JPS60100043A - Polarograph type oxygen densitometer - Google Patents
Polarograph type oxygen densitometerInfo
- Publication number
- JPS60100043A JPS60100043A JP58208143A JP20814383A JPS60100043A JP S60100043 A JPS60100043 A JP S60100043A JP 58208143 A JP58208143 A JP 58208143A JP 20814383 A JP20814383 A JP 20814383A JP S60100043 A JPS60100043 A JP S60100043A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- acid
- cathode
- densitometer
- type oxygen
- 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.)
- Pending
Links
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
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は酸素濃度計、特にポーラログラフ式酸素濃度計
に関するものであり、その目的とするところは、有機酸
と有ｍ酸のアルカリ金属塩との混合水溶液を電解液とす
ることにより、内部抵抗が小さく、寿命の長い酸素濃度
計を提供せんとするにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oxygen concentration meter, particularly a polarographic oxygen concentration meter, and its object is to mix an aqueous solution of an organic acid and an alkali metal salt of a monic acid with an electrolyte. By doing so, we aim to provide an oxygen concentration meter with low internal resistance and long life.
ポーラログラフ式酸素濃度計は、酸素検知極としてのカ
ソードとアノードと電解液とで構成される電気化学セル
のカソードとアノードとの間に定電圧の直流電圧を印加
したとき、カソードとアノードとの間に流れる電流が、
＊＊＊ｉに比例することを利用するものである。従来カ
ソードとしては、金、白金などが使用され、アノードと
して銀が用いられ、電解液として塩化カリの水溶液が用
いられているのが通例である。この場合にはカソード反
応は
０２ ＋ ２Ｈ２０＋４ｅ−→４０Ｈ−−（１）となり
、アノード反応は
４Ａａ＋ ４ＣＩ−−＞ ４ＡｏＣ１＋４ｅ−−−・（
２）となり、全反応は
０２ ＋ ２８２０＋ ＡＡＯ＋ ４ＫＣＩ→４ＫＯＨ
＋ ４ＡＯＣ＋・・・（３）となる。したがって、この
酸素濃度を長期にわたって使用すると電解液がアルカリ
性になるとともに、電解液に不溶性の〜Ｃ１（塩化銀）
が銀アノードの表面を被覆して不働態化する。電解液が
アルカリ性になると、測定の対象となる雰囲気中に＾濃
度の炭酸ガスが含まれる場合には
２ＫＯＨ＋ＣＯ２→に２ ＣＯ３＋Ｈ２０・・・（４）
なる反応により電導性の低いに２ ＣＯ３（炭酸カリ）
が生成する。塩化銀による銀アノードの被覆がこの酸素
濃度計の寿命を短くする。A polarographic oxygen concentration meter is an electrochemical cell consisting of a cathode as an oxygen sensing electrode, an anode, and an electrolyte. When a constant DC voltage is applied between the cathode and anode, the The current flowing in
***It takes advantage of the fact that it is proportional to i. Conventionally, gold, platinum, etc. have been used as the cathode, silver has been used as the anode, and an aqueous solution of potassium chloride has been used as the electrolyte. In this case, the cathode reaction becomes 02 + 2H20+4e-→40H--(1), and the anodic reaction becomes 4Aa+ 4CI--> 4AoC1+4e--(
2), and the total reaction is 02 + 2820 + AAO + 4KCI → 4KOH
+4AOC+...(3). Therefore, if this oxygen concentration is used for a long period of time, the electrolyte becomes alkaline, and ~C1 (silver chloride), which is insoluble in the electrolyte,
coats and passivates the surface of the silver anode. When the electrolyte becomes alkaline, if the atmosphere to be measured contains ^ concentration of carbon dioxide gas, 2KOH + CO2 → 2 CO3 + H20... (4)
2 CO3 (potassium carbonate) has low conductivity due to the reaction
is generated. Coating the silver anode with silver chloride shortens the life of this oximeter.
本発明は、アノードとして鉛もしくはカドミウムを用い
、電解液として、有機酸と有機酸のアルノＪり金属塩と
の酸性混合水溶液を用いることにより、炭酸ガスの影響
がなく、内部抵抗が小さく、しかも寿命が長いポーラロ
グラフ式酸素濃度計を提供するものである。すなわち、
本発明にかかる酸素濃度計では、カソード反応は
Ｑ２ ＋ ４＠＋＋４ｅ−→２Ｈ２０−（５）となり、
アノード反応は
２Ｐｂ＋ ２Ｈ２０−＞ ２ＰｂＯ＋ ４１−１＋＋４
８−− （６）または
ｃｄ−＞ｃｄ＋＋＋２０− ・・・（１）となる。（６
）式によって生成するＰＩＩＯ（酸化鉛）は、電解液の
右ｍ酸に溶解するし、（７）式でもＣＡ（カドミウム）
の反応生成物はカドミウムの有機酸塩となって電解液に
溶解する。したがって、アノード表面は絶えず更新され
、アノード電位は安定づ゛る。この型の酸素濃度計の寿
命は、アノードの反応生成物に対する電解液の溶Ｗｆ度
で決ってくるが、有機酸は一般に大きな溶解度を示す。The present invention uses lead or cadmium as the anode and an acidic mixed aqueous solution of an organic acid and an alnochloride metal salt of the organic acid as the electrolyte, thereby eliminating the influence of carbon dioxide gas and having a low internal resistance. The present invention provides a polarographic oxygen concentration meter with a long life. That is,
In the oxygen concentration meter according to the present invention, the cathode reaction is Q2 + 4@++4e-→2H20-(5),
The anode reaction is 2Pb+ 2H20-> 2PbO+ 41-1++4
8-- (6) or cd->cd+++20- (1). (6
) PIIO (lead oxide) produced by the equation (7) dissolves in the right m acid of the electrolyte, and also CA (cadmium) by the equation (7).
The reaction product becomes an organic acid salt of cadmium and dissolves in the electrolyte. Therefore, the anode surface is constantly renewed and the anode potential becomes more stable. The life of this type of oxygen concentration meter is determined by the degree of solubility of the electrolyte in the anode reaction product, and organic acids generally exhibit a high solubility.
本発明に適した有機酸としては、酢酸、プロピオン酸あ
るいはｎ−酪酸がある。しかるに、これら有機酸単独の
場合には、一般に電導度が低くすぎる。Organic acids suitable for the present invention include acetic acid, propionic acid or n-butyric acid. However, when these organic acids are used alone, the conductivity is generally too low.
この点では、有機酸のアルカリ金属塩を混合すると、電
導度が約２桁上り、酸素濃度別の内部抵抗が下がる。In this respect, when an alkali metal salt of an organic acid is mixed, the conductivity increases by about two orders of magnitude and the internal resistance depending on oxygen concentration decreases.
有機酸のアルカリ金属塩としては、酢酸塩、プロピオン
酸塩、ｎ−醋酸塩、ギ酸塩、シュウ酸塩。Examples of alkali metal salts of organic acids include acetate, propionate, n-acetate, formate, and oxalate.
マレイン酸塩、グルタミン酸塩などが使用可能である。Maleate, glutamate, etc. can be used.
一方、本発明の酸素濃度計の電解液は酸性なので、炭酸
ガスの影響は全く受けない。On the other hand, since the electrolyte of the oxygen concentration meter of the present invention is acidic, it is not affected by carbon dioxide gas at all.
以下本発明の一実施例について詳述する。An embodiment of the present invention will be described in detail below.
実施例；第１図は本発明の一実施例にかかるポーラログ
ラフ式酸素濃度計の断面構造略図を示す。Embodiment: FIG. 1 shows a schematic cross-sectional structure diagram of a polarographic oximeter according to an embodiment of the present invention.
図において、（１）は直径５１１１ｍの白金板からなる
カソード、（２）は鉛からなるアノード、（３）は２．
５モル／見の酢酸と４モル／見の酢酸カリウムとの混合
水溶液からなるｐＨ６，２の電電前液、（４）は４フッ
化エチレン−６フツ化ブチレンコポリマーからなる厚さ
２０μの隔膜、に））は０−リング、（６）はポリ塩化
ビニル製のホルダである。In the figure, (1) is a cathode made of a platinum plate with a diameter of 5111 m, (2) is an anode made of lead, and (3) is 2.
(4) is a diaphragm with a thickness of 20 μ made of tetrafluoroethylene-hexafluorobutylene copolymer; 2)) is an O-ring, and (6) is a holder made of polyvinyl chloride.
上記のカソード（１）と定電圧直流電源装置（７）とは
カソード電流線（８）とセンシング線（９）とで接続さ
れていて、センシング線（９）で検出されたカソード（
１）の電位とアノード（２）の電位との差が一定になる
ように、カソード電流線（８）に直流電流が流れる。カ
ソード電流線（８）に流れる電流値は、抵抗（１０）の
両端部での電圧を測定することによって知ることができ
る。この電流値が！！ｌ索ｍ度と比例する。The above cathode (1) and constant voltage DC power supply (7) are connected by a cathode current line (8) and a sensing line (9), and the cathode (
A direct current flows through the cathode current line (8) so that the difference between the potential of 1) and the potential of the anode (2) is constant. The value of the current flowing through the cathode current line (8) can be determined by measuring the voltage across the resistor (10). This current value! ! It is proportional to the cord m degree.
次に本発明の効果について詳述する。Next, the effects of the present invention will be explained in detail.
土）ホの実施例において、電解液徂をＩｃｃにした酸素
濃度計と、従来の５モル／発塩化カリウムの水溶液を１
ｃｃ用いた酸素濃度別とでそれぞれ空気中での連続酸素
暗度測定をおこなったところ、前者は２（「経過後も出
力電流の変化がないのに対し、５−
後者は１０ケ月で、出力電流の大幅な低下が起り寿命が
尽きた。In the example of E), an oxygen concentration meter with an electrolyte of Icc and a conventional aqueous solution of 5 mol/potassium chloride at 1
Continuous oxygen darkness measurements were performed in the air for each oxygen concentration using cc, and the former showed no change in output current even after 2 months, while the latter showed no change in output current after 10 months. A significant drop in current occurred, and the life of the device came to an end.
以上詳述した如く、本発明は寿命が長いポーラログラフ
式酸素濃度計を提供するもので、その工業的価値極めて
大である。As described in detail above, the present invention provides a polarographic oxygen concentration meter with a long life, and its industrial value is extremely large.
第１図は本発明の一実施例にかかるポーラログラフ式酸
素濃度計の断面構造略図を示す。
１・・・カソード、２・・・アノード、３・・・電解液
、４・・・隔膜、５・・・０−リング、６・・・ホルダ
、７・・・定電圧直流電源装置、８・・・カソード電流
線、９・・・センシ６一FIG. 1 shows a schematic cross-sectional structure of a polarographic oximeter according to an embodiment of the present invention. DESCRIPTION OF SYMBOLS 1... Cathode, 2... Anode, 3... Electrolyte, 4... Diaphragm, 5... O-ring, 6... Holder, 7... Constant voltage DC power supply, 8 ... Cathode current line, 9... Sensi 6-
Claims (1)
とし、鉛もしくはカドミウムをアノードとし、有機酸と
有機酸のアルカリ金属塩との混合水溶液を電解液として
なることを特徴とするポーラログラフ式酸素濃度計。1. Polarographic oxygen, characterized in that a metal with high activity in electrolytically reducing oxygen is used as the cathode, lead or cadmium is used as the anode, and a mixed aqueous solution of an organic acid and an alkali metal salt of the organic acid is used as the electrolyte. Densitometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58208143A JPS60100043A (en) | 1983-11-05 | 1983-11-05 | Polarograph type oxygen densitometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58208143A JPS60100043A (en) | 1983-11-05 | 1983-11-05 | Polarograph type oxygen densitometer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60100043A true JPS60100043A (en) | 1985-06-03 |
Family
ID=16551344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58208143A Pending JPS60100043A (en) | 1983-11-05 | 1983-11-05 | Polarograph type oxygen densitometer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60100043A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176656A (en) * | 1989-12-06 | 1991-07-31 | Tokuyama Soda Co Ltd | Oxygen electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187846A (en) * | 1982-04-27 | 1983-11-02 | Japan Storage Battery Co Ltd | Oxygen densitometer |
-
1983
- 1983-11-05 JP JP58208143A patent/JPS60100043A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187846A (en) * | 1982-04-27 | 1983-11-02 | Japan Storage Battery Co Ltd | Oxygen densitometer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176656A (en) * | 1989-12-06 | 1991-07-31 | Tokuyama Soda Co Ltd | Oxygen electrode |
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