JPH045942B2 - - Google Patents
Info
- Publication number
- JPH045942B2 JPH045942B2 JP57174616A JP17461682A JPH045942B2 JP H045942 B2 JPH045942 B2 JP H045942B2 JP 57174616 A JP57174616 A JP 57174616A JP 17461682 A JP17461682 A JP 17461682A JP H045942 B2 JPH045942 B2 JP H045942B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- internal
- silver
- liquid
- acetyl cellulose
- 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
Links
- 229940081735 acetylcellulose Drugs 0.000 claims description 16
- 229920002301 cellulose acetate Polymers 0.000 claims description 16
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 claims description 14
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 25
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】
〔発明の利用分野〕
各種イオンの活量測定に用いられる比較電極や
イオン選択性電極の内部電極に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to internal electrodes of reference electrodes and ion-selective electrodes used for measuring the activities of various ions.
PH等の各種イオンの活量を測定するために使用
される比較電極は、基準電位の提供と被検液との
電気的接続を確実安定化させるために用いられ
る。そのためには優れた内部電極を備えると共に
能率的な液絡部を有することが重要な項目とな
る。優れた内部電極の要件としては高感度で長寿
命であること、液絡部としての電気抵抗が小さ
く、内部液と被検液との間の液間電位が小さいこ
と等である。
The reference electrode used to measure the activity of various ions such as PH is used to provide a reference potential and to ensure stable electrical connection with the test liquid. To this end, it is important to have excellent internal electrodes and an efficient liquid junction. Requirements for an excellent internal electrode include high sensitivity and long life, low electrical resistance as a liquid junction, and low liquid junction potential between the internal liquid and the test liquid.
また、内部電極としては従来塩化第１水銀を用
いた甘汞電極が使用されてきた。この甘汞電極は
円筒形のガラス管の中に水銀を入れてそれに白金
線端を接触させ、水銀の下部には塩化第１水銀
（Hg2Cl2）と塩化カリウム（KCl）とを混合しペ
ースト状にして収容している。なお、その下部は
アスベスト栓で封じ、電気的に外部と導通させて
いる。 Further, as the internal electrode, a mercury electrode using mercurous chloride has conventionally been used. In this electrode, mercury is placed in a cylindrical glass tube and the end of the platinum wire is brought into contact with it. Below the mercury, mercurous chloride (Hg 2 Cl 2 ) and potassium chloride (KCl) are mixed. It is stored in a paste form. The lower part is sealed with an asbestos plug, making it electrically conductive to the outside.
このような甘汞電極は水銀化合物を使用してお
り安全衛生上好ましくないので、現在は甘汞電極
の代りに銀−塩化銀（Ag／AgCl）電極が内部電
極として一般に使用されるようになつた。この銀
−塩化銀電極に要求される特性は、時間と共に出
力電位が変化しないこと、即ち、長寿命であるこ
とである。特に、この電極は飽和塩化カリウム溶
液又は3.3MKCl溶液等の濃い内部液に接してい
るために銀−塩化銀電極は塩化カリウムとの間に
錯体を形成して短時間で劣化し易いという欠点を
もつていた。また、内部液である塩化カリウム溶
液に不溶性の塩化銀が生じて液絡部が目詰りす
る。このようになると液絡部の電気抵抗が増加
し、液間起電力の増加が原因で使用不能になると
いう問題点をもつていた。 Since these electrodes use mercury compounds, which are unfavorable in terms of safety and hygiene, silver-silver chloride (Ag/AgCl) electrodes are now generally used as internal electrodes instead of electrodes. Ta. The characteristic required of this silver-silver chloride electrode is that the output potential does not change over time, that is, it has a long life. In particular, since this electrode is in contact with a concentrated internal solution such as a saturated potassium chloride solution or a 3.3M KCl solution, the silver-silver chloride electrode has the disadvantage of forming a complex with potassium chloride and easily deteriorating in a short period of time. It was also on. Furthermore, insoluble silver chloride is generated in the potassium chloride solution, which is the internal solution, and the liquid junction becomes clogged. When this happens, the electrical resistance of the liquid junction increases, resulting in an increase in the electromotive force between the liquids, resulting in a problem that the device becomes unusable.
本発明は上記従来技術の欠点を解消し、長期間
高性能で作動する比較電極等の内部電極を提供す
ることである。
The present invention eliminates the drawbacks of the prior art described above and provides an internal electrode such as a reference electrode that operates with high performance over a long period of time.
本発明は、銀−塩化銀線をアセチルセルローズ
で被覆したものを内部電極とし、アセチルセルロ
ーズ被覆膜の厚さを10〜150μｍに形成せしめた
ことを特徴とする。
The present invention is characterized in that a silver-silver chloride wire coated with acetyl cellulose is used as an internal electrode, and the acetyl cellulose coating film is formed to have a thickness of 10 to 150 μm.
第１図は本発明の一実施例である比較電極の垂
直断面図である。この比較電極はダブルジヤンク
シヨンタイプと呼ばれるもので、リード線２と接
続片３を介して接続された銀−塩化銀製内部電極
４を浸漬している濃内部液６を収容した部分と、
その下端に取り付けたセラミツク製のポーラス栓
８を介して電気的に導通する淡内部液７を収容し
た部分とで構成され、支持管１０で一体化されて
いる。
FIG. 1 is a vertical sectional view of a comparison electrode according to an embodiment of the present invention. This reference electrode is of a double junction type, and includes a portion containing a concentrated internal liquid 6 in which a silver-silver chloride internal electrode 4 connected via a lead wire 2 and a connecting piece 3 is immersed;
It is composed of a portion containing a fresh internal liquid 7 that is electrically connected via a porous plug 8 made of ceramic attached to the lower end thereof, and is integrated with a support tube 10.
支持管１０の上端に設置したキヤツプ１は中央
孔よりリード線２を引き出して気密に封じてお
り、支持管１０の上側面に設けた孔１２ａは濃内
部液６である飽和塩化カリウム溶液の補充口であ
る。また、支持管１０の中央側面に形成した孔１
２ｂは淡内部液である希薄塩化カリウム溶液の補
充口であり、支持管１０の下端はイオン透過性薄
膜９をガイド１１で取り付けて封じている。この
イオン透過性薄膜９を介して被検液と淡内部液と
は電気的に導通している。 A cap 1 installed at the upper end of the support tube 10 has a lead wire 2 pulled out from the center hole and sealed airtightly, and a hole 12a provided on the upper side of the support tube 10 is used for replenishing the concentrated internal liquid 6, a saturated potassium chloride solution. It is the mouth. In addition, a hole 1 formed in the center side of the support tube 10
Reference numeral 2b is a replenishment port for a dilute potassium chloride solution, which is a dilute internal liquid, and the lower end of the support tube 10 is sealed by attaching an ion-permeable thin film 9 with a guide 11. The test liquid and the fresh internal liquid are electrically connected through this ion-permeable thin film 9.
上記銀−塩化銀内部電極４はテトラヒドロフラ
ン等の有機溶媒に溶かしたアセチルセルローズ溶
液に浸漬して付着させ、これを乾燥させてアセチ
ルセルローズ膜５を形成させている。 The silver-silver chloride internal electrode 4 is attached by immersing it in an acetylcellulose solution dissolved in an organic solvent such as tetrahydrofuran, and is dried to form an acetylcellulose film 5.
このように構成した比較電極は、イオン透過性
薄膜９を介して被検液が電極内に滲透しても濃内
部液６内にまで拡散侵入することがないので、長
期間高感度で安定した測定が可能となる。また、
ポーラス栓８は多数の細孔で濃内部液６と淡内部
液７とを電気的に導通し、イオン透過性薄膜９を
介して取り入れたイオン電流を内部電極４に伝え
ている。 The reference electrode configured in this way does not diffuse into the concentrated internal liquid 6 even if the test liquid permeates into the electrode through the ion-permeable thin film 9, so it is highly sensitive and stable for a long period of time. Measurement becomes possible. Also,
The porous stopper 8 electrically connects the concentrated internal liquid 6 and the lean internal liquid 7 through a large number of pores, and transmits the ionic current taken in through the ion-permeable thin film 9 to the internal electrode 4.
第２図は第１図の比較電極の銀−塩化銀電極を
被覆したアセチルセルローズの膜厚と電極の寿命
日数との関係を示す線図で、斜め実線と交わる２
つの上下方向の線分は50μ、100μ膜厚の複数電極
の寿命日数の分布を示している。即ち、膜厚50μ
のときの寿命は25〜30日であり、膜厚100μのと
きの寿命は50〜60日であつた。 Figure 2 is a diagram showing the relationship between the film thickness of the acetyl cellulose coating the silver-silver chloride electrode of the comparison electrode in Figure 1 and the lifespan of the electrode.
The two vertical line segments show the distribution of lifetimes of multiple electrodes with film thicknesses of 50μ and 100μ. That is, the film thickness is 50μ
When the film thickness was 100 μm, the lifespan was 25 to 30 days, and when the film thickness was 100 μm, the lifespan was 50 to 60 days.
このように膜厚が大となると寿命は伸びるが、
一面応答性は低下する。また、膜厚が大きいとき
は均一な厚さで被覆することは困難となる。これ
らのことより親水性のアセチルセルローズ膜５の
厚さは10μ〜150μ程度が適当で、アセチルセルロ
ーズ膜５を施さない場合の２〜３日の寿命に比較
すると２〜30倍にもなつている。尚、第２図のａ
点は膜厚が10μ程度の所で、膜厚零の場合よりは
寿命が上昇している。このようなアセチルセルロ
ーズの僅かな厚さの膜でも銀−塩化銀内部電極４
の保護作用にもつており、取り扱い時に他の部材
に接触して生じる傷や塩化銀の剥離等の劣化原因
を除くことができる。 In this way, as the film thickness increases, the lifespan increases, but
One-sided responsiveness decreases. Furthermore, when the film thickness is large, it is difficult to coat with a uniform thickness. From these facts, the appropriate thickness of the hydrophilic cellulose acetate film 5 is about 10μ to 150μ, which is 2 to 30 times longer than the 2 to 3 day lifespan when the cellulose acetate film 5 is not applied. . In addition, a in Figure 2
The point is where the film thickness is about 10μ, and the lifespan is higher than when the film thickness is zero. Even with such a small film of acetyl cellulose, the silver-silver chloride internal electrode 4
It also has a protective effect, and can eliminate causes of deterioration such as scratches caused by contact with other parts during handling and peeling of silver chloride.
本実施例の比較電極は、銀−塩化銀よりなる内
部電極に親水性のアセチルセルローズを10〜
150μ程度被覆することにより、内部電極を保護
して大幅に寿命を伸ばすことができるという効果
が得られる。 The comparative electrode of this example has hydrophilic acetyl cellulose in the internal electrode made of silver-silver chloride.
A coating of about 150 μm has the effect of protecting the internal electrodes and significantly extending their lifespan.
第３図は本発明の他の実施例であるイオン選択
性電極の垂直断面図で、第１図と同じ部分には同
一符号を付してある。この場合は支持管１３の底
部に感応膜１５を装着し、この感応膜１５を介し
て内部液１４内に浸入した被検液中のイオンを内
部電極４が検知する。この内部電極４に上記と同
様なアセチルセルローズ膜５を施すことによつ
て、同様に寿命を大幅に向上させることができ
る。 FIG. 3 is a vertical cross-sectional view of an ion-selective electrode according to another embodiment of the present invention, in which the same parts as in FIG. 1 are given the same reference numerals. In this case, a sensitive membrane 15 is attached to the bottom of the support tube 13, and the internal electrodes 4 detect ions in the test liquid that have entered the internal liquid 14 through the sensitive membrane 15. By applying an acetylcellulose film 5 similar to that described above to the internal electrode 4, the life span can be greatly improved as well.
本発明によれば、比較電極やイオン選択電極の
内部電極を適正な厚さとなるようにアセチルセル
ローズ膜で被覆するという比較的簡単な改良によ
つて、所望の応答性を維持できるにもかかわら
ず、長期間の使用が可能となる。アセチルセルロ
ーズ膜は塩化カリウム溶液などの内部液に接触し
ても銀−塩化銀線との密着性が低下しないので、
内部電極を長寿命化するのに極めて優れている。
According to the present invention, the desired responsiveness can be maintained by a relatively simple improvement of coating the internal electrodes of the reference electrode and the ion-selective electrode with an acetyl cellulose membrane to an appropriate thickness. , long-term use becomes possible. The acetyl cellulose membrane does not lose its adhesion to the silver-silver chloride wire even if it comes into contact with internal liquids such as potassium chloride solution.
Excellent for extending the life of internal electrodes.
第１図は本発明の一実施例である比較電極の垂
直断面図、第２図は第１図の比較電極の銀−塩化
銀電極を被覆したアセチルセルローズの膜厚と電
極の寿命日数との関係を示す線図、第３図は本発
明の他の実施例であるイオン選択性電極の垂直断
面図である。
１……キヤツプ、２……リード線、３……接続
片、４……内部電極（Ag−AgCl）、５……アセ
チルセルローズ膜、６……濃内部液、７……淡内
部液、８……ポーラス栓、９……イオン透過性薄
膜、１０，１３……支持管、１１……ガイド、１
２……孔、１４……内部液、１５……感応膜。
FIG. 1 is a vertical cross-sectional view of a comparative electrode according to an embodiment of the present invention, and FIG. 2 shows the relationship between the thickness of the acetyl cellulose coating the silver-silver chloride electrode of the comparative electrode of FIG. 1 and the lifespan of the electrode. A diagram showing the relationship, FIG. 3 is a vertical cross-sectional view of an ion-selective electrode according to another embodiment of the present invention. 1... Cap, 2... Lead wire, 3... Connection piece, 4... Internal electrode (Ag-AgCl), 5... Acetyl cellulose membrane, 6... Concentrated internal liquid, 7... Light internal liquid, 8 ...porous stopper, 9 ... ion-permeable thin film, 10, 13 ... support tube, 11 ... guide, 1
2... Pore, 14... Internal liquid, 15... Sensitive membrane.
Claims (1)
するのに用いられる比較電極等の内部電極であつ
て、銀−塩化銀線の表面を親水性物質で被覆した
内部電極において、上記親水性物質がアセチルセ
ルローズであり、アセチルセルローズ被覆膜の厚
さが10〜150μｍであることを特徴とする比較電
極等の内部電極。1. In an internal electrode such as a reference electrode used to electrochemically measure components in an electrolyte-containing sample, the surface of a silver-silver chloride wire is coated with a hydrophilic substance. is acetyl cellulose, and the acetyl cellulose coating film has a thickness of 10 to 150 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17461682A JPS5965248A (en) | 1982-10-06 | 1982-10-06 | Internal electrode such as comparison electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17461682A JPS5965248A (en) | 1982-10-06 | 1982-10-06 | Internal electrode such as comparison electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5965248A JPS5965248A (en) | 1984-04-13 |
| JPH045942B2 true JPH045942B2 (en) | 1992-02-04 |
Family
ID=15981699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17461682A Granted JPS5965248A (en) | 1982-10-06 | 1982-10-06 | Internal electrode such as comparison electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5965248A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5633558B2 (en) * | 1976-10-25 | 1981-08-04 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54122896U (en) * | 1978-02-17 | 1979-08-28 | ||
| JPS5633558U (en) * | 1979-08-22 | 1981-04-02 |
-
1982
- 1982-10-06 JP JP17461682A patent/JPS5965248A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5633558B2 (en) * | 1976-10-25 | 1981-08-04 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5965248A (en) | 1984-04-13 |
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