JPH02201256A - Electrode for measuring ozone - Google Patents
Electrode for measuring ozoneInfo
- Publication number
- JPH02201256A JPH02201256A JP1021852A JP2185289A JPH02201256A JP H02201256 A JPH02201256 A JP H02201256A JP 1021852 A JP1021852 A JP 1021852A JP 2185289 A JP2185289 A JP 2185289A JP H02201256 A JPH02201256 A JP H02201256A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- ozone
- measuring
- buffer solution
- opposed pole
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 6
- 239000008351 acetate buffer Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 239000004332 silver Substances 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003839 salts Chemical group 0.000 abstract description 4
- 239000007853 buffer solution Substances 0.000 abstract description 3
- 239000004809 Teflon Substances 0.000 abstract description 2
- 229920006362 Teflon® Polymers 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 6
- 239000007788 liquid Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- -1 iodide ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明はオゾン測定用電極に係り、特にオゾン測定用
電極の内部電解液に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an ozone measuring electrode, and more particularly to an internal electrolyte of the ozone measuring electrode.
実開昭６２−７１５５５号公報において、作用電極と対
極を保持体内に収納し、作用電極をオゾン透過膜で被覆
し、保持体内に内部電解液を満たしたオゾン測定電極が
開示されている。このオゾン測定電極においては内部電
解液としてリン酸塩緩衝液や酢酸緩衝液が用いられてい
る。上記電極においてはオゾン透過膜を透過したオゾン
は作用電極上で（１）式に従って還元される。Japanese Utility Model Application Publication No. 62-71555 discloses an ozone measuring electrode in which a working electrode and a counter electrode are housed in a holder, the working electrode is covered with an ozone permeable membrane, and the holder is filled with an internal electrolyte. In this ozone measuring electrode, a phosphate buffer or an acetate buffer is used as an internal electrolyte. In the above electrode, ozone that has passed through the ozone permeable membrane is reduced on the working electrode according to equation (1).
Ｕｓ ＋Ｈ，Ｕ＋ ２ｅ →Ｏ，＋ ２０Ｈ・−・−・
−（１）このとき、対極との間に電流が流れこの値は測
定対象のオゾン濃度に比例する。Us +H, U+ 2e →O, + 20H・−・−・
-(1) At this time, a current flows between the electrode and the counter electrode, and this value is proportional to the ozone concentration of the object to be measured.
また特殊な組成の内部電解液としてビーバージと１ｍＭ
ＮａＩと０．１ＭＩＪン酸塩緩衝液からなるものが報告
されている。さらにアール、ビー、スマート等（Ｒ，Ｂ
、 Ｓｍａｒｔ ｅｔａｌ、） 、アナリテイカルグラ
フ減隔膜式電極の報告がみられる。In addition, as an internal electrolyte with a special composition, Beaverage and 1mM
A solution consisting of NaI and 0.1 MIJ phosphate buffer has been reported. In addition, R, B, Smart etc. (R, B
, Smart et al.), there have been reports of analytical graph reduced diaphragm type electrodes.
しかしながら内部電解液にリン酸塩緩衝液や酢酸塩緩衝
液さらには過塩素酸を用いたオゾン測定用電極はオゾン
に対する感度が低く、電極出力が小さいという問題があ
った。その理由としては、オゾンの作用電極における還
元反応が充分活性でないためであると考えられる。However, ozone measurement electrodes using phosphate buffers, acetate buffers, or even perchloric acid as internal electrolytes have a problem of low sensitivity to ozone and low electrode output. The reason for this is thought to be that the reduction reaction of ozone at the working electrode is not sufficiently active.
またピー、バーシュ（Ｐ、Ｈｅｒｓｃｈ ） 等の内
部型Ｂｒ 塩が析出して電極面が汚染するという問題が
あった。Furthermore, there is a problem that internal type Br salts such as P, Hersch, etc. are deposited and the electrode surface is contaminated.
仁の発明は上述の共に鑑みてなされ、その目的はオゾン
と容易に反応ししかもその際、電気化学的に活性な種に
変換されるような内部電解液を用いることにより、感度
と信頼性に優れるオゾン測定用電極を提供することにあ
る。Jin's invention was made in view of the above, and its purpose was to improve sensitivity and reliability by using an internal electrolyte that readily reacts with ozone and is converted into electrochemically active species. The objective is to provide an excellent electrode for ozone measurement.
（ｉ［を題を解決するための手段〕
上述の目的はこの発明ｌζよればガス透過膜および作用
電極、対極、内部電解液を備え、ガス透過膜を透過した
オゾンを１気化学的に検出するオゾン測定用電極におい
て、ヨウ化カリウムを含む酢酸緩衝溶液からなる内部電
解液を備えることにより達成される。(Means for solving the problem) The above-mentioned object is to provide a gas-permeable membrane, a working electrode, a counter electrode, and an internal electrolyte, and to chemically detect ozone that has passed through the gas-permeable membrane. This is achieved by providing an internal electrolyte consisting of an acetate buffer solution containing potassium iodide in the ozone measuring electrode.
ガス透過膜を透過したオゾンは内部電解液に溶解すると
ともに、ＮａＩと反応しこれを酸化して（２）式に従い
オゾン量に対応するＩ、を発生させる。The ozone that has passed through the gas permeable membrane is dissolved in the internal electrolyte, reacts with NaI, oxidizes it, and generates I corresponding to the amount of ozone according to equation (2).
υｍ−ｈＨ，ｔ）＋２１ →（１）ｔ ＋Ｉ、 ＋２０
）１ ・・・・・・・・・（２）発生した１２は
作用電悌において（３）式に従いヨウ化イオンＣＩ ）
に還元される。υm−hH,t)+21 →(1)t +I, +20
)1 ・・・・・・・・・(2) The generated 12 is the iodide ion CI according to the equation (3) in the working electric field.
will be reduced to
Ｉ、＋２ｅ → ２１ ・・・・・・
・・・・・・由（３）このとき作用電極と対極の間に流
れる電流はオゾン虚に対応したものとなる。I, +2e → 21 ・・・・・・
Reason (3) At this time, the current flowing between the working electrode and the counter electrode corresponds to the ozone imaginary.
反応式（２） 、 （３７はいずれも活性で反応適度が
大きいので、全体のスリは容易に進む。Since reaction formulas (2) and (37) are both active and have a large reaction mode, the overall pickpocketing progresses easily.
次にこの発明の実施例を図−に基いて説明する。 Next, embodiments of the present invention will be described with reference to the drawings.
第１図にこの発明の−Ａ施例に係るオゾン測定用電極の
模式断面図が示される。この電極は保持体１１とオゾン
を透過するテフロンからなるガス透過膜１２と白金製作
用−極１３と銀からなる対極１４と０．１Ｍｆｆｕ［！
＠浴液（ｐＨ３）にＫＩｆｌＯｍＭになるようにｍ解し
た内部’ｉｔＭ液１５とから構成される。作用電極１３
と対極１４の間には所定の定′１圧が印加される。作用
を極では反応式（３）に従って工！が還元され、対極で
は（４）式
％式％（４）
に従い銀電極が酸化される。FIG. 1 shows a schematic cross-sectional view of an ozone measuring electrode according to Example -A of the present invention. This electrode consists of a holder 11, a gas-permeable membrane 12 made of Teflon that transmits ozone, a platinum electrode 13, a counter electrode 14 made of silver, and 0.1 Mffu [!
It consists of an internal 'itM solution 15 dissolved in a bath solution (pH 3) to give KIflOmM. Working electrode 13
A predetermined constant pressure of '1' is applied between the electrode 14 and the counter electrode 14. At the pole, the action is calculated according to reaction equation (3)! is reduced, and at the counter electrode, the silver electrode is oxidized according to formula (4).
反応式（２） 、 （３） 、 （４）から全体の反応
は（５）式０、＋Ｈ，Ｏ＋２Ａｇ→０．＋２Ａｇ ＋２
０Ｈ・・・（５）で示される。対極では酸化された銀が
ヨウ化イオンと反応してＡｇＩとなりＡｇ／ＡｇＩ対極
が形成される。From the reaction equations (2), (3), and (4), the overall reaction is as follows (5) equation 0, +H,O+2Ag→0. +2Ag +2
0H...Indicated by (5). At the counter electrode, oxidized silver reacts with iodide ions to become AgI, forming an Ag/AgI counter electrode.
（ｍＶ）との関係を示す検量線と、ＫＩを含まない電解
液を用いたオゾン測定用電極（曲線Ｂ）の検量線とが対
比して示される。(mV) and a calibration curve for an ozone measurement electrode (curve B) using an electrolyte solution that does not contain KI are shown in comparison.
第２図から明らかなように、１０ｍＭになるようにＫＩ
を添加すると、電極の出力は約１０倍に増大することが
わかる。As is clear from Figure 2, KI was adjusted to 10mM.
It can be seen that the output of the electrode increases about 10 times by adding .
ＫＩの添加量を検討するため、ＫＩ濃度を変えて測定し
たところ、３ｍＭから増大効果がみとめられた。また３
０ｍＭ以上添加すると、感度は増大するが、オゾンに対
する電極の応答が遅くなることがみられた。In order to examine the amount of KI added, measurements were performed while varying the KI concentration, and an increasing effect was observed from 3 mM. Also 3
It was found that when 0 mM or more was added, the sensitivity increased, but the response of the electrode to ozone became slower.
このため、ＫＩは３〜３０ｍＭの範囲で添加することが
望ましいことがわかった。For this reason, it was found that it is desirable to add KI in a range of 3 to 30 mM.
また、酢酸緩衝液のｐＨは２〜４が良好であった。Further, the pH of the acetate buffer was preferably 2 to 4.
この発明によればガス透過膜および作用電極。 According to the invention a gas permeable membrane and a working electrode.
対極、内部電解液を備え、ガス透過膜を透過したオゾン
を電気化学的に検出するオゾン測定用電極において、ヨ
ウ化カリウムを含む酢ば緩衝溶液からなる内部電解液を
備えるので、ヨウ化カリウムの触媒作用によりオゾンの
還元速度が大きくなり、そのためにオゾン測定用電極の
感度が向上する。In an ozone measuring electrode that is equipped with a counter electrode and an internal electrolyte and electrochemically detects ozone that has permeated through a gas permeable membrane, it is equipped with an internal electrolyte that is made of a vinegar buffer solution containing potassium iodide. The catalytic action increases the rate of ozone reduction, which improves the sensitivity of the ozone measurement electrode.
またオゾンによるヨウ化カリウムの還元は容易におこる
ので過剰の塩を用いる必要がなく塩の析出による電極汚
染がなくなる。さらにまたヨウ化カリウムにより対極で
ある銀電極がＡｇ／ＡｇＩ電極となり安定化されるなど
の理由によりオゾン測定用電極の信頼性が向上する。Further, since potassium iodide is easily reduced by ozone, there is no need to use excessive salt, and electrode contamination due to salt precipitation is eliminated. Furthermore, the reliability of the ozone measuring electrode is improved because potassium iodide stabilizes the silver electrode, which is the counter electrode, to become an Ag/AgI electrode.
第１図はこの発明の実施例に係るオゾン測定用電極を示
す模式断面図、第２図はこの発明の実施例に係るオゾン
測定用電極の検量関係を示す線図である。FIG. 1 is a schematic sectional view showing an ozone measuring electrode according to an embodiment of the present invention, and FIG. 2 is a diagram showing the calibration relationship of the ozone measuring electrode according to an embodiment of the present invention.
Claims (1)
え、ガス透過膜を透過したオゾンを電気化学的に検出す
るオゾン測定用電極において、ヨウ化カリウムを含む酢
酸緩衝溶液からなる内部電解液を備えることを特徴とす
るオゾン測定用電極。1) In an ozone measuring electrode that electrochemically detects ozone that has passed through the gas permeable membrane, it is equipped with a gas permeable membrane, a working electrode, a counter electrode, and an internal electrolyte, and the internal electrolyte consists of an acetate buffer solution containing potassium iodide. An ozone measurement electrode characterized by comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1021852A JPH02201256A (en) | 1989-01-31 | 1989-01-31 | Electrode for measuring ozone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1021852A JPH02201256A (en) | 1989-01-31 | 1989-01-31 | Electrode for measuring ozone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02201256A true JPH02201256A (en) | 1990-08-09 |
Family
ID=12066642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1021852A Pending JPH02201256A (en) | 1989-01-31 | 1989-01-31 | Electrode for measuring ozone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02201256A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062216U (en) * | 1992-06-12 | 1994-01-14 | 株式会社磯村 | Electrode device for ozone concentration measurement and ozone concentration measurement device |
-
1989
- 1989-01-31 JP JP1021852A patent/JPH02201256A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062216U (en) * | 1992-06-12 | 1994-01-14 | 株式会社磯村 | Electrode device for ozone concentration measurement and ozone concentration measurement device |
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