JPH0363702B2 - - Google Patents
Info
- Publication number
- JPH0363702B2 JPH0363702B2 JP58078923A JP7892383A JPH0363702B2 JP H0363702 B2 JPH0363702 B2 JP H0363702B2 JP 58078923 A JP58078923 A JP 58078923A JP 7892383 A JP7892383 A JP 7892383A JP H0363702 B2 JPH0363702 B2 JP H0363702B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- oxygen
- oxygen sensor
- acid
- aqueous solution
- 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 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
- G01N27/403—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)
- Measuring Oxygen Concentration In Cells (AREA)
Description
【発明の詳細な説明】
技術分野
本発明は気体及び液体中の酸素を検出するガル
バニ電池式酸素センサに関する。DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to galvanic cell oxygen sensors for detecting oxygen in gases and liquids.
従来技術
ガルバニ電池式酸素センサは、電解質として従
来はアルカリ性水溶液を使用したが、水酸化カリ
ウムまたは水酸化ナトリウムの水溶液はアルカリ
濃度が通常3.5重量％であつて、−５℃で凍結し、
これによる体積膨張のために、酸素透過性隔膜が
ふくれたり、破損する欠点があり、さらに測定気
体が酸素のほかに、酸性気体たとえば二酸化炭素
を含むときは、これを吸収して、アルカリ濃度が
変化するので、長期間にわたつて使用することが
できない欠点があつた。Prior Art Galvanic cell type oxygen sensors have conventionally used an alkaline aqueous solution as an electrolyte, but the aqueous solution of potassium hydroxide or sodium hydroxide usually has an alkaline concentration of 3.5% by weight and freezes at -5°C.
Due to the volumetric expansion caused by this, the oxygen-permeable diaphragm may swell or break. Furthermore, if the gas to be measured contains acidic gases such as carbon dioxide in addition to oxygen, this will be absorbed and the alkaline concentration will increase. It has the disadvantage that it cannot be used for a long period of time because it changes.
発明の目的
本発明の目的は上記欠点を解消するガルバニ電
池式酸素センサを提供することである。OBJECTS OF THE INVENTION It is an object of the invention to provide a galvanic cell oxygen sensor which overcomes the above-mentioned drawbacks.
発明の構成
本出願の一つの発明は、陽極、陰極、酸素透過
性隔膜および電解質を有するガルバニ電池式酸素
センサにおいて、電解質が、過塩素酸、テトラフ
ルオロほう酸、またはヘキサフルオロけい酸から
なることを特徴とするガルバニ電池式酸素センサ
である。Structure of the Invention One invention of the present application is a galvanic cell oxygen sensor having an anode, a cathode, an oxygen-permeable diaphragm, and an electrolyte, in which the electrolyte is made of perchloric acid, tetrafluoroboric acid, or hexafluorosilicic acid. This is a galvanic cell type oxygen sensor.
本発明のガルバニ電池式酸素センサは陽極金属
を鉛とすることができ、また電解質水溶液にはコ
ロイド状無水けい酸を混入して、ゾルまたはゲル
状とすることが好ましい。また過塩素酸、テトラ
フルオロほう酸、またはヘキサフルオロけい酸を
20〜50重量％水溶液として使用すれば、凝固点が
−20℃以下になるので、低温で使用することがで
きる。 In the galvanic cell type oxygen sensor of the present invention, the anode metal can be lead, and it is preferable that colloidal silicic anhydride is mixed in the electrolyte aqueous solution to form a sol or gel. Also, do not use perchloric acid, tetrafluoroboric acid, or hexafluorosilicic acid.
When used as a 20 to 50% by weight aqueous solution, the freezing point is -20°C or lower, so it can be used at low temperatures.
作 用
一般に、ガルバニ電池式酸素センサは、第１図
に示すように、容器１はポリエチレンまたは塩化
ビニルなどの絶縁材料からなり、陰極２は金また
は白金などの貴金属からなり、陽極３は鉛などの
卑金属からなる。酸素透過性隔膜４は液体不透過
性であつて、容器１内の電解質５に測定雰囲気を
接触させて電解質５に酸素を溶解させる、多孔性
のポリエチレンまたはポリ四ふつ化エチレンなど
からなる。酸素は陰極２面で反応するので、酸素
透過性隔膜４は陰極２面に接して配置し、陰極２
面上の電解質５に測定雰囲気中の酸素量に対応し
た酸素濃度を与える。両極における反応は次のと
おりである。Function Generally, in a galvanic cell type oxygen sensor, as shown in Fig. 1, the container 1 is made of an insulating material such as polyethylene or vinyl chloride, the cathode 2 is made of a noble metal such as gold or platinum, and the anode 3 is made of lead or the like. consisting of base metals. The oxygen-permeable diaphragm 4 is liquid-impermeable and is made of porous polyethylene or polytetrafluoroethylene, etc., and allows the measurement atmosphere to come into contact with the electrolyte 5 in the container 1 to dissolve oxygen in the electrolyte 5. Since oxygen reacts on the two surfaces of the cathode, the oxygen permeable diaphragm 4 is placed in contact with the two surfaces of the cathode.
An oxygen concentration corresponding to the amount of oxygen in the measurement atmosphere is applied to the electrolyte 5 on the surface. The reactions at both poles are as follows.
陰極 O2＋4H+＋4e-→2H2O (1)
陽極 2Pb＋2H2O→2PbO＋4H+＋4e- (2)
すなわち陰極においては、O2がH+と反応して
H2Oを生成し、外部回路からe-を取入れる。陽
極においては、PbがH2Oと反応してPbOとなり、
H+を生成し、かつ外部回路にe-を供給する。流
れる電流は酸素濃度に比例するので電流を測定す
ることにより酸素濃度を知ることができる。生成
したPbOが陽極であるPb表面をおおうと、電極
反応が進行しなくなるので、電解質の酸はPbOと
反応して溶解させる必要がある。Cathode O 2 +4H + +4e - →2H 2 O (1) Anode 2Pb+2H 2 O→2PbO+4H + +4e - (2) In other words, at the cathode, O 2 reacts with H +
Generates H 2 O and takes in e - from an external circuit. At the anode, Pb reacts with H 2 O to become PbO,
Generates H + and supplies e - to external circuits. Since the flowing current is proportional to the oxygen concentration, the oxygen concentration can be determined by measuring the current. If the generated PbO covers the Pb surface of the anode, the electrode reaction will not proceed, so the electrolyte acid must react with the PbO and dissolve it.
また電解質は通常の使用において凍結してはな
らないので、酸濃度20〜50重量％において凝固点
が−20℃以下とする。 Furthermore, since the electrolyte must not freeze during normal use, the freezing point should be -20°C or lower at an acid concentration of 20 to 50% by weight.
さらに電解質は陽極のPbを溶解してはならな
い。また電解質の酸は使用中に分解または揮発し
てはならない。 Furthermore, the electrolyte must not dissolve the Pb in the anode. Also, the acid in the electrolyte must not decompose or volatilize during use.
これらの条件をすべて満足する酸としては、過
塩素酸、テトラフルオロほう酸またはヘキサフル
オロけい酸を使用することができる。 Perchloric acid, tetrafluoroboric acid, or hexafluorosilicic acid can be used as the acid that satisfies all of these conditions.
なお、電解質５をゲル状とすることによつて、
陰極２と酸素透過性隔膜４との間にはさまれた電
解質層の厚みを一定に保持し、かつセンサの姿勢
変化に伴なう両極間の液絡の変化を防止し、これ
によつて、良好な応答特性を維持することができ
る。 In addition, by making the electrolyte 5 into a gel state,
The thickness of the electrolyte layer sandwiched between the cathode 2 and the oxygen-permeable diaphragm 4 is maintained constant, and the liquid junction between the two electrodes is prevented from changing due to changes in the sensor's posture. , good response characteristics can be maintained.
実施例
第１図に示す装置を使用して、二酸化炭素含量
を変えた酸素・窒素混合雰囲気を、従来のアルカ
リ性電解質を使用する酸素センサと本発明の電解
質を使用する酸素センサで測定したときの経過期
間と出力電圧との関係を第２図に示す。Example Using the apparatus shown in Fig. 1, an oxygen/nitrogen mixed atmosphere with varying carbon dioxide content was measured using an oxygen sensor using a conventional alkaline electrolyte and an oxygen sensor using the electrolyte of the present invention. FIG. 2 shows the relationship between elapsed period and output voltage.
測定雰囲気は10％CO2、20.9％O2、残部N2、ま
たは0.03％CO2、20.9％O2、残部N2とし、従来の
電解質として、3.5重量％NaOH水溶液Ｎ、本発
明の電解質として、44重量％HClO4水溶液にコ
ロイド状無水けい酸を４重量％添加したものＣ、
41重量％H2SiF6水溶液にコロイド状無水けい酸
を４重量％添加したものＳ、および33重量％
HBF4水溶液にコロイド状無水けい酸を４重量％
添加したものＢとした。従来のアルカリ性電解質
Ｎは10％CO2の場合ａは、50日を過ぎると出力が
低下し、0.03％CO2の場合ｂは、300日後には出
力が低下した。これに対して、本発明の電解質は
いずれも、CO2濃度が10％の場合ａも、0.03％の
場合ｂも900日経過後にようやく出力が低下しは
じめた。 The measurement atmosphere was 10% CO 2 , 20.9% O 2 , balance N 2 , or 0.03% CO 2 , 20.9% O 2 , balance N 2 , and the conventional electrolyte was 3.5% NaOH aqueous solution N, and the electrolyte of the present invention was 3.5% NaOH aqueous solution N. , 4% by weight of colloidal silicic anhydride added to a 44% by weight HClO 4 aqueous solution C,
41 wt% H 2 SiF 6 aqueous solution with 4 wt% colloidal silicic anhydride added, and 33 wt%
4% by weight of colloidal silicic anhydride in HBF 4 aqueous solution
Added product B was added. In the case of conventional alkaline electrolyte N with 10% CO 2 , the output decreased after 50 days in case a, and in the case of 0.03% CO 2 in case b the output decreased after 300 days. On the other hand, in all of the electrolytes of the present invention, the output began to decrease only after 900 days had elapsed in both cases (a) when the CO 2 concentration was 10% and cases (b) when the CO 2 concentration was 0.03%.
第１図はガルバニ電池式酸素センサの略断面図
であり、第２図は本発明および従来技術のガルバ
ニ電池式酸素センサの経過期間と出力電圧との関
係を示すグラフである。
１……容器、２……陰極、３……陽極、４……
酸素透過性隔膜、５……電解質、Ｎ……3.5％
NaOHセンサ、Ｃ……44％HClO4センサ、Ｓ…
…41％H2SiF6センサ、Ｂ……33％HBF4センサ、
ａ……10％CO2、ｂ……0.03％CO2。
FIG. 1 is a schematic cross-sectional view of a galvanic cell type oxygen sensor, and FIG. 2 is a graph showing the relationship between the elapsed period and the output voltage of the galvanic cell type oxygen sensor of the present invention and the prior art. 1... Container, 2... Cathode, 3... Anode, 4...
Oxygen permeable diaphragm, 5...electrolyte, N...3.5%
NaOH sensor, C...44%HClO 4 sensor, S...
...41% H2SiF 6 sensors, B...33%HBF 4 sensors,
a...10% CO2 , b...0.03% CO2 .
Claims (1)
有するガルバニ電池式酸素センサにおいて、電解
質が過塩素酸、テトラフルオロほう酸、またはヘ
キサフルオロけい酸の水溶液であることを特徴と
するガルバニ電池式酸素センサ。 ２ 陽極金属が鉛である、特許請求の範囲第１項
記載の酸素センサ。 ３ 電解質水溶液にコロイド状無水けい酸を混入
してゾルまたはゲル状とした、特許請求の範囲第
１項記載の酸素センサ。[Scope of Claims] 1. A galvanic cell oxygen sensor having an anode, a cathode, an oxygen-permeable diaphragm, and an electrolyte, characterized in that the electrolyte is an aqueous solution of perchloric acid, tetrafluoroboric acid, or hexafluorosilicic acid. Galvanic cell type oxygen sensor. 2. The oxygen sensor according to claim 1, wherein the anode metal is lead. 3. The oxygen sensor according to claim 1, wherein colloidal silicic anhydride is mixed into an electrolyte aqueous solution to form a sol or gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58078923A JPS59204754A (en) | 1983-05-07 | 1983-05-07 | Galvanic cell type oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58078923A JPS59204754A (en) | 1983-05-07 | 1983-05-07 | Galvanic cell type oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59204754A JPS59204754A (en) | 1984-11-20 |
| JPH0363702B2 true JPH0363702B2 (en) | 1991-10-02 |
Family
ID=13675375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58078923A Granted JPS59204754A (en) | 1983-05-07 | 1983-05-07 | Galvanic cell type oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59204754A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2813844B1 (en) * | 2013-06-13 | 2017-02-08 | Honeywell International Inc. | Oxygen galvanic sensor based on noble metals |
Family Cites Families (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
- 1983-05-07 JP JP58078923A patent/JPS59204754A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59204754A (en) | 1984-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4132616A (en) | Gas sensor | |
| EP1959253B1 (en) | Electrochemical sensor | |
| US3296113A (en) | Gas-stream monitor | |
| EP1332358A1 (en) | Acid gas measuring sensors and method of making same | |
| US4622105A (en) | Method for measuring gaseous sulfur dioxide | |
| US4477403A (en) | Method of making an electrochemical sensor | |
| JPH0363702B2 (en) | ||
| US4981567A (en) | Lithium-salt reference half-cell for potentiometric determinations | |
| GB2140566A (en) | Powdered liquid electrolyte | |
| JPH0239740B2 (en) | ||
| JP2001289816A (en) | Controlled potential electrolysis type gas sensor | |
| US4149948A (en) | Electrochemical cell for detecting hydrogen sulphide in a gaseous mixture | |
| JPH041495Y2 (en) | ||
| JPS60112266A (en) | Specific gravity sensor for lead storage battery | |
| JPS63231258A (en) | Sensor | |
| JPS5944649A (en) | Electrochemical device for measuring partial pressure of oxygen in gas or liquid atmosphere | |
| JPH0334824B2 (en) | ||
| JPH0334690Y2 (en) | ||
| JPH0346371Y2 (en) | ||
| JPH0625746B2 (en) | Electrochemical acid gas detector | |
| JPH0336190B2 (en) | ||
| JPH0425753A (en) | Gas sensor | |
| JPH032258B2 (en) | ||
| JPS59145954A (en) | Oxygen sensor | |
| JPS5937455A (en) | Gas sensor |