JPH0781980B2 - Ion-selective modified electrode - Google Patents
Ion-selective modified electrodeInfo
- Publication number
- JPH0781980B2 JPH0781980B2 JP1143375A JP14337589A JPH0781980B2 JP H0781980 B2 JPH0781980 B2 JP H0781980B2 JP 1143375 A JP1143375 A JP 1143375A JP 14337589 A JP14337589 A JP 14337589A JP H0781980 B2 JPH0781980 B2 JP H0781980B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ion
- solution
- selective
- modified electrode
- 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
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】 ［技術分野］ 本発明は、イオン選択性を有する新型の電極に関するも
のである。TECHNICAL FIELD The present invention relates to a new type of electrode having ion selectivity.
［従来技術］ 従来、イオン選択性電極はpH応答ガラス電極に代表され
るように、イオン感応膜を介して内部液と呼ばれるイオ
ン活量一定の溶液と被測定溶液とを対置させ、感応膜の
両側に発生する電位差を検出することにより、被測定溶
液中のイオン濃度を知るという原理に基づいていた。こ
の原理を応用し、特定のイオンと錯形成能力を有する化
合物を高分子膜等に含浸させた可塑剤（溶媒）中に含ま
せ、極めて高いイオン選択性を持たせたものがいわゆる
液膜型イオン選択性電極である。これとは別に難溶性固
体物質を直接電極とし、イオン選択性電極を構成してい
るものもあるが、難溶性塩の種類が限られ、測定可能な
イオンの種類もあまり多くない。[Prior Art] Conventionally, an ion-selective electrode is typified by a pH-responsive glass electrode, and a solution having a constant ion activity called an internal solution and a solution to be measured are opposed to each other through an ion-sensitive membrane to form a sensitive membrane. It was based on the principle of knowing the ion concentration in the solution to be measured by detecting the potential difference generated on both sides. Applying this principle, a compound having a specific ion-complexing ability is contained in a plasticizer (solvent) that is impregnated in a polymer membrane to give extremely high ion selectivity. It is an ion-selective electrode. In addition to this, there is also one in which a sparingly soluble solid substance is directly used as an electrode to form an ion selective electrode, but the kinds of sparingly soluble salts are limited and the kinds of measurable ions are not very large.
液膜型イオン選択性電極は、目的イオンに対し高い選択
性を有する錯形成物質を合成し、感応剤として用いうる
という優れた特徴を有しているが、内部参照電極／内部
液／イオン感応膜／被測定液という構成が不可欠なた
め、近年要望されている電極の微少化を図ることは物理
的に困難であった。これに代わる方法として、イオン感
応膜の成分を白金や銀線などの固体電極上に直接塗布す
る方法で構成する、いわゆる被覆線型イオン選択性電極
が提唱されている。しかしこの方法は電極作成に熟練を
要し、しかも応答速度やドリフトに対する安定性などの
性能において、液膜型イオン選択性電極に著しく劣ると
いう問題があった。The liquid membrane type ion-selective electrode has an excellent feature that it can be used as a sensitizer by synthesizing a complex-forming substance having high selectivity to target ions. It is physically difficult to miniaturize the electrodes that have been demanded in recent years, because the structure of membrane / solution to be measured is indispensable. As an alternative method, a so-called coated wire type ion-selective electrode has been proposed, which is configured by directly coating the components of the ion-sensitive film on a solid electrode such as platinum or silver wire. However, this method has a problem that it requires skill in electrode preparation and is significantly inferior to the liquid membrane type ion-selective electrode in performance such as response speed and stability against drift.
「目 的」 本発明は応答速度に優れると共にその構造が複雑ではな
く、微小化に適したイオン選択性修飾電極を提供するこ
とを目的とする。"Objective" The present invention has an object to provide an ion-selective modified electrode which is excellent in response speed and has a complicated structure, and which is suitable for miniaturization.
本発明によれば、固体電極表面上に、イオン感応剤と電
解重合法により重合可能な物質とからなる混合物を電解
重合させて得られる、イオン感応剤を含む高分子膜が被
覆されていることを特徴とするイオン選択性修飾電極が
提供される。According to the present invention, the solid electrode surface is coated with a polymer film containing an ion-sensitive agent, which is obtained by electrolytically polymerizing a mixture of the ion-sensitive agent and a substance polymerizable by an electrolytic polymerization method. An ion-selective modified electrode is provided.
本発明では、目的イオンと錯形成能力を有するイオン感
応物質をピロール又はその誘導体、チオフェン又はその
誘導体、ビニルピリジン又はその誘導体など、電解重合
法により重合可能な物質とともにアセトニトリル、ベン
ゾニトリル、ニトロベンゼン、二塩化メタン、ジメチル
スルホキシド、エタノール、アセトン、水などの溶媒、
あるいはそれらの混合溶媒中に溶解させ、pH調節を行っ
た後、白金、金、グラファイト、タンタル等不溶解性の
固体電極をこの溶液中に浸せきさせ、電気化学的にアノ
ード又はカソード電解重合を行わせることにより、重合
皮膜中にイオン感応物質を取り込ませ、イオン選択性電
極を構成する。In the present invention, an ion-sensitive substance capable of forming a complex with a target ion is combined with a substance that can be polymerized by an electrolytic polymerization method such as pyrrole or a derivative thereof, thiophene or a derivative thereof, vinylpyridine or a derivative thereof, and acetonitrile, benzonitrile, nitrobenzene, or dinitrobenzene. Solvents such as methane chloride, dimethyl sulfoxide, ethanol, acetone, water,
Alternatively, after dissolving in a mixed solvent thereof and adjusting the pH, an insoluble solid electrode such as platinum, gold, graphite, and tantalum is immersed in this solution, and anodic or cathodic electrolytic polymerization is performed electrochemically. By doing so, the ion-sensitive substance is incorporated into the polymerized film to form an ion-selective electrode.
この際、イオン感応物質のイオン荷電、疎水性、分子の
大きさ等に応じて重合物質やそれらを溶解させる溶媒の
種類、電解重合条件等を選択することによって、最適の
イオン選択性修飾電極が構成される。At this time, the optimum ion-selective modified electrode can be obtained by selecting the type of the polymeric substance and the solvent for dissolving them, the electrolytic polymerization conditions, etc. according to the ionic charge, hydrophobicity, molecular size, etc. of the ion-sensitive substance. Composed.
本発明において用いる電解重合溶液の添加成分を割合及
び電解重合条件は、イオン感応物質0.001〜1mole/dm3、
重合物質0.01〜1mole/dm3、電解重合時電流密度１×10
-6〜１×10-1A/cm2等である。The ratio and the electropolymerization conditions of the additive components of the electropolymerization solution used in the present invention are ion-sensitive substances 0.001 to 1 mole / dm 3 ,
Polymerization substance 0.01-1mole / dm 3 , current density during electropolymerization 1 × 10
-6 to 1 × 10 -1 A / cm 2 etc.
次に、図面（第１図）により、本発明の修飾電極をイオ
ン選択性電極として用い、被測定溶液中のイオン活量を
測定する場合の具体例を示す。１は修飾電極を作成する
ための適当な固体電極であり、電極の微小化のためには
線状のものが望ましい。２はこの固体電極上に電解重合
法により形成された重合被膜であり、重合反応中に取り
込まれたイオン感応物質を含む。３は参照電極、４は電
位差計であり、被測定溶液Ａ中に含まれる目的イオンの
活量に応じて、修飾電極１と参照電極３との間に電位差
が発生することを利用し、予め作成した検量値を用い
て、この電位差からイオンの活量を換算することができ
る。Next, with reference to the drawing (FIG. 1), a specific example of the case where the modified electrode of the present invention is used as an ion-selective electrode to measure the ion activity in a solution to be measured is shown. Reference numeral 1 is an appropriate solid electrode for forming a modified electrode, and a linear electrode is desirable for miniaturization of the electrode. Reference numeral 2 denotes a polymerized film formed on the solid electrode by an electrolytic polymerization method, and contains an ion-sensitive substance incorporated during the polymerization reaction. Reference numeral 3 is a reference electrode, and 4 is a potentiometer, which utilizes the fact that a potential difference is generated between the modified electrode 1 and the reference electrode 3 depending on the activity of the target ions contained in the solution A to be measured. Using the prepared calibration value, the ion activity can be converted from this potential difference.
本発明のイオン選択性修飾電極は前記構成からなり、複
雑な層構成を採ることがないコンパクトなものであるか
ら、微小化に好適なものであり、しかもイオン応答速度
やドリフトに対する安定性の諸性能においても優れたも
のである。Since the ion-selective modified electrode of the present invention has the above-mentioned structure and is compact without adopting a complicated layer structure, it is suitable for miniaturization and has various stability with respect to ion response speed and drift. It is also excellent in performance.
［実施例］ 次に、本発明を実施例によりさらに詳細な説明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
実施例 Ｉ （１）修飾電極の調整 0.01mole/dm31,3,6−ナフタレントリスルホン酸ナトリ
ウム、0.10mole/dm3ピロールの溶液を水１容対アセトニ
トリル９容の混合溶媒を用いて作成し、過塩素酸により
pHを１〜２とした後、窒素ガスをこの溶液中に導入して
溶存酸素を除去した。室温においてこの溶液中に表面積
0.5cm2の白金板電極を浸せきし、２×10-4A/cm2の電流
密度で0.72クーロン/cm2の電気量だけアノード電解重合
反応を行わせた（電極Ｉ−ａ）。なお、対極には白金網
を用いた。Example I (1) Preparation of Modified Electrode 0.01mole / dm 3 Sodium 1,3,6-naphthalenetrisulfonate and 0.10mole / dm 3 Pyrrole solution was prepared using a mixed solvent of 1 volume of water and 9 volumes of acetonitrile. With perchloric acid
After adjusting the pH to 1-2, nitrogen gas was introduced into this solution to remove dissolved oxygen. Surface area in this solution at room temperature
A platinum plate electrode of 0.5 cm 2 was dipped, and an anodic electropolymerization reaction was carried out with an electric quantity of 0.72 coulomb / cm 2 at a current density of 2 × 10 −4 A / cm 2 (electrode Ia). A platinum mesh was used for the counter electrode.
比較のため、1,3,6−ナフタレントリスルホン酸ナトリ
ウムの代わりに、イオン感応性を示さないテトラエチル
アンモニウムテトラフルオロボレートを0.01mole/dm3含
む以外は、（１）と同様な条件で電解重合を行わせるこ
とにより電極Ｉ−ｂを、さらに電解重合反応の行わない
白金電極（電極Ｉ−ｃ）を調整した。For comparison, electrolytic polymerization was conducted under the same conditions as in (1) except that sodium 1,3,6-naphthalene trisulfonate was replaced by 0.01 mole / dm 3 of tetraethylammonium tetrafluoroborate, which does not show ion sensitivity. The electrode I-b was further adjusted by performing the above step, and the platinum electrode (electrode I-c) in which the electrolytic polymerization reaction was not performed was adjusted.
（２）陽イオンを含む試料溶液に対する応答起電力の測
定 25℃の条件で、次の一連の試料溶液中における電極Ｉ−
ａ、Ｉ−ｂ、Ｉ−ｃの銀−塩化銀参照電極に対する発生
起電力を測定し、検量線を作成した。(2) Measurement of response electromotive force for sample solution containing cations Electrode I- in the following series of sample solutions under the condition of 25 ° C.
The electromotive force generated with respect to the silver-silver chloride reference electrode of a, Ib, and Ic was measured, and the calibration curve was created.
LiCl 1×10-5〜1 規定 NaCl 1×10-5〜1 規定 KCl 1×10-5〜1 規定 MgCl2 2×10-6〜２×10-1 規定 CaCl2 2×10-6〜２×10-1 規定 HCl 1×10-6〜１×10-1 規定 （３）測定結果 電極Ｉ−ａ、Ｉ−ｂ、Ｉ−ｃのイオン応答の検量線を第
２図−ａ、ｂ、ｃに示す。電極Ｉ−ｂ、Ｉ−ｃにおいて
は起電力が生じないかあるいは非ネルンスト応答である
のに対し、修飾電極Ｉ−ａは１価カチオンに対しネルン
スト応答を示した。LiCl 1 × 10 -5 to 1 normal NaCl 1 × 10 -5 to 1 normal KCl 1 × 10 -5 to 1 normal MgCl 2 2 × 10 -6 to 2 × 10 -1 normal CaCl 2 2 × 10 -6 to 2 × 10 -1 normal HCl 1 × 10 -6 to 1 × 10 -1 normal (3) Measurement results The calibration curves of the ion response of the electrodes Ia, Ib, and Ic are shown in Figs. It is shown in c. Electrodes I-b and I-c did not generate electromotive force or had a non-Nernst response, whereas the modified electrode I-a exhibited a Nernst response to monovalent cations.
なお、電極の応答速度（起電力が一定値を示すまでの時
間）は10〜30秒であった。The electrode response speed (time until the electromotive force shows a constant value) was 10 to 30 seconds.
実施例 II 0.01mole/dm3ビス［ジ−（ｎ−オクチルフェニル）ホス
フェート］カルシウム（II）塩、0.10mole/dm3ピロール
を含む溶液を水１溶対二塩化メタン９溶の混合溶媒を用
いて作成し、過塩素酸によりpHを１〜２とした後窒素ガ
スを導入して溶存酸素を除去した。室温においてこの溶
液中に表面積0.25cm2のパイロリティックグラファイト
を浸せきし、４×10-5A/cm2の電流密度で1.44クーロン/
cm2電気量だけアノード電解重合を行わせることにより
電極II−ａを得た。また比較のため電解重合を行わせな
いパイロリティックグラファイト電極II−ｂを用意し
た。Example II A solution containing 0.01 mole / dm 3 bis [di- (n-octylphenyl) phosphate] calcium (II) salt and 0.10 mole / dm 3 pyrrole was used as a mixed solvent of 1 solution of water and 9 solutions of methane dichloride. The pH was adjusted to 1-2 with perchloric acid, and then nitrogen gas was introduced to remove dissolved oxygen. Pyrolytic graphite with a surface area of 0.25 cm 2 was immersed in this solution at room temperature, and at a current density of 4 × 10 -5 A / cm 2 , 1.44 coulomb /
Electrode II-a was obtained by carrying out anodic electropolymerization by the amount of cm 2 electricity. For comparison, a pyrolytic graphite electrode II-b which was not subjected to electrolytic polymerization was prepared.
（２）応答起電力の測定 25℃において、前述の一連の試料溶液に対する電極II−
ａ、II−ｂの銀−塩化銀参照電極に対する発生起電力を
測定し、検量線を作成した。(2) Measurement of response electromotive force Electrode II-
The electromotive force generated with respect to the silver-silver chloride reference electrode of a and II-b was measured, and the calibration curve was created.
（３）測定結果 電極II−ａ、II−ｂのイオン応答の検量線を図３−ａ、
ｂに示す。電極II−ｂは非ネルンスト応答しか示さない
のに対し、修飾電極II−ａはビス［ジ−（ｎ−オクチル
フェニル）ホスフェート］カルシウム（II）塩が、配位
能を示すカルシウムイオンに対し選択性を示した。ま
た、応答時間は10〜30秒であった。(3) Measurement results The calibration curves of the ionic response of the electrodes II-a and II-b are shown in FIG.
Shown in b. The electrode II-b shows only a non-Nernst response, whereas the modified electrode II-a has a bis [di- (n-octylphenyl) phosphate] calcium (II) salt which is selected for the coordinating calcium ion. Showed sex. The response time was 10 to 30 seconds.
第１図は本発明の修飾電極を用いて、被測定溶液中のイ
オンの活量を測定する場合の説明図である。 １……固体電極、２……重合皮膜、３……参照電極、４
……電位差計、Ａ……被測定溶液 第２図及び第３図は本発明の修飾電極、及び修飾しない
電極における各種イオンを含む溶液中における起電力応
答（検量線）の測定例である。 第２図ａ……1,3,6ナフタレントリスルホン酸ナトリウ
ムを含む修飾電極の検量線、 第２図ｂ……テトラエチルアンモニウムテトラフルオロ
ボレートを含む電極の検量線、 第２図ｃ……白金電極（非修飾）の検量線、 第３図ａ……ビス［ジ−（ｎ−オクチルフェニル）ホス
フェート］カルシウム（II）塩を含む修飾電極の検量
線、第３図ｂ……パイロリティックグラファイト電極
（非修飾）の検量線。FIG. 1 is an explanatory diagram for measuring the activity of ions in a solution to be measured using the modified electrode of the present invention. 1 ... Solid electrode, 2 ... Polymerized film, 3 ... Reference electrode, 4
... Potentiometer, A ... Solution to be measured FIGS. 2 and 3 are examples of measurement of electromotive force response (calibration curve) in a solution containing various ions in the modified electrode of the present invention and the unmodified electrode. Fig. 2a: Calibration curve of modified electrode containing sodium 1,3,6 naphthalene trisulfonate, Fig. 2b: Calibration curve of electrode containing tetraethylammonium tetrafluoroborate, Fig. 2c: Platinum electrode (Unmodified) calibration curve, FIG. 3 a ... Calibration curve of modified electrode containing bis [di- (n-octylphenyl) phosphate] calcium (II) salt, FIG. 3 b ... Pyrolytic graphite electrode ( Calibration curve (unmodified).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−118153（ＪＰ，Ａ) 特開 昭63−311157（ＪＰ，Ａ) 特開 平１−272957（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-118153 (JP, A) JP-A-63-311157 (JP, A) JP-A-1-272957 (JP, A)
Claims (1)
合法により重合可能な物質とからなる混合物を電解重合
させて得られる、イオン感応剤を含む高分子膜が被覆さ
れていることを特徴とするイオン選択性修飾電極。1. A solid electrode surface coated with a polymer film containing an ion sensitive agent, which is obtained by electrolytically polymerizing a mixture of an ion sensitive agent and a substance polymerizable by an electrolytic polymerization method. Characterized ion-selective modified electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143375A JPH0781980B2 (en) | 1989-06-05 | 1989-06-05 | Ion-selective modified electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1143375A JPH0781980B2 (en) | 1989-06-05 | 1989-06-05 | Ion-selective modified electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH039258A JPH039258A (en) | 1991-01-17 |
| JPH0781980B2 true JPH0781980B2 (en) | 1995-09-06 |
Family
ID=15337326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1143375A Expired - Lifetime JPH0781980B2 (en) | 1989-06-05 | 1989-06-05 | Ion-selective modified electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0781980B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2596184Y2 (en) * | 1991-12-11 | 1999-06-07 | 東陶機器株式会社 | Sanitary washing equipment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57118153A (en) * | 1981-01-14 | 1982-07-22 | Terumo Corp | Ph sensor |
| JPS63311157A (en) * | 1987-06-12 | 1988-12-19 | Bridgestone Corp | Ion sensor |
| JPH01272957A (en) * | 1988-04-25 | 1989-10-31 | Terumo Corp | Ion sensitive film its production and ion sensor |
-
1989
- 1989-06-05 JP JP1143375A patent/JPH0781980B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH039258A (en) | 1991-01-17 |
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