JPS6356497B2 - - Google Patents
Info
- Publication number
- JPS6356497B2 JPS6356497B2 JP19729381A JP19729381A JPS6356497B2 JP S6356497 B2 JPS6356497 B2 JP S6356497B2 JP 19729381 A JP19729381 A JP 19729381A JP 19729381 A JP19729381 A JP 19729381A JP S6356497 B2 JPS6356497 B2 JP S6356497B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- cell
- aqueous
- aqueous solvent
- capillary
- 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
Links
- 239000003125 aqueous solvent Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229920001817 Agar Polymers 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 239000008272 agar Substances 0.000 description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 229940075397 calomel Drugs 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011491 glass wool Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012047 saturated solution Substances 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
- 239000000126 substance Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 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
- G01N27/301—Reference electrodes
Description
【発明の詳細な説明】
本発明は非水溶媒用基準電極に関し、さらに詳
しくは非水溶媒中で電解用陽極試料を所定電位に
保持し定電位電解を行なう場合、その他電気化
学、金属工学分野において用いられる非水溶媒用
半電池基準電極に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reference electrode for non-aqueous solvents, and more particularly to reference electrodes for use in non-aqueous solvents when electrolytic anode samples are held at a predetermined potential to perform constant potential electrolysis, and in other fields of electrochemistry and metal engineering. This invention relates to a half-cell reference electrode for non-aqueous solvents used in.
鋼中非金属介在物の電解分析を例として以下説
明する。鋼中非金属介在物の分析方法としては、
鉄マトリツクスを電気化学的に溶解除去して介在
物を抽出分離した後、得られた残渣を再度電解に
供し、化合物別に分別する手法がとられている。
この場合に、例えばメタノールを溶媒とする非水
系電解液を用い定電位電解により分離定量を行な
う方法が、介在物の化学的溶損が少なく精度のよ
い方法として近年多用されており、定電位電解に
供する陽極試料を所定電位に保持するために非水
溶媒用基準電極が用いられる。 The electrolytic analysis of nonmetallic inclusions in steel will be explained below as an example. As a method for analyzing nonmetallic inclusions in steel,
After the iron matrix is electrochemically dissolved and removed to extract and separate inclusions, the resulting residue is subjected to electrolysis again and separated into compounds.
In this case, for example, a method of separating and quantifying by constant potential electrolysis using a non-aqueous electrolyte with methanol as a solvent has been widely used in recent years as a highly accurate method with less chemical erosion of inclusions. A non-aqueous solvent reference electrode is used to maintain the anode sample at a predetermined potential.
非水溶媒用の基準電極には、測定溶液と同じ溶
媒を用いて作つたものもあるが、従来から使用が
容易で電極電位が明確な飽和カロメル電極や銀、
塩化銀電極など水溶液用の電極を塩橋に浸して用
いるのが一般的である。 Some reference electrodes for non-aqueous solvents are made using the same solvent as the measurement solution, but traditional electrodes such as saturated calomel electrodes, which are easy to use and have a clear electrode potential, silver electrodes, etc.
It is common to use an electrode for aqueous solutions, such as a silver chloride electrode, immersed in a salt bridge.
第１図は鋼中非金属介在物分析を目的とした電
解分析に用いられる電解装置の断面側面図を例示
し、水溶液半電池電極を定電位制御に使用し塩橋
を架橋したものである。図において、１は非水電
解液を収納した電解槽、２は試料支持台、３は試
料（陽極）、４は白金板（陰極）、５は白金線、６
ａは寒天塩橋の非水溶媒部、６ｂは寒天塩橋の寒
天部、７は塩化カリ飽和溶液、８はカロメル電
極、９は定電位電解装置である。このようにカロ
メル電極８と非水溶媒との液絡部には寒天塩橋６
ａ，６ｂを架橋する測定方法がられてきた。 FIG. 1 illustrates a cross-sectional side view of an electrolytic device used for electrolytic analysis for the purpose of analyzing nonmetallic inclusions in steel, in which an aqueous solution half-cell electrode is used for constant potential control and a salt bridge is bridged. In the figure, 1 is an electrolytic cell containing a non-aqueous electrolyte, 2 is a sample support stand, 3 is a sample (anode), 4 is a platinum plate (cathode), 5 is a platinum wire, and 6
a is the non-aqueous solvent part of the agar salt bridge, 6b is the agar part of the agar salt bridge, 7 is a potassium chloride saturated solution, 8 is a calomel electrode, and 9 is a constant potential electrolyzer. In this way, an agar salt bridge 6 is provided at the liquid junction between the calomel electrode 8 and the nonaqueous solvent.
Measurement methods for crosslinking a and 6b have been developed.
この装置は、寒天塩橋を用いることから装置が
複雑化し、寒天部の保守、更新が繁雑であり、ま
た塩橋先端のキヤピラリー６ｃがガラス製のため
破損しやすい等の欠点があつた。 This device had drawbacks such as the use of an agar salt bridge, which made the device complicated, the maintenance and renewal of the agar section was complicated, and the capillary 6c at the tip of the salt bridge being made of glass, it was easily damaged.
本発明の目的は、電解質水溶液を収納した半電
池電極を利用した非水溶媒用基準電極であつて、
上記欠点を解消した基準電極を提供することにあ
る。すなわち、非水測定液中の電解電位を一定電
位に制御する際、寒天塩橋等を用いる必要がなく
非水溶媒中の電極に直接セツトすることができ、
保守および取扱いの容易な基準電極である。 An object of the present invention is to provide a reference electrode for non-aqueous solvents using a half-cell electrode containing an aqueous electrolyte solution,
The object of the present invention is to provide a reference electrode that eliminates the above drawbacks. That is, when controlling the electrolytic potential in the non-aqueous measurement solution to a constant potential, there is no need to use an agar salt bridge, etc., and it can be directly set on the electrode in the non-aqueous solvent.
It is a reference electrode that is easy to maintain and handle.
本発明の実施例を第２図に示す。 An embodiment of the invention is shown in FIG.
本発明の基準電極１０は、半電池電極部１１、
非水溶媒セル部１２、キヤピラリー１３より成
り、半電池電極部１１と非水溶媒セル部１２とを
一体に連接して成形したものである。図において
半電池電極部１１はカロメル電極の場合を示し、
外筒には飽和塩化カリ水溶液７、内筒にはカロメ
ル泥２２、水銀２３、グラスウール２４が収納さ
れ、電極底部には開孔２１があり、グラスウール
２４を介して外筒内の飽和塩化カリ水溶液７に連
通している。 The reference electrode 10 of the present invention includes a half-cell electrode part 11,
It consists of a non-aqueous solvent cell part 12 and a capillary 13, and is formed by integrally connecting the half-cell electrode part 11 and the non-aqueous solvent cell part 12. In the figure, the half-cell electrode part 11 is a calomel electrode,
The outer cylinder houses a saturated potassium chloride aqueous solution 7, and the inner cylinder houses calomel mud 22, mercury 23, and glass wool 24. There is an opening 21 at the bottom of the electrode, and the saturated potassium chloride aqueous solution inside the outer cylinder is stored through the glass wool 24. It is connected to 7.
半電池電極底部には毛細孔１６が設けられ、飽
和塩化カリ水溶液７と非水溶媒セル部１２とを毛
細連通する。この毛細孔１６は塩橋の機能を果す
ものである。 Capillary pores 16 are provided at the bottom of the half-cell electrode to provide capillary communication between the saturated potassium chloride aqueous solution 7 and the non-aqueous solvent cell section 12 . This capillary pore 16 functions as a salt bridge.
非水溶媒セル部１２には、非水溶媒注入孔１４
ａ，１４ｂが設けられ、それぞれシリコンゴム栓
１８およびゴムキヤツプ１７によつて施蓋され
る。ゴムキヤツプ１７は伸縮自在とし、キヤピラ
リー１３内の気泡除去に使用される。また非水溶
媒セル部１２にはグラスフイルター１５を備え
る。グラスフイルター１５はカロメル電極からの
水分が非水測定液に混入するのを防ぎ、またカロ
メル電極毛細孔１６に析出した塩化カリ結晶の非
水測定液への落下混入を防止する。 A non-aqueous solvent injection hole 14 is provided in the non-aqueous solvent cell section 12.
a and 14b are provided, and each is covered with a silicone rubber stopper 18 and a rubber cap 17. The rubber cap 17 is expandable and retractable and is used to remove air bubbles within the capillary 13. Further, the non-aqueous solvent cell section 12 is equipped with a glass filter 15. The glass filter 15 prevents moisture from the calomel electrode from entering the non-aqueous measurement liquid, and also prevents potassium chloride crystals deposited in the calomel electrode capillary pores 16 from falling into the non-aqueous measurement liquid.
キヤピラリー１３は、電解液に安定で破損しに
くい電気絶縁体例えば四弗化エチレン樹脂製等が
望ましく、孔径200μｍ程度のものである。非水
測定液中の試料の表面にできるだけ近づけて使用
する。 The capillary 13 is preferably made of an electrical insulator, such as tetrafluoroethylene resin, which is stable in the electrolyte and is not easily damaged, and has a pore diameter of about 200 μm. Use it as close as possible to the surface of the sample in the non-aqueous measurement solution.
第３図は本発明の基準電極を使用した電解装置
の実施例を示し、従来のような塩化カリ水溶液槽
および塩橋を要せず、基準電極１０を試料３に直
接セツトすることができ、キヤピラリーの破損も
なく、保守および取扱いが容易となつた。 FIG. 3 shows an embodiment of an electrolytic device using the reference electrode of the present invention, in which the reference electrode 10 can be directly set on the sample 3 without requiring a conventional potassium chloride aqueous solution tank and a salt bridge. There was no damage to the capillary, making maintenance and handling easier.
以上の説明では、電解分析を例として説明した
が、本発明の基準電極は、近年非水溶媒の利用が
盛んとなつて来た電気化学の分野、金属工学の分
野において、例えば電位の測定、活量や濃度の測
定、電位の制御による選択的なイオン種の析出ま
たは溶出、電解エツチング、アノード処理による
酸化被膜の形成、その他極めて広範囲の工程にお
ける電極電位の測定、照合、制御に適用可能であ
る。 In the above explanation, electrolytic analysis was explained as an example, but the reference electrode of the present invention can be used in the fields of electrochemistry and metallurgy, where the use of non-aqueous solvents has become popular in recent years, for example, for measuring potential. It can be applied to the measurement, verification, and control of electrode potentials in a wide range of processes, including activity and concentration measurement, selective precipitation or elution of ionic species by controlling potential, electrolytic etching, and formation of oxide films through anode treatment. be.
第１図は寒天塩橋を用いる従来の電解装置の一
部断面側面図、第２図は本発明の基準電極の実施
例の縦断面図、第３図は本発明の実施例を使用し
た電解装置の一部断面側面図である。
１……非水電解液収納電解槽、２……試料支持
台、３……試料（陽極）、４……白金板（陰極）、
５……白金線、６ａ……寒天塩橋の非水溶媒部、
６ｂ……寒天塩橋の寒天部、６ｃ……キヤピラリ
ー、７……飽和塩化カリ水溶液、８……カロメル
電極、９……定電位電解装置、１０……本発明の
非水溶媒用基準電極、１１……半電池電極部、１
２……非水溶媒セル部、１３……キヤピラリー、
１４ａ，１４ｂ……非水溶媒注入口、１５……グ
ラスフイルター、１６……毛細孔、１７……ゴム
キヤツプ、１８……シリコンゴム栓、１９……Ｕ
ジヨイント、２０……白金線、２１……開孔、２
２……カロメル泥、２３……水銀、２４……グラ
スウール。
Fig. 1 is a partial cross-sectional side view of a conventional electrolysis device using an agar-salt bridge, Fig. 2 is a vertical cross-sectional view of an embodiment of the reference electrode of the present invention, and Fig. 3 is an electrolyzer using an embodiment of the present invention. FIG. 2 is a partially sectional side view of the device. 1...Non-aqueous electrolyte storage electrolytic cell, 2...Sample support stand, 3...Sample (anode), 4...Platinum plate (cathode),
5...Platinum wire, 6a...Non-aqueous solvent part of agar salt bridge,
6b... Agar part of the agar salt bridge, 6c... Capillary, 7... Saturated potassium chloride aqueous solution, 8... Calomel electrode, 9... Constant potential electrolyzer, 10... Reference electrode for nonaqueous solvents of the present invention, 11...Half-cell electrode part, 1
2...Nonaqueous solvent cell part, 13...Capillary,
14a, 14b...Nonaqueous solvent inlet, 15...Glass filter, 16...Capillary pore, 17...Rubber cap, 18...Silicone rubber stopper, 19...U
Joint, 20...Platinum wire, 21...Open hole, 2
2...Calomel mud, 23...Mercury, 24...Glass wool.
Claims (1)
に収納された電極部と、電極部に接触する電線
と、外筒の下端に設けられた毛細孔と、外筒と内
筒との間に注入された電解質水溶液とを有する半
電池電極と； 半電池電極の下端に一体に連接されており、中
間部に配設されたグラスフイルターにより上部と
下部とに分割され、上部と下部とにそれぞれ施蓋
された非水溶媒注入口を有する非水溶媒セルと； 非水溶媒セルの下端に連接されたキヤピラリ
ー； とよりなることを特徴とする非水溶媒用基準電
極。[Scope of Claims] 1. An outer cylinder, an inner cylinder having an opening at the lower end, an electrode part housed in the inner cylinder, an electric wire in contact with the electrode part, and a capillary hole provided at the lower end of the outer cylinder. and a half-cell electrode having an electrolyte aqueous solution injected between the outer cylinder and the inner cylinder; The half-cell electrode is integrally connected to the lower end of the half-cell electrode, and the upper and lower parts are separated by a glass filter disposed in the middle. A non-aqueous solvent cell which is divided into a non-aqueous solvent cell and has a non-aqueous solvent inlet each covered at an upper part and a lower part; a capillary connected to a lower end of the non-aqueous solvent cell; Reference electrode for solvents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19729381A JPS5897652A (en) | 1981-12-08 | 1981-12-08 | Reference electrode for nonaqueous solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19729381A JPS5897652A (en) | 1981-12-08 | 1981-12-08 | Reference electrode for nonaqueous solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5897652A JPS5897652A (en) | 1983-06-10 |
| JPS6356497B2 true JPS6356497B2 (en) | 1988-11-08 |
Family
ID=16372047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19729381A Granted JPS5897652A (en) | 1981-12-08 | 1981-12-08 | Reference electrode for nonaqueous solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5897652A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001022600A (en) | 1999-07-06 | 2001-01-26 | Matsushita Electric Ind Co Ltd | Digital signal processor |
-
1981
- 1981-12-08 JP JP19729381A patent/JPS5897652A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5897652A (en) | 1983-06-10 |
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