JPH0650932A - Galvanic-cell type oxidizing gas sensor - Google Patents
Galvanic-cell type oxidizing gas sensorInfo
- Publication number
- JPH0650932A JPH0650932A JP4223435A JP22343592A JPH0650932A JP H0650932 A JPH0650932 A JP H0650932A JP 4223435 A JP4223435 A JP 4223435A JP 22343592 A JP22343592 A JP 22343592A JP H0650932 A JPH0650932 A JP H0650932A
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- oxidizing gas
- counter electrode
- lead
- alkaline earth
- 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.)
- Granted
Links
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は気相あるいは水中に溶存
するオゾンや塩素などの酸化性ガスの濃度を測定するた
めのガスセンサに係わり、更に詳しくは、上記被測定ガ
スの濃度に比例して自ら出力するガルバニ電池式酸化性
ガスセンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas sensor for measuring the concentration of an oxidizing gas such as ozone or chlorine dissolved in a gas phase or water, more specifically, in proportion to the concentration of the gas to be measured. The present invention relates to a galvanic cell type oxidizing gas sensor that outputs itself.
【０００２】[0002]
【従来の技術】気中あるいは水中のオゾンまたは塩素ガ
ス等の酸化ガスの濃度を測定するためには、一般的にガ
ルバニ電池式あるいはポ−ラロ式ガスセンサが使用され
る。2. Description of the Related Art A galvanic cell type or polaro type gas sensor is generally used to measure the concentration of ozone or an oxidizing gas such as chlorine gas in air or water.
【０００３】両センサとも、ガスの透過を制限するため
の隔膜と、電気化学的に酸化性ガスを還元するための作
用極と、還元生活物質よりなる対極と、電解液と、これ
らを収納する容器とで基本的に構成されている。前者は
作用極と対極とが抵抗を介して常時接続されており常に
自ら被検知ガスの濃度に比例して出力するのに対し、後
者は外部から両電極間に一定電圧を印加して作動させそ
の時のみガス濃度に比例した出力が得られる点が異なる
が、両者とも、隔膜の劣化等により経時ドリフトすなわ
ち時間の経過に伴う出力低下を生じるため、定期的な較
正を必要とする。Both sensors house a diaphragm for limiting gas permeation, a working electrode for electrochemically reducing the oxidizing gas, a counter electrode made of a reducing living substance, an electrolytic solution, and the like. It is basically composed of a container. In the former, the working electrode and the counter electrode are always connected via a resistor and always output in proportion to the concentration of the gas to be detected, whereas the latter is operated by applying a constant voltage between both electrodes from the outside. Only at that time, an output proportional to the gas concentration is obtained, but both of them require periodic calibration because drift over time, that is, output reduction with time, occurs due to deterioration of the diaphragm or the like.
【０００４】センサの較正には標準ガスを用いるのがも
っとも一般的であるが、ポ−ラロ式ガスセンサの一部に
は、外部の定電位印加装置により作用極の電位を各々の
ガスの還元反応を生じさせるのに適した固有の電位に自
由に設定できというポ−ラロ式の利点を生かして、大気
中の酸素（通常２１％）に対する出力のドリフト分を求
め、その値を酸素以外のガスに適用して標準ガスなしで
較正することができるようにしたものがある。It is most common to use a standard gas for the calibration of the sensor, but in some polaro gas sensors, the potential of the working electrode is reduced by an external constant potential applying device to reduce each gas. Taking advantage of the polaro formula that can be freely set to a proper electric potential suitable for generating the It has been applied to the standard and can be calibrated without standard gas.
【０００５】[0005]
【発明が解決しようとする課題】一方、ガルバニ電池式
センサの場合には、作用極の電位は対極の電位で自動的
に決定されポ−ラロ式センサのように作用極の電位を自
由に変えることができないため、上記較正方法を採用す
ることはできない。標準ガスで構成するためには常に標
準ガスを常に携帯していなければ成らず、また操作が煩
雑である。On the other hand, in the case of the galvanic cell type sensor, the potential of the working electrode is automatically determined by the potential of the counter electrode, and the potential of the working electrode is freely changed like the polaro sensor. Therefore, the above calibration method cannot be adopted. In order to compose the standard gas, it is necessary to always carry the standard gas, and the operation is complicated.
【０００６】この発明は上記のような課題を解決するた
めに成されたものであり、その目的とするところは、標
準ガスを必要とせず、大気を利用し現場で容易に較正可
能なガルバニ電池式酸化性ガスセンサを提供することで
ある。The present invention has been made in order to solve the above-mentioned problems, and its purpose is not to use a standard gas but to use the atmosphere and to easily calibrate a galvanic battery on site. A type of oxidizing gas sensor is provided.
【０００７】[0007]
【課題を解決するための手段】本発明にかかるガルバニ
電池式酸化性ガスセンサは、オゾンや塩素ガス等の酸化
性ガスおよび酸素ガスの電気化学的還元反応を引き起こ
す作用極と、酸化性ガスに対する出力を求めるための銀
−塩化銀よりなる第一の対極と、大気中の酸素に対する
出力を求めるための鉛よりなる第二の対極と、電解液と
を備え、電解液が酢酸、プロピオン酸、酪酸などの有機
酸と、酢酸鉛、酸化鉛などの鉛化合物と、塩化カリウ
ム、塩化ナトリウム、酸化カルシウム等のアルカリ金属
若しくはアルカリ土類金属の塩化物との混合水溶液であ
ること、又は、電解液が、塩化カリウム、塩化ナトリウ
ム、塩化カルシウム等のアルカリ金属もしくはアルカリ
土類金属の塩化物と、水酸化カリウム、水酸化ナトリウ
ム、水酸化カルシウム等のアルカリ金属もしくはアルカ
リ土類金属の塩基との混合水溶液であること、を特徴と
するものである。A galvanic cell type oxidizing gas sensor according to the present invention has a working electrode that causes an electrochemical reduction reaction of oxidizing gas such as ozone or chlorine gas and oxygen gas, and an output to the oxidizing gas. To prepare a first counter electrode made of silver-silver chloride, a second counter electrode made of lead for obtaining the output for oxygen in the atmosphere, and an electrolytic solution, the electrolytic solution is acetic acid, propionic acid, butyric acid Being a mixed aqueous solution of organic acid such as lead acid, lead compound such as lead acetate and lead oxide, and chloride of alkali metal or alkaline earth metal such as potassium chloride, sodium chloride and calcium oxide, or the electrolytic solution Alkali metal or alkaline earth metal chlorides such as potassium chloride, sodium chloride, calcium chloride and potassium hydroxide, sodium hydroxide, calcium hydroxide It is a mixed aqueous solution of an alkali metal or alkaline earth metal bases etc., it is characterized in.
【０００８】[0008]
【作用】本発明にかかるガルバニ電池式酸化性ガスセン
サにおいて、作用極でオゾン、塩素ガス等酸化性ガスの
還元反応が生じた際の各々対極の反応、電極電位は下記
のように表わされる。 ［銀−塩化銀電極の反応、電極電位］ Ａｇ＋Ｃｌ- →ＡｇＣｌ＋ｅ ＥAg＝０．２２２−０．０５９１×ｌｏｇ［Ｃｌ- ］ ［鉛電極（酸性の場合）の反応、電極電位］ Ｐｂ→Ｐｂ2+＋２ｅ ＥPb＝−０．１２６＋０．０２９５×ｌｏｇ［Ｐｂ2+］ ［鉛電極（アルカリ性の場合）の反応、電極電位］ Ｐｂ＋２ＯＨ- ＝ＰｂＯ＋Ｈ2 Ｏ＋２ｅ ＥPb＝−０．２４８−０．０５９１×ｐＨ （注）［Ｃｌ- ］、［Ｐｂ2+］は、それぞれ電解液中の
鉛イオン、塩素イオン濃度（ｍｏｌ／リットル）を表
す。In the galvanic cell type oxidizing gas sensor according to the present invention, each counter electrode reaction and electrode potential when a reducing reaction of oxidizing gas such as ozone and chlorine gas occurs at the working electrode are expressed as follows. [Reaction of silver-silver chloride electrode, electrode potential] Ag + Cl − → AgCl + e E Ag = 0.222-0.0591 × log [Cl − ] [Reaction of lead electrode (in the case of acidic), electrode potential] Pb → Pb 2 ++ 2e E Pb = -0.126 + 0.0295 × log [Pb 2+ ] [Reaction of lead electrode (in the case of alkaline), electrode potential] Pb + 2OH − = PbO + H 2 O + 2e E Pb = −0.248-0.0591 × pH (Note) [Cl − ] and [Pb 2+ ] respectively represent lead ion and chloride ion concentrations (mol / liter) in the electrolytic solution.
【０００９】上式より、銀−塩化銀電極（第一の対極）
の電位は電解液中の塩素イオンのみにより、鉛電極（第
二の対極）の電位は鉛イオンまたはＰＨのみにより、そ
れぞれ決定されることがわかる。つまり、第一の対極の
電位は塩素イオン濃度を適当に調整することにより作用
極で酸化性ガスの還元反応を促すのに適した電位に、第
二の対極の電位は鉛イオン濃度またはｐＨを適当に調整
することにより作用極の酸素の還元反応を促すのに適し
た電位に、それぞれ独立して設定することが可能であ
る。さらに、各々の対極での生成物は他方の対極の反応
に全く関与しないため、各対極の電位は長期間安定とな
る。従って、大気を用いて較正することが可能となる。From the above formula, the silver-silver chloride electrode (first counter electrode)
It can be seen that the potential of 1 is determined only by chlorine ions in the electrolytic solution, and the potential of the lead electrode (second counter electrode) is determined by only lead ions or PH. That is, the potential of the first counter electrode is set to a potential suitable for promoting the reduction reaction of the oxidizing gas at the working electrode by appropriately adjusting the chloride ion concentration, and the potential of the second counter electrode is set to the lead ion concentration or pH. It is possible to independently set the potentials suitable for promoting the oxygen reduction reaction of the working electrode by adjusting appropriately. Furthermore, since the product at each counter electrode does not participate in the reaction of the other counter electrode at all, the potential of each counter electrode becomes stable for a long period of time. Therefore, it becomes possible to calibrate using the atmosphere.
【００１０】尚、酢酸、プロピオン酸、酪酸などの有機
酸と、酢酸鉛、酸化鉛などの鉛化合物および塩化カリウ
ム、塩化ナトリウム、酸化カルシウム等のアルカリ金属
若しくはアルカリ土類金属の塩化物とからなる混合水溶
液である電解液において、有機酸は電解液の溶解度を高
くし、先のＰｂ→Ｐｂ2+＋２ｅの反応がすみやかに生ず
るようにするためのものである。It is composed of an organic acid such as acetic acid, propionic acid and butyric acid, a lead compound such as lead acetate and lead oxide and a chloride of an alkali metal or alkaline earth metal such as potassium chloride, sodium chloride and calcium oxide. In the electrolytic solution which is a mixed aqueous solution, the organic acid is for increasing the solubility of the electrolytic solution so that the above-mentioned reaction of Pb → Pb 2+ + 2e occurs promptly.
【００１１】[0011]
【実施例】本発明を好適な実施例を用いて説明する。図
１は本発明の一実施例にかかるガルバニ電池式オゾンセ
ンサの断面構造図である。本センサはＡＢＳ樹脂製の容
器１とポ−ラスカ−ボンに金を蒸着した触媒電極とその
外側に設けられた４フッ化エチレン−６フッ化プロピレ
ン共重合体膜の隔膜とでなる作用極２、銀−塩化銀電極
よりなる第一の対極３、鉛よりなる酸素用の第二の対極
４、酢酸と酢酸鉛と塩化カリウムとの混合水溶液からな
る電解液５より構成されており、作用極２と対極３また
は４とは抵抗６を介して外部で閉じており、その時の対
極３または４の選択は切換えスイッチ７により行なわ
る。オゾン測定時には作用極２は第一の対極３と接続さ
れ、酸素測定時、つまり較正時には第二の対極４と接続
される。EXAMPLES The present invention will be described using preferred examples. FIG. 1 is a sectional structural view of a galvanic cell type ozone sensor according to an embodiment of the present invention. This sensor has a working electrode 2 composed of a container 1 made of ABS resin, a catalyst electrode formed by vapor-depositing gold on porous carbon, and a diaphragm of a tetrafluoroethylene-6-fluoropropylene copolymer film provided outside thereof. , A first counter electrode 3 composed of a silver-silver chloride electrode, a second counter electrode 4 composed of lead for oxygen, and an electrolytic solution 5 composed of a mixed aqueous solution of acetic acid, lead acetate and potassium chloride. 2 and the counter electrode 3 or 4 are externally closed via a resistor 6, and the selection of the counter electrode 3 or 4 at that time is performed by a changeover switch 7. The working electrode 2 is connected to the first counter electrode 3 during ozone measurement, and is connected to the second counter electrode 4 during oxygen measurement, that is, during calibration.
【００１２】このガルバニ電池式オゾンセンサのオゾン
濃度１０ vol％における、出力電圧Ｖａ（第一の対極３
使用）及び大気中での出力電圧Ｖｏ（第二の対極４使
用）の変化を図２に、各々の出力比（Ｖａ／Ｖｏ）の変
化を図３に示す。図２に示すように濃度計出力は時間の
経過とともに低下するが、図３に示すようにＶａ／Ｖｏ
の値は一定であること、すなわちオゾンでのドリフトは
酸素でのドリフトと同じであり大気での較正が可能なこ
とがわかる。When the ozone concentration of this galvanic cell type ozone sensor is 10 vol%, the output voltage Va (first counter electrode 3
2) shows changes in the output voltage Vo (using the second counter electrode 4) in the atmosphere) and FIG. 3 shows changes in each output ratio (Va / Vo). As shown in FIG. 2, the output of the densitometer decreases with time, but as shown in FIG.
It can be seen that the value of is constant, that is, the drift in ozone is the same as the drift in oxygen and can be calibrated in air.
【００１３】[0013]
【発明の効果】以上、述べたように本発明にかかるガル
バニ電池式酸化性ガスセンサは、酸化性ガスおよび酸素
ガスの電気化学的還元反応を引き起こす作用極と、酸化
性ガスに対する出力を求めるための銀−塩化銀よりなる
第一の対極と、大気中の酸素に対する出力を求めるため
の鉛よりなる第二の対極と、有機酸と鉛化合物とアルカ
リ金属もしくはアルカリ土類金属の塩化物との混合水溶
液である電解液、又は、アルカリ金属もしくはアルカリ
土類金属の塩化物とアルカリ金属もしくはアルカリ土類
金属の塩基との混合水溶液である電解液とを備えたこと
を特徴とするものである。かかる構成により、標準ガス
を必要とせず、測定現場で煩雑な操作なしに大気中での
較正が可能となった。本発明の価値は極めて大きい。As described above, the galvanic cell type oxidizing gas sensor according to the present invention has a working electrode for causing an electrochemical reduction reaction of oxidizing gas and oxygen gas and an output for the oxidizing gas. Mixing a first counter electrode composed of silver-silver chloride, a second counter electrode composed of lead for obtaining an output for oxygen in the atmosphere, an organic acid, a lead compound, and a chloride of an alkali metal or an alkaline earth metal. It is characterized by comprising an electrolytic solution which is an aqueous solution or an electrolytic solution which is a mixed aqueous solution of a chloride of an alkali metal or an alkaline earth metal and a base of an alkali metal or an alkaline earth metal. With such a configuration, it is possible to perform calibration in the atmosphere without requiring a standard gas and without complicated operation at the measurement site. The value of the present invention is extremely great.
【図１】本発明の一実施例に係るガルバニ電池式オゾン
センサの断面構造図である。FIG. 1 is a sectional structural view of a galvanic cell type ozone sensor according to an embodiment of the present invention.
【図２】ガルバニ電池式オゾンセンサのオゾン濃度１０
vol％における、出力電圧Ｖａ（第一の対極３使用）及
び大気中での出力電圧Ｖｏ（第二の対極４使用）の変化
を示す図である。Fig. 2 Ozone concentration of galvanic cell type ozone sensor 10
It is a figure which shows the change of the output voltage Va (1st counter electrode 3 use) and the output voltage Vo in the atmosphere (2nd counter electrode 4 use) in vol%.
【図３】ガルバニ電池式オゾンセンサのオゾン濃度１０
vol％における、出力電圧Ｖａ（第一の対極３使用）及
び大気中での出力電圧Ｖｏ（第二の対極４使用）の出力
比（Ｖａ／Ｖｏ）の変化を示す図である。Fig. 3 Ozone concentration of galvanic cell type ozone sensor 10
It is a figure which shows the change of the output ratio (Va / Vo) of the output voltage Va (using the first counter electrode 3) and the output voltage Vo in the atmosphere (using the second counter electrode 4) at vol%.
１ 容器 ２ 作用極 ３ 第一の対極 ４ 第二の対極 ５ 電解液 1 Container 2 Working Electrode 3 First Counter Electrode 4 Second Counter Electrode 5 Electrolyte
Claims (2)
酸素ガスの電気化学的還元反応を引き起こす作用極
（２）と、酸化性ガスに対する出力を求めるための銀−
塩化銀よりなる第一の対極（３）と、大気中の酸素に対
する出力を求めるための鉛よりなる第二の対極（４）
と、電解液（５）とを備え、 電解液（５）が、酢酸、プロピオン酸、酪酸などの有機
酸と、酢酸鉛、酸化鉛などの鉛化合物と、塩化カリウ
ム、塩化ナトリウム、酸化カルシウム等のアルカリ金属
若しくはアルカリ土類金属の塩化物との混合水溶液であ
ることを特徴とするガルバニ電池式酸化性ガスセンサ。1. A working electrode (2) for causing an electrochemical reduction reaction of an oxidizing gas such as ozone or chlorine gas and an oxygen gas, and silver for obtaining an output for the oxidizing gas.
A first counter electrode (3) made of silver chloride and a second counter electrode (4) made of lead for obtaining the output for oxygen in the atmosphere.
And an electrolytic solution (5), wherein the electrolytic solution (5) is an organic acid such as acetic acid, propionic acid or butyric acid, a lead compound such as lead acetate or lead oxide, potassium chloride, sodium chloride or calcium oxide. A galvanic cell-type oxidizing gas sensor, which is a mixed aqueous solution of the alkali metal or alkaline earth metal chloride of 1.
ム、塩化カルシウム等のアルカリ金属またはアルカリ土
類金属の塩化物と、水酸化カリウム、水酸化ナトリウ
ム、水酸化カルシウム等のアルカリ金属またはアルカリ
土類金属の塩基との混合水溶液であることを特徴とする
請求項１記載のガルバニ電池式酸化性ガスセンサ。2. The electrolytic solution is a chloride of an alkali metal or alkaline earth metal such as potassium chloride, sodium chloride or calcium chloride, and an alkali metal or alkaline earth such as potassium hydroxide, sodium hydroxide or calcium hydroxide. The galvanic cell type oxidizing gas sensor according to claim 1, which is a mixed aqueous solution of a metal and a base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4223435A JPH07117521B2 (en) | 1992-07-29 | 1992-07-29 | Galvanic battery type oxidizing gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4223435A JPH07117521B2 (en) | 1992-07-29 | 1992-07-29 | Galvanic battery type oxidizing gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0650932A true JPH0650932A (en) | 1994-02-25 |
| JPH07117521B2 JPH07117521B2 (en) | 1995-12-18 |
Family
ID=16798104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4223435A Expired - Lifetime JPH07117521B2 (en) | 1992-07-29 | 1992-07-29 | Galvanic battery type oxidizing gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07117521B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005134135A (en) * | 2003-10-28 | 2005-05-26 | Ai Denshi Kogyo:Kk | Apparatus for measuring concentration of ozone water |
| CN111175451A (en) * | 2020-01-13 | 2020-05-19 | 宁波渤川废液处置有限公司 | Detection method and treatment device of Cl2 detector in waste acid treatment |
-
1992
- 1992-07-29 JP JP4223435A patent/JPH07117521B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005134135A (en) * | 2003-10-28 | 2005-05-26 | Ai Denshi Kogyo:Kk | Apparatus for measuring concentration of ozone water |
| CN111175451A (en) * | 2020-01-13 | 2020-05-19 | 宁波渤川废液处置有限公司 | Detection method and treatment device of Cl2 detector in waste acid treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07117521B2 (en) | 1995-12-18 |
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