the ozone in the gas were determined. The results are shown in Table 1. In the measurement of each sample, the materials of the counter electrode solution, the diaphragm, the working electrode solution, and the sample permeation tube are shown in Table 1.
The length of the tube loaded in the working electrode chamber was 150 mm. Table 1 shows that the detector of the present invention can easily perform high-precision absolute quantification.
【0011】[0011]
【表1】 [Table 1]
【0012】*1:ヨウ素滴定法により測定した値と一
致した。 *2:水を加熱蒸発させて測定したCOD含量は11p
pmであった。 *3:カールフィッシャー法により測定した値と一致し
た。 *4:NDIR法(非分散赤外線法)により測定した値
と一致した。 *5:吸収、ヨウ素滴定法により測定した値と一致し
た。* 1: It was consistent with the value measured by the iodine titration method. * 2: COD content measured by heating and evaporating water is 11p
pm. * 3: The value was consistent with the value measured by the Karl Fischer method. * 4: In agreement with the value measured by the NDIR method (non-dispersive infrared method). * 5: It was consistent with the values measured by absorption and iodine titration.
【0013】[0013]
【発明の効果】本発明のクーロメトリー検出器によれ
ば、作用極室内にイオン交換膜等からなるチューブを装
填して試料を通過させることにより、試料中の被定量物
質のみを効率よく作用極室内に透過、拡散させることが
できるため、以下の効果が得られる。 (1) 連続した絶対定量が可能であり、従って、標準試料
等は一切不要となる。 (2) 被定量物質の拡散効率に優れるため、応答性に優
れ、ほぼリアルタイムのオンライン計測が可能となる。 (3) チューブ材質および電解液の選択により、各種試料
(ガス、水溶液、非水液、スラリー)に含まれる被定量
物質の測定が可能となる。 (4) メンテナンスが容易で、また長期にわたるメンテナ
ンスフリーの検出器を提供することができる。 (5) 検出器の構成が簡単であり、低コスト化が図れる。According to the coulometric detector of the present invention, a tube made of an ion-exchange membrane or the like is loaded into the working electrode chamber and the sample is allowed to pass through, so that only the substance to be determined in the sample can be efficiently used in the working electrode chamber. Can be transmitted and diffused, so that the following effects can be obtained. (1) Continuous absolute quantification is possible, and therefore no standard sample is required. (2) Since the diffusion efficiency of the analyte is excellent, the response is excellent and almost real-time online measurement is possible. (3) By selecting the tube material and the electrolytic solution, it becomes possible to measure the substances to be determined contained in various samples (gas, aqueous solution, non-aqueous liquid, slurry). (4) It is possible to provide a detector that is easy to maintain and maintenance-free for a long time. (5) The structure of the detector is simple, and the cost can be reduced.
【図面の簡単な説明】[Brief description of the drawings]
【図1】本発明の一実施例によるクーロメトリー検出器
の説明図。FIG. 1 is an explanatory diagram of a coulometric detector according to one embodiment of the present invention.
1…クーロメトリー検出器、2…試料透過チューブ、3
…作用極室、4…対極室、5…隔膜、6…試料供給口、
7…試料流出口、8…対極液供給口、9…対極液流出
口。1: Coulometric detector, 2: Sample transmission tube, 3
... working electrode room, 4 ... counter electrode room, 5 ... diaphragm, 6 ... sample supply port,
7: sample outlet, 8: counter electrode supply port, 9: counter electrode outlet.
Claims (1)
作用極室と対極室が隔膜を挟んで対向配置されたクーロ
メトリー検出器において、前記作用極室内にイオン交換
膜、半透膜および微多孔膜の少なくとも1種からなるチ
ューブを装填し、該チューブ内に流動性試料を通過させ
て該試料中の被定量物質を前記作用極室内に透過、拡散
させるようにしたことを特徴とするクーロメトリー検出
器。1. A coulometric detector in which a working electrode chamber having a porous electrode impregnated with an electrolyte and a counter electrode chamber are opposed to each other with a diaphragm interposed therebetween. A tube comprising at least one porous membrane is loaded, and a fluid sample is passed through the tube.
The substance to be determined in the sample into the working electrode chamber
Coulometry detector, characterized in that the causes manner.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27992792A JP3188772B2 (en) | 1992-10-19 | 1992-10-19 | Coulometric detector |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27992792A JP3188772B2 (en) | 1992-10-19 | 1992-10-19 | Coulometric detector |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06130032A JPH06130032A (en) | 1994-05-13 |
JP3188772B2 true JP3188772B2 (en) | 2001-07-16 |
Family
ID=17617853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27992792A Expired - Fee Related JP3188772B2 (en) | 1992-10-19 | 1992-10-19 | Coulometric detector |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3188772B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE227844T1 (en) | 1997-02-06 | 2002-11-15 | Therasense Inc | SMALL VOLUME SENSOR FOR IN-VITRO DETERMINATION |
US6338790B1 (en) | 1998-10-08 | 2002-01-15 | Therasense, Inc. | Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator |
-
1992
- 1992-10-19 JP JP27992792A patent/JP3188772B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH06130032A (en) | 1994-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3367850A (en) | Method and apparatus for determining moisture content of hydrocarbon fluids | |
US4844097A (en) | Apparatus and method for testing liquids | |
Alber et al. | Solid‐state amperometric sensors for gas phase analytes: A review of recent advances | |
CN213875514U (en) | Measuring device for membrane ion migration number | |
JP3188772B2 (en) | Coulometric detector | |
US4460448A (en) | Calibration unit for gases | |
CN102072930A (en) | Flow injection serially connected microelectrode electrochemical automatic method and device for simultaneous measurement of various electrolytes in blood sample | |
US5238853A (en) | Process and apparatus for the electrochemical determination of oxygen in a blood gas analyzer | |
EP0215446A2 (en) | Device and method for measuring ion activity | |
CN102103088A (en) | Device and method for measuring water quality chemical oxygen demand by ozone method for acquiring total light intensity | |
JP2003075394A (en) | Detector for oxidizing-gas | |
JPH08145944A (en) | Electrical analyzing method for cod and cod measuring device | |
JPH07113605B2 (en) | Gas analyzer | |
CN219285089U (en) | Reference electrode system of solid-liquid layering pH sensor | |
US3413209A (en) | Currentimetric sensor | |
Scarano et al. | High sensitivity carbon dioxide analyzer | |
Nozoye | Exponential dilution flask | |
JP2752201B2 (en) | Electrical analysis method | |
JP2764986B2 (en) | Nitrite determination device | |
Riesel et al. | A modified zimm‐myerson‐type osmometer | |
JPH0583862B2 (en) | ||
Heineman et al. | International Symposium on Electroanalysis and Sensors in Biomedical, Environmental and Industrial Sciences | |
JPH01191035A (en) | Method for measuring concentration of dissolved oxygen in liquid | |
JPH08262005A (en) | Method and apparatus for determination of ammonia in solution | |
JPS5811021B2 (en) | ozone electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20010410 |
|
LAPS | Cancellation because of no payment of annual fees |