JP3669231B2 - Indicator for measuring dissolved oxygen concentration - Google Patents
Indicator for measuring dissolved oxygen concentration Download PDFInfo
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- JP3669231B2 JP3669231B2 JP30615999A JP30615999A JP3669231B2 JP 3669231 B2 JP3669231 B2 JP 3669231B2 JP 30615999 A JP30615999 A JP 30615999A JP 30615999 A JP30615999 A JP 30615999A JP 3669231 B2 JP3669231 B2 JP 3669231B2
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- Prior art keywords
- dissolved oxygen
- oxygen concentration
- indicator
- dye
- reducing agent
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- 0 CC1C(*)=C(*)C(*)=C(*)C1NC(C=O)=C(C)C(C(CC(*)C(*)=C1*)=C1N)=O Chemical compound CC1C(*)=C(*)C(*)=C(*)C1NC(C=O)=C(C)C(C(CC(*)C(*)=C1*)=C1N)=O 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Description
【０００１】
【発明の属する技術分野】
この発明は、試料溶液中に含まれる溶存酸素濃度を検知するための溶存酸素濃度測定用指示薬に関する。
【０００２】
【従来の技術】
周知のように、ボイラなどの鋼鉄製圧力容器では、給水される水中の溶存酸素を主原因として腐食されるので、脱酸素装置等を通して水中の溶存酸素を減少させ、圧力容器の腐食を防止している。
【０００３】
従来、試料溶液中に含まれる溶存酸素濃度を検知するためにインジゴカルミンを発色色素とした溶存酸素濃度測定用指示薬が使われている。しかし、還元型インジゴカルミンは、空気に接触すると直ちに変色する。そのため、溶存酸素濃度測定用指示薬の発色色素としてインジゴカルミンを用いる場合には、真空封入等の空気との接触を完全に防ぐ必要があった。
【０００４】
【発明が解決しようとする課題】
この発明は、水中の酸素と接触すると変色する溶存酸素濃度測定用指示薬として、
▲１▼溶存酸素濃度が０のときの色を基準にした濃淡により溶存酸素の有無を判断することができる。
▲２▼熱安定性（６０℃にて２４時間以内に分解等を起こさない）が良い。
▲３▼色素と還元剤の反応速度が早すぎず，遅すぎない，程よい反応性（数分では還元反応が終了しないが、２４時間以内には還元反応が終了する）を有する。
▲４▼色素還元後も水に溶解する。
等の条件を満たす還元剤を必要とする。そして、これらの条件を満たす還元剤の中でも、空気中の酸素を還元せず、水に入ったときはじめて還元剤としてはたらく程度の反応速度を有する還元剤が求められている。
【０００５】
【課題を解決するための手段】
この発明は、前記課題を解決するためになされたものであって、請求項１に記載の発明は、一般式（Ｉ）もしくは一般式（II）で表される色素と、ハイドロサルファイト，ロンガリット，塩化スズ，水素化ホウ素塩のうちの少なくとも１種を含む還元剤とからなることを特徴としている。
【０００６】
【化４】
【化５】
請求項２に記載の発明は、前記色素は、一般式（II）で表される色素であることを特徴としている。
【０００９】
【化６】
請求項３に記載の発明は、前記色素は、インジゴカルミンもしくはインジゴトリスルホン酸塩であることを特徴としている。
【００１３】
【発明の実施の形態】
つぎに、この発明の実施の形態について説明する。この発明は、試料溶液，たとえばボイラへの給水の溶存酸素濃度を検知するのに好適に実施することができる。この発明における溶存酸素濃度検出指示薬の主成分として、酸素により変色する色素が適用される。一般式（Ｉ）に記載の色素を使用する利点として、モル吸光係数が大きいので、少量の色素添加でのはっきりとした吸収を示し、また色素の還元状態での安定性が良いことが挙げられる。
【００１４】
【化７】
一般式（II）に記載の色素を使用する利点として、酸化反応が速く測定時間が短くて済み、測定の再現性が良いことが挙げられる。この発明における溶存酸素濃度検出指示薬中の発色色素として、メチレンブルー，インジゴカルミン等が適用されている。
【００１６】
【化８】
還元剤としては、空気中の酸素を還元することなく、水に入ったとき、はじめて還元剤としてはたらく程度の反応性を有するものが必要である。この発明における溶存酸素濃度測定用指示薬中の還元剤として、価数がIII〜IVの硫黄を含む還元剤，すなわちハイドロサルファイト，ロンガリット等が適用され、さらには塩化スズ，水素化ホウ素塩等が適用される。
【００１８】
この発明の溶存酸素濃度測定用指示薬によれば、溶存酸素濃度が０のときの色を基準にした濃淡により溶存酸素の有無を判断することができ、また熱安定性も良い。また、色素の還元速度が速すぎて製造中に酸化するということがないことはもちろん、逆に遅すぎて指示薬として使えないということもない。すなわち、色素と還元剤の反応速度が早すぎず，遅すぎない，程よい反応性を有し、色素還元後も水に溶解するといった条件を満たすことができる。
【００１９】
【実施例】
つぎに、この発明の具体的実施例を詳細に説明する。この発明における溶存酸素濃度測定用指示薬の主成分として、まず発色色素について説明する。発色色素として、まず一般式（Ｉ）で表されるものの具体例として、メチレンブルーについて説明する。メチレンブルーは、モル吸光係数が大きいので、少量の色素添加でもはっきりとした吸収を示し、色素の還元状態での安定性が良いという利点があり、溶存酸素の存在を無色から青色に変化することで検知するようになっている。
【００２０】
【化９】
つぎに、一般式（II）で表されるものの具体例として、インジゴカルミンおよびインジゴトリスルホン酸塩について説明する。インジゴカルミンおよびインジゴトリスルホン酸塩は、酸化反応が速く測定時間が短くて済み、測定の再現性が良いという利点があり、溶存酸素の存在を無色から青色に変化することで検知するようになっている。
【００２２】
【化１０】
ところで、前記メチレンブルーや前記インジゴカルミンおよび前記インジゴトリスルホン酸塩は、還元状態で空気に接すると直ちに酸化され、酸化型として市販されているので、溶存酸素濃度測定用指示薬として使うためには、一度還元剤により還元型に転換する必要がある。さらに、空気中での保存時の酸化を抑えるためにも還元剤を必要とする。
【００２４】
そこで、前記両色素の酸化型から還元型への転換の目的と、空気中での酸化を抑える目的を満たす還元剤について説明する。前記両色素の空気中での酸化を抑える好適な還元剤を特定するために、表１に示した還元剤について、還元性テストおよび保存安定性テストを行い、総合評価を行った。ここにおいて、表１に示した各還元剤の配合量は、前記インジゴカルミン１モルに対して４モルとし、脱酸素条件下で透明バイアルに封入し、それぞれ還元性テストと保存安定性テストを行った。
【００２５】
【表１】
還元性テストとして、常温で５分，常温で２４時間，６０℃で４時間および６０℃で２４時間のテストを行った。この還元性テストの結果を表１に示す。判断基準として、「〇」は、目視で還元されていることを確認できる。「△」は、還元性が不十分である。「×」は、還元されていない。表１から明らかのように、ハイドロサルファイト，ロンガリット，グルコース，塩化スズ，シアノトリヒドロホウ酸ナトリウムおよび水素化ホウ素ナトリウムが還元性を示していることから、還元剤としての条件を満たしている。
【００２７】
保存安定性テストとして、還元剤テストで還元された溶液が６０℃で１週間保存した場合における着色の有無を調査した。この保存安定性テストの結果を表１に示す。判断基準として、「〇」は、還元状態と変化なし。「×」は、透明度が消える。「−」は、還元されなかった溶液である。表１から明らかのように、ハイドロサルファイト，ロンガリット，塩化スズ，シアノトリヒドロホウ酸ナトリウムおよび水素化ホウ素ナトリウムが還元剤として保存安定性を示していることから、還元剤の条件を満たしている。
【００２８】
還元性テストならびに保存安定性テストの結果から、発明者らは、前記インジゴカルミンの空気中での酸化を抑えることに有効な還元剤を評価し、その結果を表１に示した（総合評価欄参照）。判断基準として、「◎」は、最適な還元剤である。「〇」は、備考欄に記載の問題点があるが使用可能である。「×」は、還元剤として不適である。
【００２９】
したがって、還元性ならびに保存安定性のある還元剤が溶存酸素濃度測定用指示薬として必須条件であるので、前記条件を満たす還元剤として、価数がIII〜IVの硫黄を含むハイドロサルファイトおよびロンガリットが有効であり、また塩化スズも有効であり、さらには水素化ホウ素塩のシアノトリヒドロホウ酸ナトリウムおよび水素化ホウ素ナトリウムが有効である。
【００３０】
さらに、発明者らは、前記メチレンブルーについても、前記インジゴカルミンと同様、表１に示した還元剤について、還元性テストおよび保存安定性テストを行い、総合評価を行った。その結果は、前記インジゴカルミンの総合評価とほぼ同様であることを確認した。
【００３１】
【発明の効果】
以上のように、この発明によれば、溶存酸素濃度が０のときの色を基準にした濃淡により溶存酸素の有無を判断することができ、熱安定性が良く、色素と還元剤の反応速度が早すぎず，遅すぎない，程よい反応性を有し、色素還元後も水に溶解する溶存酸素濃度測定用指示薬を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an indicator for measuring dissolved oxygen concentration for detecting the dissolved oxygen concentration contained in a sample solution.
[0002]
[Prior art]
As is well known, steel pressure vessels such as boilers are corroded mainly due to dissolved oxygen in the water being supplied, so the dissolved oxygen in the water is reduced through a deoxidizer to prevent corrosion of the pressure vessel. ing.
[0003]
Conventionally, an indicator for measuring dissolved oxygen concentration using indigo carmine as a coloring dye has been used to detect the dissolved oxygen concentration contained in a sample solution. However, reduced indigo carmine changes color immediately upon contact with air. For this reason, when indigo carmine is used as the coloring pigment of the indicator for measuring the dissolved oxygen concentration, it is necessary to completely prevent contact with air such as vacuum sealing.
[0004]
[Problems to be solved by the invention]
This invention is an indicator for measuring dissolved oxygen concentration that changes color when contacted with oxygen in water.
(1) The presence or absence of dissolved oxygen can be determined from the density based on the color when the dissolved oxygen concentration is 0.
(2) Good thermal stability (no decomposition etc. within 24 hours at 60 ° C.)
(3) The reaction rate of the dye and the reducing agent is neither too fast nor too slow, and has a moderate reactivity (the reduction reaction does not end within a few minutes, but the reduction reaction ends within 24 hours).
(4) It dissolves in water after dye reduction.
A reducing agent that satisfies the above conditions is required. Among the reducing agents that satisfy these conditions, there is a demand for a reducing agent that does not reduce oxygen in the air and has a reaction rate that only works as a reducing agent when it enters water.
[0005]
[Means for Solving the Problems]
The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 includes a dye represented by the general formula (I) or the general formula (II), hydrosulfite, and longalite. And a reducing agent containing at least one of tin chloride and borohydride.
[0006]
[Formula 4]
[Chemical formula 5]
The invention described in claim 2 is characterized in that the dye is a dye represented by the general formula (II).
[0009]
[Chemical 6]
The invention described in claim 3 is characterized in that the dye is indigo carmine or indigo trisulfonate.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Next, an embodiment of the present invention will be described. The present invention can be suitably implemented to detect the dissolved oxygen concentration of sample solution, for example, water supplied to a boiler. As the main component of the dissolved oxygen concentration detection indicator in this invention, a dye that changes color with oxygen is applied. Advantages of using the dye described in the general formula (I) are that the molar extinction coefficient is large, so that it shows clear absorption with a small amount of dye added, and the dye has good stability in the reduced state. .
[0014]
[Chemical 7]
The advantage of using the dye described in the general formula (II) is that the oxidation reaction is fast and the measurement time is short, and the measurement reproducibility is good. Methylene blue, indigo carmine and the like are applied as the coloring dye in the dissolved oxygen concentration detection indicator in this invention.
[0016]
[Chemical 8]
The reducing agent needs to have a reactivity that can only act as a reducing agent when it enters water without reducing oxygen in the air. As the reducing agent in the indicator for measuring dissolved oxygen concentration in this invention, a reducing agent containing sulfur having a valence of III to IV, that is, hydrosulfite, Rongalite, etc. is applied, and further, tin chloride, borohydride salt, etc. Applied.
[0018]
According to the indicator for measuring the dissolved oxygen concentration of the present invention, the presence or absence of dissolved oxygen can be determined from the density based on the color when the dissolved oxygen concentration is 0, and the thermal stability is good. Also, it does not mean that the reduction rate of the dye is too fast to oxidize during production, and conversely, it is not too slow to be used as an indicator. In other words, the reaction rate of the dye and the reducing agent is not too fast and not too slow, and has a moderate reactivity, and can satisfy the condition that it dissolves in water even after the dye reduction.
[0019]
【Example】
Next, specific embodiments of the present invention will be described in detail. As a main component of the indicator for measuring dissolved oxygen concentration in the present invention, first, a coloring dye will be described. First, methylene blue will be described as a specific example of the coloring dye represented by the general formula (I). Methylene blue has a large molar extinction coefficient, so it shows clear absorption even with the addition of a small amount of dye, and has the advantage of good stability in the reduced state of the dye. By changing the presence of dissolved oxygen from colorless to blue It comes to detect.
[0020]
[Chemical 9]
Next, indigo carmine and indigo trisulfonate will be described as specific examples of those represented by the general formula (II). Indigo carmine and indigo trisulfonate have the advantages of fast oxidation reaction, short measurement time, and good measurement reproducibility, and the presence of dissolved oxygen is detected by changing from colorless to blue. ing.
[0022]
[Chemical Formula 10]
By the way, the methylene blue, the indigo carmine, and the indigo trisulfonate are immediately oxidized when they come into contact with air in a reduced state and are commercially available as oxidized forms. It is necessary to convert to a reduced form by a reducing agent. Furthermore, a reducing agent is required to suppress oxidation during storage in air.
[0024]
Therefore, a reducing agent that satisfies the purpose of converting both the dyes from the oxidized form to the reduced form and suppressing the oxidation in air will be described. In order to identify a suitable reducing agent that suppresses the oxidation of both the dyes in the air, the reducing agents shown in Table 1 were subjected to a reducing test and a storage stability test, and an overall evaluation was performed. Here, the amount of each reducing agent shown in Table 1 is 4 moles per 1 mole of the indigo carmine, sealed in a transparent vial under deoxygenated conditions, and subjected to a reducing test and a storage stability test, respectively. It was.
[0025]
[Table 1]
As a reducing test, tests were performed at room temperature for 5 minutes, at room temperature for 24 hours, at 60 ° C. for 4 hours, and at 60 ° C. for 24 hours. The results of this reducing test are shown in Table 1. As a criterion, “◯” can be confirmed to be reduced visually. “Δ” is insufficient in reducibility. “X” is not reduced. As is apparent from Table 1, hydrosulfite, longalite, glucose, tin chloride, sodium cyanotrihydroborate, and sodium borohydride show reducibility, so that the conditions as a reducing agent are satisfied.
[0027]
As a storage stability test, the presence or absence of coloring was investigated when the solution reduced by the reducing agent test was stored at 60 ° C. for 1 week. The results of this storage stability test are shown in Table 1. As a criterion, “◯” is the same as the reduced state. “X” means the transparency disappears. "-" Is a solution that has not been reduced. As is apparent from Table 1, hydrosulfite, longalite, tin chloride, sodium cyanotrihydroborate and sodium borohydride exhibit storage stability as reducing agents, and thus satisfy the conditions for reducing agents. .
[0028]
From the results of the reduction test and the storage stability test, the inventors evaluated a reducing agent effective in suppressing the oxidation of the indigo carmine in the air, and the results are shown in Table 1 (Comprehensive evaluation column). reference). As a criterion for judgment, “で” is an optimum reducing agent. “O” can be used although there are problems described in the remarks column. “X” is not suitable as a reducing agent.
[0029]
Therefore, since a reducing agent having reducibility and storage stability is an indispensable condition as an indicator for measuring dissolved oxygen concentration, hydrosulfite and longalite containing sulfur having a valence of III to IV are used as reducing agents satisfying the above conditions. Effective, tin chloride is also effective, and the borohydride salts sodium cyanotrihydroborate and sodium borohydride are effective.
[0030]
Furthermore, the inventors also conducted a comprehensive evaluation on the methylene blue by performing a reducing test and a storage stability test on the reducing agents shown in Table 1 in the same manner as the indigo carmine. The result confirmed that it was substantially the same as the comprehensive evaluation of the said indigo carmine.
[0031]
【The invention's effect】
As described above, according to the present invention, the presence or absence of dissolved oxygen can be determined based on the density based on the color when the dissolved oxygen concentration is 0, the thermal stability is good, and the reaction rate between the dye and the reducing agent is high. Therefore, it is possible to provide an indicator for measuring dissolved oxygen concentration, which is not too early and not too late, has a moderate reactivity, and dissolves in water even after dye reduction.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30615999A JP3669231B2 (en) | 1999-10-28 | 1999-10-28 | Indicator for measuring dissolved oxygen concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30615999A JP3669231B2 (en) | 1999-10-28 | 1999-10-28 | Indicator for measuring dissolved oxygen concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001124760A JP2001124760A (en) | 2001-05-11 |
| JP3669231B2 true JP3669231B2 (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30615999A Expired - Lifetime JP3669231B2 (en) | 1999-10-28 | 1999-10-28 | Indicator for measuring dissolved oxygen concentration |
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| Country | Link |
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| JP (1) | JP3669231B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001124699A (en) * | 1999-10-28 | 2001-05-11 | Miura Co Ltd | Indicator for measuring dissolved oxygen concentration |
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| JP2001124760A (en) | 2001-05-11 |
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