JPS62259054A - Reference electrode - Google Patents
Reference electrodeInfo
- Publication number
- JPS62259054A JPS62259054A JP10092386A JP10092386A JPS62259054A JP S62259054 A JPS62259054 A JP S62259054A JP 10092386 A JP10092386 A JP 10092386A JP 10092386 A JP10092386 A JP 10092386A JP S62259054 A JPS62259054 A JP S62259054A
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- JP
- Japan
- Prior art keywords
- electrode
- liquid
- chamber
- electrode chamber
- temperature
- 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.)
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- 239000007788 liquid Substances 0.000 claims abstract description 31
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000003411 electrode reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001103 potassium chloride Substances 0.000 claims abstract description 11
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000012795 verification Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000005373 porous glass Substances 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 7
- 238000007789 sealing Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000000740 bleeding effect Effects 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- -1 silver-silver halide Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔腫莱上の利用分ｅＪ
本発明は照□ｅｒ ’ｔｉｔ捕に詠り１時に高温ボイラ
ー。DETAILED DESCRIPTION OF THE INVENTION [Usage of the tumor eJ] The present invention is aimed at capturing a high temperature boiler at 1 o'clock.
原子炉冷却設備および高−高圧純水課税下の金属表面の
腐食挙動を評価するためのに極−位測定七／すとしての
高−尿、原子炉冷却系１石油火カ発電用復水器等用とし
て好適な内部照合型の照合電極に関するものである。Reactor cooling system 1 Condenser for oil-fired power generation The present invention relates to an internal verification type reference electrode suitable for applications such as the following.
従来、高４高圧水中に２ける金属の電極４位測定の基準
として用いらｎている照合電極には、測疋４位の再現性
がよく、長時間、熱力学的（で正しい動作を示し、かつ
、測定環境液との適せ性があるなどの電性が要ポされて
いる。Conventionally, the reference electrode used as a standard for measuring the 4th position of metal electrodes in high-pressure water has good reproducibility of the 4th position measurement and shows correct thermodynamic (thermodynamic) behavior over a long period of time. In addition, electrical properties such as compatibility with the measurement environment liquid are required.
従来の照貧′１極には、第５図に代表されるように、高
温高圧容器上蓋３１に固定されている石英ｇ３２などを
通し゛Ｃ高温高圧水３３を高温高圧容器外へ導出し、こ
れを第５図中の水冷ジャケット３４ンこよう６却して照
会電極型へ送り、電位測定を行う外部層ｄ型といわれる
照合電極があった。In the conventional irradiation method, as typified by FIG. On the other hand, there was a reference electrode called an external layer d type, which was sent to the reference electrode type and measured the potential in the water-cooled jacket 34 shown in Figure 5.
３５は濾紙プラグ、Ｅぼアフロン絶縁物でろる。35 is a filter paper plug, and E is filled with an Aphron insulator.
・コア’ｔ、 ＶＣ−）イテｄ Ｉ 、１ｔｍ４貧誌、
ｊ５，４７（１９７１）の膝井らの一又に記１し“ｃｈ
る。また、ポウアペイクス エム（ｐｏｕｒｂａｔｘ
Ｍ）による「アトラス１ブ エレクトロケミカル エキ
ュイリイビリアイ／ アキュアス ソルユーゾヨンＪ
（Ａｔｌａｓｏｆ Ｅｌｅｃｔｒｏｃｈｍｉｃａ
ｌ Ｅｑｕ＋ｌ１ｂｒｃａ １ｎＡｑｕｅｏｕｓＳ
ｏｌｕｔ＋ｏｎ ） （１ｇ６６年）に示してある第６
図に代表さルるように、銀−ハロゲン化銀電極（ここで
は銀−項化尿電極）がテフロンと多孔質アルミナｆに保
護された電極室（以下、保護管という）の中Ｖこ設置さ
ノし、ここに塩化カリウノ・溶液を封入して、電極反応
に行わせる装置全体が高温高圧水中に浸漬さル、テフロ
ン製ルギン管３７から導入される部製高圧水がアスベス
ト芯３８を介してテフロン製蓋３９を通ってＫ Ｃを溶
液を含浸したＡ１２ｏｚ粉を充填した電極室４０に入シ
、これにより高温高圧容器内の金属の表面電位を照合す
る内部照合型といわれる照合電極がある。これについて
は、杉本％相馬による１９ｉ：１０年の腐食防食協会
８０春期学術講演会予稿集の１８５頁にも記載してある
。なお、４１は銀電極、４２は高温高圧容器上蓋、４３
は多孔質アルミナ管、４４はＫＣ１内部液、４５はテフ
ロン容器である。・Core't, VC-) Ited I, 1tm4 Samurai,
J5, 47 (1971), “ch.
Ru. Also, pourbatx
"Atlas 1B Electrochemical Equilibrium/Acurus Solyuzoyon J" by M)
(Atlas of Electrochmica
l Equ+l1brca 1nAqueousS
olut+on) (1g66)
As represented in the figure, a silver-silver halide electrode (in this case, a silver-silver halide electrode) is installed in a V-shaped electrode chamber (hereinafter referred to as a protective tube) protected by Teflon and porous alumina. Then, potassium chloride solution is sealed here and the entire apparatus is immersed in high-temperature, high-pressure water for electrode reaction. The electrode chamber 40 filled with A12 oz powder impregnated with K C solution passes through the Teflon lid 39, and there is a reference electrode called an internal reference type that verifies the surface potential of the metal inside the high temperature and high pressure container. . Regarding this, see 19i: 10 Years of Corrosion Prevention Association by Sugimoto% Soma.
It is also mentioned on page 185 of the 1980 Spring Academic Lecture Proceedings. In addition, 41 is a silver electrode, 42 is a high-temperature, high-pressure container top lid, and 43 is a silver electrode.
44 is a porous alumina tube, 44 is a KC1 internal liquid, and 45 is a Teflon container.
ここで、電極室における電極反応電位は、銀−塩化銀電
極では次の（１）式の工うに表わされる（日本化学会の
化学便覧（基礎編１）１９６６年、丸＠曹店発行を参照
）。Here, the electrode reaction potential in the electrode chamber is expressed by the following formula (1) for the silver-silver chloride electrode (see Chemical Society of Japan's Chemical Handbook (Basic Edition 1) published by Maru@Sodian in 1966). ).
ここに、Ａｇ’；ｇ（７）反応平衡’ｌｊ１位（Ｖ／５
ＨＥ）ＥＡヨｃｔ０．塩化銀の反応平衡電位
（Ｖ／５）ｉＥ）
Ｒ；気体常数（８，３１４ジユ一ル／ＭＯＬＫ）Ｔ；絶
対温度（０Ｋ）
Ｆ；ファラデイ一定数（９６５００クーロン）ａＣｌ−
、塩素イオン活量
こｎらの電極のうち、外部照合型の照合電極では、扁温
筒圧容器から試験液を液絡の之めに絶えず流出させる必
要がらり、このための圧力シール部（第５図では濾紙プ
ラグ３５）の７−リング方法が繊しく、この部分では減
圧される液中の溶存ガスが気泡となって液絡を阻害した
り、あるいは。Here, Ag';g(7) reaction equilibrium'lj1 position (V/5
HE) EA Yoct0. Reaction equilibrium potential of silver chloride (V/5) iE) R: Gas constant (8,314 units/MOLK) T: Absolute temperature (0K) F: Faraday constant (96,500 coulombs) aCl-
, chloride ion activity Among these electrodes, the external reference type reference electrode requires the test liquid to constantly flow out from the cryotubular pressure vessel toward the liquid junction, and a pressure seal part (no. In Figure 5, the 7-ring method of the filter paper plug 35) is delicate, and in this part, dissolved gas in the liquid being depressurized becomes bubbles and obstructs the liquid junction.
高温液を冷却して常温度で測定するため、電位補正を行
わなければならないが、それが難しいなどの問題がある
。Since the high-temperature liquid is cooled and measured at room temperature, it is necessary to perform potential correction, but there are problems such as the difficulty of doing so.
一方、内部照合型の照合電極においては、測定した試料
電極の電位を熱力学的取り扱いに便利なＳＨＥ基準値に
換算できるものの、電極内の封入液が漏出して電極室に
おける反応電位があらかじめ熱力学的に確認された挙動
と異ってくるという欠点がある。On the other hand, with internal reference type reference electrodes, although the measured potential of the sample electrode can be converted into the SHE reference value, which is convenient for thermodynamic handling, the liquid sealed inside the electrode leaks and the reaction potential in the electrode chamber is heated up in advance. The disadvantage is that the behavior differs from the mechanically confirmed behavior.
〔発、１明が解決しようとする問題点〕従来の内部照合
型の照合電極においては、液箱部を通して＾温高圧容器
の高圧水を取シ込む構造となっているが、このために電
極室内のＣｌ−がすこから容器中に拡散するかもしくは
電極が絶縁さｎている絶縁物との界面を通って高ｍ高圧
容器外に漏出することがめシ、このような場合、（１）
式に示したＷＬ憔至内の電極反応電位を正確に把掴でき
ないという問題点があった。[Problems to be solved by the authors] Conventional internal reference type reference electrodes have a structure in which high-pressure water from a high-temperature and high-pressure container is pumped through the liquid box. In such a case, (1) Cl- in the room may diffuse into the container or leak out of the high-pressure container through the interface with the insulating material in which the electrode is insulated.
There was a problem in that the electrode reaction potential within the WL gap shown in the formula could not be accurately determined.
本発明の目的は、高温高圧純水環境における金属表面の
電極電位を安定に測定でき、また、電極呈内に一定量の
Ｃｌ−を供給可能でめり、しかも。An object of the present invention is to be able to stably measure the electrode potential of a metal surface in a high-temperature, high-pressure pure water environment, and to be able to supply a certain amount of Cl- into the electrode.
高温高圧容器内への電極反応液の逆拡散をないようにで
きる内部照合型の照合電極を提供することにるる。It is an object of the present invention to provide an internal reference type reference electrode that can prevent back diffusion of an electrode reaction liquid into a high-temperature, high-pressure container.
上記目的は、銀−塩化銀からなる金属電極を設置した外
界から隔離絶縁された電極室と、この電極室の上記金属
電極を覆うように設けた塩化カリウム粉末を含む保護管
と、上記′成極室内に高温高圧容器内の純水を−ｄＤ込
む液絡管とを備え、上記電極室内のｎｔｔｍ反応に必要
な一定虚のＣｌ−を供給して上記高温高圧容器内の供試
金属表面電位を測定する構成として達成するようにした
。The above purpose is to provide an electrode chamber isolated and insulated from the outside world in which a metal electrode made of silver-silver chloride is installed, a protective tube containing potassium chloride powder provided to cover the metal electrode in this electrode chamber, and The electrode chamber is equipped with a liquid junction tube that introduces -dD of pure water in a high-temperature, high-pressure container, and a constant imaginary Cl- necessary for the nttm reaction in the electrode chamber is supplied to increase the surface potential of the test metal in the high-temperature, high-pressure container. This was achieved through a configuration for measuring.
電極室内に塩化カリウムを高温高圧水に一定の割合で供
給する塩化カリウム粉末を含む保護管でｎｔ電極室内金
属電極を覆うようにしたので、高温高圧純水環境におけ
る金属異面の電極電位を安定に測定でき、また、高温高
圧水の漏失に対応して塩化カリウムを供給できるので、
封入電解質の漏失を阻止することができる。またｉ成極
室内には高温高圧容器内の純水を斌絡管を介して取シ込
むようにしたので、照合電極から高温高圧容器内への電
極反応液の逆拡散をなくすことができる。さらに、高温
舗王水を一定流量で高温高圧容器外へ漏失させるように
したので、そのｐＪ、／＃ｔの電気伝導度より電極室内
のＣｌ−活量を予知できる。The metal electrode in the NT electrode chamber is covered with a protective tube containing potassium chloride powder that supplies potassium chloride to high-temperature, high-pressure water at a constant rate in the electrode chamber, which stabilizes the electrode potential of different metal surfaces in a high-temperature, high-pressure pure water environment. In addition, potassium chloride can be supplied in response to leaks of high-temperature, high-pressure water.
Leakage of the encapsulated electrolyte can be prevented. Furthermore, since the pure water in the high-temperature, high-pressure container is introduced into the i-polarization chamber through the torrent tube, it is possible to eliminate back diffusion of the electrode reaction liquid from the reference electrode into the high-temperature, high-pressure container. Furthermore, since the high-temperature aqua regia is allowed to leak out of the high-temperature and high-pressure container at a constant flow rate, the Cl- activity in the electrode chamber can be predicted from the electrical conductivity of pJ, /#t.
以ド本発明を第１図、第２図に示した実施例および第３
図、第４図を用いて詳細に説明する。Embodiments of the present invention shown in FIGS. 1 and 2 and 3.
This will be explained in detail using FIGS.
第１図は本発明の内部照合型の照合磁極の一実施例を示
す概要図でるる。第１図の照合１！極は。FIG. 1 is a schematic diagram showing an embodiment of an internal verification type verification magnetic pole of the present invention. Figure 1 matching 1! The pole is.
電極２．電極室３．電極反応液の液抵抗の検出系を主要
構成要素としている。照合電極は高温高圧“容器上蓋１
に図示のように固定されてお９．電極２は銀−塩化銀を
用いて構成してろシ、図示のような断面形状を有してお
シ、突起を有する。そして、ｔＪＬ極室３に接する面は
溶融接着塩化銀４によって電極室３に接着してある。Electrode 2. Electrode chamber 3. The main component is a detection system for the resistance of the electrode reaction solution. The reference electrode is high temperature and high pressure.
9. is fixed as shown in the figure. The electrode 2 is made of silver-silver chloride, has a cross-sectional shape as shown in the figure, and has protrusions. The surface in contact with the tJL electrode chamber 3 is adhered to the electrode chamber 3 with melt adhesive silver chloride 4.
また、電極２は、塩化銀４がある部分を除き。Moreover, the electrode 2 except for the part where the silver chloride 4 is present.
全表面がテフロン焼付けなどによう絶縁被覆してるり、
この電極２はテフロンなどの絶縁物を加工して表作した
絶縁固定具５，６により密着固定してある。The entire surface is coated with insulation such as Teflon baking,
This electrode 2 is closely fixed by insulating fixtures 5 and 6 made of an insulating material such as Teflon.
電極室３は、絶縁固定具６と絶縁スリーブ７とで構成さ
れた空間であり、その内側に電極２を覆うように保護管
８が設置してある。保護管８は。The electrode chamber 3 is a space made up of an insulating fixture 6 and an insulating sleeve 7, and a protective tube 8 is installed inside thereof so as to cover the electrode 2. Protection tube 8.
塩化カリウム微粉末をパーライト、バーミキュライト、
ソーダ石灰ガラス、Ｓ化ケイ素などの多孔質ガラスで被
覆した後、これらを粘土質材料を用いて焼結結合して保
護管状にしたものである。Potassium chloride fine powder is combined with perlite, vermiculite,
After being coated with porous glass such as soda lime glass or silicon sulfide, these are sintered and bonded using a clay material to form a protective tube.
また、電極室３には、外部からの尚王水によシ絶縁スリ
ーブ７や保護管８が損傷するのを防止すｌるため固定ア
スベスト、アルミナ（ｋｔｚｏｓ ）などの焼結微粒子
が充填してある。In addition, the electrode chamber 3 is filled with sintered fine particles of fixed asbestos, alumina (ktzos), etc. to prevent damage to the insulating sleeve 7 and protective tube 8 due to aqua regia from the outside. be.
さらに、絶縁スリーブ７には、図示のような液絡９が設
置してろυ、固定具１０に取シ付けてあり、かつ、上記
と同じ充填物を充填した液絡管１１より高′ｔＭＡ王水
が電極室３内に浸入する。Furthermore, a liquid junction 9 as shown in the figure is installed in the insulating sleeve 7, which is attached to the fixture 10, and has a higher tMA than the liquid junction pipe 11 filled with the same filling material as above. Water enters into the electrode chamber 3.
１２．１３はｅ縁固足具５の支持具である。12.13 is a support for the e-edge fixture 5.
−万、高鴎洲圧谷器上蓋１の外側に取り出された電憾２
の固定用絶縁固定具５の先端にはシーリングリング１４
が設置してｓｂ、これをシーリングキャンプ１５のネジ
によシ適当な強さに圧縮することにより、電極２と絶縁
固定具５との界面よシ滲出する電極反応液の流速を制御
するようにしてあるっ ・
さらに、シーリングキャップ１５には微小な液絡−ｇ１
６が設置してあり、参出液は液絡管１６を通過して電解
セル１７に導かれ、ここで計測器１８によ多液間抵抗が
測定され、電極反応液中のＣｌ−濃度が推定される。- 10,000, Takaozu Pressure Valley Apparatus Upper Lid 1 Taken out from the outside 2
A sealing ring 14 is attached to the tip of the insulating fixture 5 for fixing the
sb is installed and compressed to an appropriate strength by the screw of the sealing camp 15 to control the flow rate of the electrode reaction liquid seeping out from the interface between the electrode 2 and the insulating fixture 5.・ In addition, there is a minute liquid junction -g1 in the sealing cap 15.
6 is installed, and the participating liquid passes through the liquid junction pipe 16 and is led to the electrolytic cell 17, where the multi-liquid resistance is measured by the measuring device 18, and the Cl- concentration in the electrode reaction liquid is measured. Presumed.
′また。この方法によシミ極室３内の電極反応液は高温
高圧容器内に逆拡散することが避けられる。'Also. This method prevents the electrode reaction liquid in the stain electrode chamber 3 from back-diffusion into the high-temperature and high-pressure container.
次に、電極反応に関与する事項について説明する。まず
、高温高圧容器中の環流液−は、第１図の液絡管１１よ
シ浸入し、電極ヱ３内に充満すると。Next, matters related to electrode reactions will be explained. First, the reflux liquid in the high-temperature, high-pressure container enters through the liquid junction pipe 11 in FIG. 1 and fills the electrode 3.
保護管８より次の（２）式にしたがって塩化カリウム（
ＫＯ２）の溶解が起シ。Potassium chloride (
Dissolution of KO2) occurs.
電極室３内にＣｌ−が供給される。Cl- is supplied into the electrode chamber 3.
ここで、塩化銀電極２の表面では１次の（３）弐に示す
電極反応が行われ、
その電極電位は塩素イオンの活量で決定される。Here, on the surface of the silver chloride electrode 2, the primary electrode reaction shown in (3) 2 takes place, and the electrode potential is determined by the activity of chloride ions.
また、＠度による影＃は、（１）式によシ示される。Further, the shadow # due to @ degree is expressed by equation (1).
次に、効果を確認するため１本発明に係る照合電極を高
温高圧容器上蓋に第１図に示すように取シ付け、第２図
に示す実施例の測定回路によって金属試験片の陽分極曲
線を測定によって求゛めた。Next, in order to confirm the effect, a reference electrode according to the present invention was attached to the upper lid of a high-temperature and high-pressure container as shown in FIG. was determined by measurement.
第２図中の高温高圧容器１９は、温度３００Ｃ１圧力１
５０ａｔｍまでのものを用い、これに金属試験片２０お
よび電位走引用電極２１として試験片２０と同−狭面積
を有する白金ｉｔ極を設置し、さらに本発明に係る照合
電極２２を設置し、それぞれの導電線をポテンショスタ
ンド２３に接続した。The high temperature and high pressure vessel 19 in Fig. 2 has a temperature of 300C and a pressure of 1.
A metal test piece 20 and a platinum IT electrode having the same narrow area as the test piece 20 were installed as a metal test piece 20 and a potential running electrode 21, and a reference electrode 22 according to the present invention was further installed. The conductive wire was connected to the potentiometer stand 23.
そして、ポテンションスタンド２３によシミ位を自動走
引して得られる電流値を直流記録計２４と電位記録計２
５に記録し、このデータをもとにして金属試験片２０の
陽分極曲線をプロッター２６に作図する工うＫした。Then, the current value obtained by automatically running the stain position using the potentiometer stand 23 is measured by the DC recorder 24 and the potential recorder 2.
5, and based on this data, a positive polarization curve of the metal test piece 20 was plotted on the plotter 26.
この操作を温度１５０Ｃ，２００ｒ、２５０Ｃについて
行った結果、第３図に示すような陽分極曲線が得られた
。第３図のａ曲ｌＢは１５０Ｃ，１）曲森は２００Ｃ，
Ｃ曲線は２５０Ｃの場合で、同図から金属試験片２０の
電極反応の平衡電位に近似する電位（腐＊屯征）に、温
度の上昇とともに′４−位側に移行し、平衡反応の熱力
学Ｖζおいて示されている温度−平衡電位の関係に近似
していることが認められた。また、同図から金属試験片
２０の腐Ｓ：を流に直き換えられる電流に、１度の上昇
とともに増加する温間が認められる。As a result of performing this operation at temperatures of 150C, 200r, and 250C, an anodic polarization curve as shown in FIG. 3 was obtained. In Figure 3, the a song IB is 150C, 1) The song Mori is 200C,
The C curve is for the case of 250C, and from the same figure, as the temperature rises, the potential approximates the equilibrium potential of the electrode reaction of the metal test piece 20 (ro*tonsei), and shifts to the '4-position side, and the heat of the equilibrium reaction increases. It was found that the relationship between temperature and equilibrium potential is similar to that shown in the dynamics Vζ. Furthermore, from the same figure, it can be seen that the current that converts the corrosion S: of the metal test piece 20 directly into a current has a warm temperature that increases as the temperature rises by 1 degree.
さらに、金属試犠片２０の不一悪化の峨向け。Furthermore, the unevenness of the metal sacrificial piece 20 is becoming worse.
温度の上昇とともに不安定となってくることも認められ
ることより、本発明に係る照合電極２２は。Since it is recognized that the reference electrode 22 according to the present invention becomes unstable as the temperature rises.
このような４境に２いて十分安定した状態でこれらの電
像反応を測定し得るものであることが確認できた。It was confirmed that these electromagnetic reactions could be measured in a sufficiently stable state within these four boundaries.
一方１本発明に係る照会電極２２０一度一＠度に、第４
図に示すように、保護管８からの塩化カリウムの電極室
溶液への溶解度が温度の上昇とともに増加するため、そ
の増加分だけ換算が必要である。While one interrogation electrode 220 according to the present invention once at a time, the fourth
As shown in the figure, the solubility of potassium chloride from the protective tube 8 in the electrode chamber solution increases as the temperature rises, so it is necessary to convert by the amount of increase.
以上説明したように１本発明によれば、高温高圧純水環
境における金属表面の電極電位を安定に測定でき、また
、電極案内に一定量のＣｌ−を供給可能であプ、電極呈
内の電解液質のＣｌ−ａ度を測定可能であり、しかも、
照会電極から高温高圧容器内へのｗＬ極反応液の逆拡散
がないという効果がある。As explained above, according to the present invention, it is possible to stably measure the electrode potential of a metal surface in a high-temperature, high-pressure pure water environment, and it is also possible to supply a certain amount of Cl- to the electrode guide. It is possible to measure the Cl-a degree of electrolyte, and
This has the advantage that there is no back-diffusion of the wL electrode reaction liquid from the inquiry electrode into the high temperature and high pressure vessel.
第１図は本発明の内部照合型の照会電極の一実施例を示
す概要図、第２図は第１図の照合電極を高温高圧容器上
蓋に４ｕ）付けた場合の測定回路の一実施例を示す回路
図、第３図は金属の陽分極曲線の実験結果を示す線図、
第４図は塩化銀の溶解度に及ぼす温度の影響を示す線図
、第５図は従来の外部照合型照合電極の例を示す概要図
、第６図は従来の内部照合型照合電極の例を示す概要図
である。
１・・・高温高圧容器上蓋、２・・・電極、３・・・電
極室、４・・・溶融接着塩化銀、５，６・・・絶縁固定
具、７・・・絶縁スリーブ、８・・・保護管、９・・・
液絡、ｌＯ・・・固定具、１１，１６・・・液絡管、１
４・・・シーリングリング、１５・・・シーリングキャ
ップ、１７・・・電解セル、１８・・・計測器。Figure 1 is a schematic diagram showing an embodiment of the internal verification type inquiry electrode of the present invention, and Figure 2 is an example of a measurement circuit when the reference electrode of Figure 1 is attached to the upper lid of a high-temperature, high-pressure container. Figure 3 is a diagram showing the experimental results of the anodic polarization curve of metal.
Figure 4 is a diagram showing the effect of temperature on the solubility of silver chloride, Figure 5 is a schematic diagram showing an example of a conventional external reference type reference electrode, and Figure 6 is an example of a conventional internal reference type reference electrode. FIG. DESCRIPTION OF SYMBOLS 1... Upper lid of high temperature and high pressure container, 2... Electrode, 3... Electrode chamber, 4... Melt bonding silver chloride, 5, 6... Insulating fixture, 7... Insulating sleeve, 8...・Protection tube, 9...
Liquid junction, lO... Fixture, 11, 16... Liquid junction pipe, 1
4... Sealing ring, 15... Sealing cap, 17... Electrolytic cell, 18... Measuring instrument.
Claims (1)
定し、それとあわせて分極特性などを測定する内部照合
型の照合電極において、銀−塩化銀からなる金属電極を
設置した外界から隔離絶縁された電極室と、該電極室内
の前記金属電極を覆うように設けた塩化カリウム微粉末
を含む保護管と、前記電極室内に高温高圧容器内の純水
を取り込む液絡管とを備え、前記電極室内に電極反応に
必要な一定量のＣｌ＾−を供給して前記高温高圧容器内
の供試金属表面電位を測定する構成としたことを特徴と
する照合電極。 ２、前記金属電極の前記高温高圧容器外側の端部には前
記電極室内の液体を一定流速で前記高圧容器外に滲出さ
せて、前記電極室内の電極反応液のＣｌ＾−を測定可能
とする手段を備えている特許請求の範囲第１項記載の照
合電極。 ３、前記液絡管は、前記電極室の電極反応液を前記高温
高圧容器内に逆拡散させないようにするために固定アス
ベスト、アルミナなどの焼結微粒子を充填してある特許
請求の範囲第１項または第２項記載の照合電極。 ４、前記保護管は、塩化カリウム微粉末を多孔質ガラス
で被覆した後、粘土質材料を用いて焼結結合した構成と
してある特許請求の範囲第１項または第２項または第３
項記載の照合電極。[Scope of Claims] 1. A metal electrode made of silver-silver chloride is installed in an internal verification type reference electrode that measures the electrode potential of a metal surface in a high-temperature, high-pressure pure water environment and also measures polarization characteristics. an electrode chamber isolated and insulated from the outside world, a protective tube containing fine potassium chloride powder provided to cover the metal electrode in the electrode chamber, and a liquid junction tube that introduces pure water in a high-temperature and high-pressure container into the electrode chamber. A reference electrode characterized in that it is configured to supply a certain amount of Cl^- necessary for an electrode reaction into the electrode chamber and measure the surface potential of a test metal in the high temperature and high pressure container. 2. At the outer end of the high temperature and high pressure container of the metal electrode, the liquid in the electrode chamber is allowed to ooze out of the high pressure container at a constant flow rate, so that Cl^- of the electrode reaction liquid in the electrode chamber can be measured. A reference electrode according to claim 1, comprising means. 3. The liquid junction tube is filled with sintered fine particles such as fixed asbestos or alumina in order to prevent the electrode reaction liquid in the electrode chamber from back diffusing into the high temperature and high pressure container. Reference electrode according to item 1 or 2. 4. The protection tube is constructed by coating potassium chloride fine powder with porous glass and then sintering and bonding it using a clay material.
Reference electrode as described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10092386A JPS62259054A (en) | 1986-05-02 | 1986-05-02 | Reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10092386A JPS62259054A (en) | 1986-05-02 | 1986-05-02 | Reference electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62259054A true JPS62259054A (en) | 1987-11-11 |
Family
ID=14286866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10092386A Pending JPS62259054A (en) | 1986-05-02 | 1986-05-02 | Reference electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62259054A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006177678A (en) * | 2004-12-20 | 2006-07-06 | Dkk Toa Corp | Reference electrode |
| JP2019113316A (en) * | 2017-12-20 | 2019-07-11 | ラピスセミコンダクタ株式会社 | Reference electrode |
-
1986
- 1986-05-02 JP JP10092386A patent/JPS62259054A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006177678A (en) * | 2004-12-20 | 2006-07-06 | Dkk Toa Corp | Reference electrode |
| JP2019113316A (en) * | 2017-12-20 | 2019-07-11 | ラピスセミコンダクタ株式会社 | Reference electrode |
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