JP2009122077A - Method for measuring chlorite ion - Google Patents
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本発明は、被検液中の亜塩素酸イオン濃度を測定する方法に関する。 The present invention relates to a method for measuring a chlorite ion concentration in a test solution.
遊泳用プール水等の消毒剤には、次亜塩素酸ナトリウム等の塩素剤が使用されているが、近年、塩素剤と合わせて二酸化塩素を使用する施設が見られるようになった。
二酸化塩素は、塩素剤に比較して酸化力が弱く、トリハロメタンの生成が少ないことや塩素臭がない等の優れた特徴がある一方、消毒副生成物としてメトヘモグロビン血症を引き起こすとされる亜塩素酸イオンが生成される。
そのため、プール水の水質基準には、二酸化塩素を使用するときの上限を０．４ｍｇ／Ｌとすることに加えて、亜塩素酸イオンについても１．２ｍｇ／Ｌ以下とするとの基準値が定められており、管理項目として、二酸化塩素及び亜塩素酸イオン濃度の測定を１日に３回以上行うことが義務付けられている。
二酸化塩素濃度を測定するための従来の分析方法としては、ジエチル−ｐ−フェニレンジアミン（以下、ＤＰＤと略称する）吸光光度法等が挙げられ、亜塩素酸イオン濃度を測定するための従来の分析方法としては、イオンクロマトグラフ法が挙げられる。
尚、この様な従来技術に関しては、当業者の間で広く知られているが、この点について言及した適切な特許文献は見当らない。
Chlorine agents such as sodium hypochlorite are used for disinfectants such as swimming pool water. Recently, however, facilities that use chlorine dioxide together with chlorine agents have been seen.
Chlorine dioxide is weaker than chlorinating agents and has excellent characteristics such as less generation of trihalomethane and no odor of chlorine. On the other hand, chlorine dioxide is considered to cause methemoglobinemia as a disinfection by-product. Chlorate ions are generated.
Therefore, in addition to the upper limit when using chlorine dioxide is 0.4 mg / L, the standard value for the quality of pool water is 1.2 mg / L or less for chlorite ions. As a management item, it is obliged to measure chlorine dioxide and chlorite ion concentrations at least three times a day.
Conventional analysis methods for measuring chlorine dioxide concentration include diethyl-p-phenylenediamine (hereinafter abbreviated as DPD) absorptiometry and the like, and conventional analysis for measuring chlorite ion concentration. Examples of the method include ion chromatography.
In addition, although such a prior art is widely known among those skilled in the art, there is no appropriate patent document that mentions this point.
二酸化塩素や、亜塩素酸イオンは、試料採取後直ちに測定する必要があるため、施設管理者等が、プール水中の二酸化塩素や亜塩素酸イオンの水質管理を的確に遂行するためには、現場で簡便に測定できる分析方法が必要である。
これまで、二酸化塩素濃度を簡便に測定し得る方法については幾つか知られているが、亜塩素酸イオン濃度については、高価な分析機器や専門的知識、技術を必要とするイオンクロマトグラフ法以外知られておらず、遊泳用プール施設や温泉施設等の現場で簡便に測定することができなかった。
Chlorine dioxide and chlorite ions need to be measured immediately after sampling. Therefore, in order for facility managers to properly manage the quality of chlorine dioxide and chlorite ions in pool water, Analytical methods that can be measured easily and easily are necessary.
Up to now, several methods have been known that can easily measure the chlorine dioxide concentration, but the chlorite ion concentration is other than the ion chromatographic method that requires expensive analytical instruments, specialized knowledge, and techniques. It was not known and could not be measured easily on the spot such as swimming pool facilities and hot spring facilities.
本発明は、上記実情に鑑みてなされたものであって、その目的は、遊泳用プール施設や温泉施設等において被検液中の亜塩素酸イオン濃度を簡便に測定し得る方法を提供するものである。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a method capable of easily measuring the concentration of chlorite ions in a test solution in a swimming pool facility, a hot spring facility, or the like. It is.
上記の目的を達成するため、本発明では、被検液中の亜塩素酸イオン濃度を測定する方法であって、
前記被検液に由来する第１被検液に対して、酸、デンプン、及びヨウ素化合物を添加して発色させて、その発色度を測定する第１工程；
前記被検液に由来する第２被検液に対して、ジエチル−ｐ−フェニレンジアミンを添加して発色させて、その発色度を測定する第２工程；
前記被検液に由来する第３被検液に対して、グリシン溶液を添加した後、ジエチル−ｐ−フェニレンジアミンを添加して発色させて、その発色度を測定する第３工程；
前記第２工程により得られた測定値から、前記第３工程により得られた測定値を差し引く第４工程；
前記第１工程により得られた測定値から、前記第３工程及び前記第４工程の測定値を基にして得られた値を差し引く第５工程；
を包含することを特徴とする。
In order to achieve the above object, the present invention is a method for measuring the concentration of chlorite ions in a test liquid,
A first step in which acid, starch, and iodine compound are added to the first test solution derived from the test solution to develop color, and the degree of color development is measured;
A second step of measuring the degree of color development by adding diethyl-p-phenylenediamine to the second test liquid derived from the test liquid to cause color development;
A third step of adding a glycine solution to the third test solution derived from the test solution, then adding diethyl-p-phenylenediamine to cause color development, and measuring the degree of color development;
A fourth step of subtracting the measurement value obtained in the third step from the measurement value obtained in the second step;
A fifth step of subtracting a value obtained based on the measurement values of the third step and the fourth step from the measurement value obtained by the first step;
It is characterized by including.
〔作用及び効果〕
本発明における第１工程は、以下の化学反応式；
［化１］
ＣｌＯ2 -＋４Ｉ-＋４Ｈ+→２Ｉ2＋２Ｈ2Ｏ＋Ｃｌ-
に基づき、亜塩素酸イオン（ＣｌＯ2 -）の存在下で遊離したヨウ素分子をヨウ素デンプン反応により発色させることによって、間接的に被検液中の亜塩素酸イオンを検出するものである。
[Action and effect]
The first step in the present invention includes the following chemical reaction formula:
[Chemical 1]
ClO 2 − + 4I − + 4H + → 2I 2 + 2H 2 O + Cl −
In this method, iodine molecules released in the presence of chlorite ions (ClO 2 − ) are colored by iodine starch reaction to indirectly detect chlorite ions in the test solution.
尚、被検液中には、亜塩素酸イオンだけでなく、二酸化塩素と、有効塩素（塩素、次亜塩素酸イオン）が共存する場合が多い。 In addition, not only chlorite ions but also chlorine dioxide and effective chlorine (chlorine, hypochlorite ions) often coexist in the test solution.
第１工程による亜塩素酸イオンの検出方法は、亜塩素酸イオンに対する特異性が低い。そのため、被検液中に二酸化塩素や有効塩素が含まれている場合には、亜塩素酸イオンだけでなく、二酸化塩素や有効塩素も同時に検出されることとなり、その測定値は誤差を含み得る。 The method for detecting chlorite ions in the first step has low specificity for chlorite ions. Therefore, when chlorine dioxide or effective chlorine is contained in the test liquid, not only chlorite ions but also chlorine dioxide and effective chlorine will be detected at the same time, and the measured value may contain errors. .
本発明における第２工程は、ジエチル−ｐ−フェニレンジアミン（以下、ＤＰＤと略称する）によって、被検液中の二酸化塩素及び有効塩素を検出することができる。
また、本発明における第３工程は、ＤＰＤとグリシンによって、被検液中の二酸化塩素のみを特異的に検出することができる。
In the second step of the present invention, chlorine dioxide and available chlorine in the test liquid can be detected with diethyl-p-phenylenediamine (hereinafter abbreviated as DPD).
In the third step of the present invention, only chlorine dioxide in the test solution can be specifically detected by DPD and glycine.
従って、本発明における第４工程において、第２工程により得られた測定値から、第３工程により得られた測定値を差し引くことによって、被検液中の有効塩素に由来する測定値を得ることができる。 Therefore, in the fourth step of the present invention, a measurement value derived from the effective chlorine in the test liquid is obtained by subtracting the measurement value obtained in the third step from the measurement value obtained in the second step. Can do.
そして、本発明における第５工程において、第１工程により得られた測定値から、第３工程及び第４工程の測定値を基にして得られた値（即ち、第３工程及び第４工程において得られた各測定値に、それぞれ適当な補正処理を施して得られた２つの値）を差し引くことによって、第１工程において得られた測定値の誤差を修正して、被検液中の亜塩素酸イオンのみに由来する測定値（修正値）を得ることが可能であり、結果、当該修正値を用いて被検液中の亜塩素酸イオン濃度を算出することができる。 In the fifth step of the present invention, the value obtained from the measurement value obtained in the first step based on the measurement value in the third step and the fourth step (that is, in the third step and the fourth step). By subtracting two values obtained by applying appropriate correction processing to each measurement value obtained, the error in the measurement value obtained in the first step is corrected, and the sub-sample in the test solution is corrected. A measurement value (correction value) derived only from chlorate ions can be obtained, and as a result, the chlorite ion concentration in the test liquid can be calculated using the correction value.
従って、本発明によれば、例え、被検液中に亜塩素酸イオンだけでなく、二酸化塩素や有効塩素が共存する場合であっても、被検液中の亜塩素酸イオン濃度を正確に測定することができる。 Therefore, according to the present invention, for example, not only chlorite ions but also chlorine dioxide and effective chlorine coexist in the test solution, the chlorite ion concentration in the test solution is accurately determined. Can be measured.
さらに、第１工程〜第３工程における被検液の発色度を測定する操作については、持ち運びに便利で、且つ操作も容易な簡易比色計を用いて実施することが可能である。
従って、本発明は、遊泳用プール施設や温泉施設等の現場において簡便に実施し得るものであり、被検液中の亜塩素酸イオン濃度を簡便に測定することができる。
Furthermore, the operation for measuring the color development degree of the test solution in the first to third steps can be performed using a simple colorimeter that is convenient to carry and easy to carry.
Therefore, the present invention can be easily carried out at a site such as a swimming pool facility or a hot spring facility, and the chlorite ion concentration in the test solution can be easily measured.
本発明の実施の形態を説明する前に、特許請求の範囲及び明細書にて用いられる用語について以下に説明する。
（被検液）
本発明を適用し得る被検液とは、塩素化合物（塩素、次亜塩素酸イオン、二酸化塩素、亜塩素酸イオン等）を含有し得る水溶液を意味するものであり、例えば、遊泳用プール水、温泉水等が挙げられるが、これらに限定されるものではない。
Before describing embodiments of the present invention, terms used in the claims and specification will be described below.
(Test solution)
The test liquid to which the present invention can be applied means an aqueous solution that can contain a chlorine compound (chlorine, hypochlorite ion, chlorine dioxide, chlorite ion, etc.), for example, swimming pool water , Hot spring water and the like, but are not limited thereto.
（酸）
本発明に適用し得る酸とは、被検液のｐＨを酸性にするために使用されるものであり、例えば、塩酸や硫酸等が挙げられるが、これらに限定されるものではない。
(acid)
The acid that can be applied to the present invention is used to make the pH of the test solution acidic, and examples include, but are not limited to, hydrochloric acid and sulfuric acid.
（デンプン）
本発明に適用し得るデンプンとは、被検液に可溶なデンプンを意味するものであり、例えば、トウモロコシデンプンや馬鈴薯デンプン等が挙げられるが、これらに限定されるものではない。
尚、本発明においては、上記デンプンを含有する所定濃度の水溶液を調製して、被検液に添加するようにしても良い。このようなデンプン水溶液の濃度としては、特に限定されるものではないが、０．１％〜１％であることが好ましい。
(Starch)
The starch applicable to the present invention means a starch that is soluble in a test solution, and examples thereof include corn starch and potato starch, but are not limited thereto.
In the present invention, an aqueous solution having a predetermined concentration containing the starch may be prepared and added to the test solution. The concentration of such an aqueous starch solution is not particularly limited, but it is preferably 0.1% to 1%.
（ヨウ素化合物）
本発明に適用し得るヨウ素化合物としては、例えば、ヨウ化カリウム、ヨウ化ナトリウム等が挙げられる。
尚、本発明においては、上記ヨウ素化合物を含有する所定濃度の水溶液を調製して、被検液に添加するようにしても良い。このようなヨウ素化合物溶液の濃度としては、特に限定されるものではないが、１％〜３０％であることが好ましい。
(Iodine compound)
Examples of iodine compounds that can be applied to the present invention include potassium iodide and sodium iodide.
In the present invention, an aqueous solution having a predetermined concentration containing the iodine compound may be prepared and added to the test solution. The concentration of the iodine compound solution is not particularly limited, but is preferably 1% to 30%.
次いで、以下に本発明の実施の形態を説明する。
〔実施形態〕
本発明は、以下の工程手順に沿って実施し得るものであるが、必ずしも以下の順序で実施する必要はなく、適宜、その手順を変更することも可能である（例えば、ヨウ素法（手順１及び２）、ＤＰＤ法（手順３及び４）、ＤＰＤ−グリシン法（手順５及び６）については、その順序を問わず実施し得るものであり、あるいは、先に手順７〜９を実施して基準値を得ておくなどしても良い）。
Next, embodiments of the present invention will be described below.
Embodiment
The present invention can be carried out according to the following process procedures, but is not necessarily carried out in the following order, and the procedures can be appropriately changed (for example, iodine method (procedure 1 And 2), the DPD method (procedures 3 and 4), and the DPD-glycine method (procedures 5 and 6) can be performed regardless of the order, or the procedures 7 to 9 are performed first. You may get a reference value).
手順１
被検液のサンプリングを行う（第１被検液の採取）。
Step 1
The test solution is sampled (collection of the first test solution).
手順２（ヨウ素法）
第１被検液に対して、酸、デンプン、及びヨウ素化合物を添加して発色させて、その発色度を測定して測定値１を得る（亜塩素酸イオン、二酸化塩素、及び有効塩素の検出）。
尚、手順２の工程は、以下の化学反応式；
［化２］
ＣｌＯ2 -＋４Ｉ-＋４Ｈ+→２Ｉ2＋２Ｈ2Ｏ＋Ｃｌ-
に基づき、亜塩素酸イオン（ＣｌＯ2 -）の存在下で遊離したヨウ素分子をヨウ素デンプン反応により発色させることによって、間接的に亜塩素酸イオンを検出する方法である（以下、ヨウ素法と称する）。しかしながら、このヨウ素法は、亜塩素酸イオンに対する特異性が低く、被検液中に二酸化塩素や有効塩素が含まれている場合には、亜塩素酸イオンだけでなく、二酸化塩素や有効塩素も同時に検出され得る。
Procedure 2 (Iodine method)
Acid, starch, and iodine compound are added to the first test solution to cause color development, and the color development degree is measured to obtain a measurement value 1 (detection of chlorite ions, chlorine dioxide, and effective chlorine) ).
In addition, the process of the procedure 2 has the following chemical reaction formula;
[Chemical 2]
ClO 2 − + 4I − + 4H + → 2I 2 + 2H 2 O + Cl −
In this method, iodine molecules liberated in the presence of chlorite ions (ClO 2 − ) are colored by iodine starch reaction to detect chlorite ions indirectly (hereinafter referred to as iodine method). ). However, this iodine method has low specificity to chlorite ions, and when the sample liquid contains chlorine dioxide and effective chlorine, not only chlorite ions but also chlorine dioxide and effective chlorine are contained. Can be detected simultaneously.
手順３
再び被検液のサンプリングを行う（第２被検液の採取）。
Step 3
The test liquid is sampled again (collection of the second test liquid).
手順４（ＤＰＤ法）
第２被検液に対して、ジエチル−ｐ−フェニレンジアミン（ＤＰＤ）を添加して発色させて、その発色度を測定して測定値２を得る（二酸化塩素、及び有効塩素の検出）。
尚、手順４の工程は、ＤＰＤによって被検液中の有効塩素を検出する方法（以下、ＤＰＤ法と称する）である。しかしながら、ＤＰＤ法は、有効塩素に対する特異性が低く、被検液中に二酸化塩素が含まれている場合には、有効塩素だけでなく、二酸化塩素も同時に検出され得る。
尚、有効塩素とは、塩素、又は次亜塩素酸イオンを意味するが、アルカリ性条件下（天然アルカリ温泉水等）では、次亜塩素酸イオンとして存在する場合が多い。
Procedure 4 (DPD method)
Diethyl-p-phenylenediamine (DPD) is added to the second test solution to cause color development, and the degree of color development is measured to obtain measurement value 2 (detection of chlorine dioxide and effective chlorine).
Step 4 is a method for detecting effective chlorine in the test solution by DPD (hereinafter referred to as DPD method). However, the DPD method has low specificity for effective chlorine, and when chlorine dioxide is contained in the test solution, not only effective chlorine but also chlorine dioxide can be detected simultaneously.
In addition, although effective chlorine means chlorine or a hypochlorite ion, it exists in many cases as a hypochlorite ion under alkaline conditions (natural alkaline hot spring water etc.).
手順５
再び被検液のサンプリングを行う（第３被検液の採取）。
Step 5
The test liquid is sampled again (collection of the third test liquid).
手順６（ＤＰＤ−グリシン法）
第３被検液に対して、グリシン溶液を添加して、次にジエチル−ｐ−フェニレンジアミン（ＤＰＤ）を添加して発色させて、その発色度を測定して測定値３を得る（二酸化塩素の検出）。
尚、手順６の工程は、ＤＰＤ及びグリシンによって被検液中の二酸化塩素のみを特異的に検出し得る方法である（以下、ＤＰＤ−グリシン法と称する）。
Procedure 6 (DPD-glycine method)
To the third test solution, a glycine solution is added, then diethyl-p-phenylenediamine (DPD) is added to cause color development, and the degree of color development is measured to obtain measurement value 3 (chlorine dioxide). Detection).
The step 6 is a method capable of specifically detecting only chlorine dioxide in the test solution with DPD and glycine (hereinafter referred to as DPD-glycine method).
手順７
所定の二酸化塩素濃度（例えば、１ｐｐｍ程度）を有する基準液１を用意し、この基準液１に対して、上記手順２のヨウ素法、及び上記手順６のＤＰＤ−グリシン法を実施して、それぞれ基準値１、及び基準値２を得る。
Step 7
A reference solution 1 having a predetermined chlorine dioxide concentration (for example, about 1 ppm) is prepared, and the iodine method of the procedure 2 and the DPD-glycine method of the procedure 6 are performed on the reference solution 1, A reference value 1 and a reference value 2 are obtained.
手順８
所定の次亜塩素酸イオン濃度（例えば、１ｐｐｍ程度）を有する基準液２を用意し、この基準液２に対して、上記手順２のヨウ素法、及び上記手順４のＤＰＤ法を実施して、それぞれ基準値３、及び基準値４を得る。
Step 8
A reference solution 2 having a predetermined hypochlorite ion concentration (for example, about 1 ppm) is prepared, and the iodine method of the procedure 2 and the DPD method of the procedure 4 are performed on the reference solution 2, Reference value 3 and reference value 4 are obtained, respectively.
手順９
所定の亜塩素酸イオン濃度（例えば、１ｐｐｍ）を有する基準液３を用意し、この基準液３に対して、上記手順２のヨウ素法を実施して、基準値５を得る。
Step 9
A reference solution 3 having a predetermined chlorite ion concentration (for example, 1 ppm) is prepared, and the iodine method of the above procedure 2 is performed on the reference solution 3 to obtain a reference value 5.
手順１０
上記手順４で得られた測定値２から、上記手順６で得られた測定値３を差し引いて測定値４を得る。
Step 10
A measurement value 4 is obtained by subtracting the measurement value 3 obtained in the procedure 6 from the measurement value 2 obtained in the procedure 4.
手順１１
上記各手順にて得られた測定値１、測定値３、測定値４、基準値１〜４を以下の計算式；
「修正値１＝測定値１−（測定値３×基準値１÷基準値２）−（測定値４×基準値３÷基準値４）」
に入力して、測定値１の誤差を修正して、修正値１を算出する。
即ち、本手順においては、測定値１から、測定値３に補正処理を施して得られた値と、測定値４に補正処理を施して得られた値とを差し引くことによって、測定値１の誤差を修正して、被検液中の亜塩素酸イオンのみに由来する測定値（修正値１）を得ることができる。
Step 11
Measurement value 1, measurement value 3, measurement value 4, and reference values 1 to 4 obtained by the above procedures are calculated as follows:
“Corrected value 1 = measured value 1− (measured value 3 × reference value 1 ÷ reference value 2) − (measured value 4 × reference value 3 ÷ reference value 4)”
To correct the error of the measured value 1 and calculate the corrected value 1.
That is, in this procedure, from the measured value 1, the value obtained by performing the correction process on the measured value 3 and the value obtained by performing the correction process on the measured value 4 are subtracted. By correcting the error, it is possible to obtain a measured value (corrected value 1) derived only from chlorite ions in the test liquid.
手順１２
上記手順１１にて得られた修正値１、上記手順９にて得られた基準値５、及び基準液３の亜塩素酸イオン濃度を以下の計算式；
「被検液中の亜塩素酸イオンの濃度＝修正値１÷基準値５×（基準液３の亜塩素酸イオン濃度）」
に入力して、被検液中の亜塩素酸イオンの濃度を算出する。
Step 12
The corrected value 1 obtained in the procedure 11 above, the reference value 5 obtained in the procedure 9 above, and the chlorite ion concentration of the reference solution 3 are calculated as follows:
“Concentration of chlorite ion in test solution = corrected value 1 ÷ reference value 5 × (chlorite ion concentration in reference solution 3)”
To calculate the concentration of chlorite ions in the test solution.
〔その他の実施形態〕
前述の実施形態においては、被検液中の二酸化塩素及び次亜塩素酸イオンの濃度を同時に算出することも可能である。
[Other Embodiments]
In the above-described embodiment, the concentrations of chlorine dioxide and hypochlorite ions in the test solution can be calculated simultaneously.
即ち、被検液中の二酸化塩素濃度を求めるためには、上記手順６にて得られた測定値３、上記手順７にて得られた基準値２、及び基準液１の二酸化塩素濃度を以下の計算式；
「被検液中の二酸化塩素の濃度＝測定値３÷基準値２×（基準液１の二酸化塩素濃度）」
に入力して、被検液中の二酸化塩素濃度を算出する。
That is, in order to obtain the chlorine dioxide concentration in the test solution, the measured value 3 obtained in the procedure 6 above, the reference value 2 obtained in the procedure 7 and the chlorine dioxide concentration in the reference solution 1 are as follows: Formula of
“Concentration of chlorine dioxide in the test solution = measured value 3 ÷ reference value 2 × (chlorine dioxide concentration in reference solution 1)”
To calculate the chlorine dioxide concentration in the test solution.
また、被検液中の次亜塩素酸イオン濃度を求めるためには、上記手順１０にて得られた測定値４、上記手順８にて得られた基準値４、及び基準液２の次亜塩素酸イオン濃度を以下の計算式；
「被検液中の次亜塩素酸イオンの濃度＝測定値４÷基準値４×（基準液２の次亜塩素酸イオン濃度）」
に入力して、被検液中の次亜塩素酸イオン濃度を算出する。
Further, in order to obtain the hypochlorite ion concentration in the test solution, the measured value 4 obtained in the above procedure 10, the reference value 4 obtained in the above procedure 8, and the hypochlorite of the reference solution 2 are used. Chlorate ion concentration is calculated as follows:
“Concentration of hypochlorite ion in test solution = measured value 4 ÷ reference value 4 × (concentration of hypochlorite ion in reference solution 2)”
To calculate the hypochlorite ion concentration in the test solution.
〔参考例〕ヨウ素法による亜塩素酸イオン濃度の測定
１．試薬及び基準液の調製
Ａ試薬：１Ｎ硫酸（２５ｍＬ）と１％デンプン水溶液（２５ｍＬ）とを混合して調製した。
Ｂ試薬：２０％ ヨウ化カリウム溶液（５０ｍＬ）
基準液３：２５％ 亜塩素酸ナトリウム（２ｇ）を水（５００ｍＬ）に溶解して原液を調製し（原液の亜塩素酸イオン濃度は７４５ｐｐｍ）、その原液１．３４２ｇに９００ｍＬの水を加え、そのｐＨを１２に合わせた後、さらに水を加えてその全量を１Ｌとしたものを基準液（亜塩素酸イオン濃度：１．０００ｐｐｍ）とした。尚、この基準液は１０日過ぎれば原液から再調製する。
[Reference Example] Measurement of chlorite ion concentration by iodine method Preparation of Reagent and Reference Solution A Reagent: Prepared by mixing 1N sulfuric acid (25 mL) and 1% aqueous starch solution (25 mL).
Reagent B: 20% potassium iodide solution (50 mL)
Reference solution 3: 25% sodium chlorite (2 g) was dissolved in water (500 mL) to prepare a stock solution (the concentration of chlorite ions in the stock solution was 745 ppm), 900 mL of water was added to 1.342 g of the stock solution, The pH was adjusted to 12, and water was further added to make the total amount 1 L, which was used as a standard solution (chlorite ion concentration: 1.000 ppm). This reference solution is re-prepared from the stock solution after 10 days.
２．試料の調製
所定の濃度の亜塩素酸イオンを含有する試料１〜３（試料１：０．０１ｐｐｍ、試料２：０．２０ｐｐｍ、試料３：５．００ｐｐｍ）を調製した。
2. Sample Preparation Samples 1 to 3 (sample 1: 0.01 ppm, sample 2: 0.20 ppm, sample 3: 5.00 ppm) containing a predetermined concentration of chlorite ion were prepared.
３．測定器
比色計としては、ＤＩＧＩＴＡＬ ＣＬ２ ＴＥＳＴＥＲ ＤＣＴ−１００（タクミナ社製）を使用したが、この他にポケット残留塩素計（ハック社製）、デジタルパックテスト型式ＤＰＭ−ＣＬＯ２（共立理化化学研究所製）等が使用可能である。
3. As a colorimeter, DIGITAL CL2 TESTER DCT-100 (manufactured by Takumina) was used, but in addition, a pocket residual chlorine meter (manufactured by Hack), a digital pack test model DPM-CLO2 (Kyoritsu Rika Chemical Laboratory) Etc.) can be used.
４．測定操作
（１）測定セルに７．５ｍＬの純水を入れてブランクとした。
（２）測定セルに７．５ｍＬの基準液３を入れて基準とした。
（３）測定セルに７．５ｍＬの各試料を入れて試料とした。
（４）各セルにＡ試薬を入れて混合し、さらに各セルにＢ試薬を入れて振り混ぜた後、１０分間暗所に静置する。
（５）ブランクセルで測定器をゼロに合わせた。
（６）各セルを測定器で測定した。
（７）測定結果は次の計算式で算出した。
各試料の亜塩素酸イオン濃度＝各試料の測定値／基準液の測定値×１．０００ｐｐｍ
尚、上記試料１〜３については、公知のイオンクロマトグラフ法によっても亜塩素酸イオン濃度を測定した。
4). Measurement operation (1) 7.5 mL of pure water was put into a measurement cell to make a blank.
(2) 7.5 mL of the reference solution 3 was added to the measurement cell as a reference.
(3) 7.5 mL of each sample was put in a measurement cell to prepare a sample.
(4) A reagent is put in each cell and mixed, and further, B reagent is put in each cell and shaken and mixed, and then left in a dark place for 10 minutes.
(5) The measuring instrument was set to zero with a blank cell.
(6) Each cell was measured with a measuring instrument.
(7) The measurement result was calculated by the following formula.
Chlorite ion concentration of each sample = measured value of each sample / measured value of reference solution × 1.000 ppm
In addition, about the said samples 1-3, the chlorite ion density | concentration was measured also by the well-known ion chromatograph method.
５．測定結果
測定結果を以下の表１に示す。ヨウ素法による亜塩素酸イオン濃度の測定結果は、従来のイオンクロマトグラフ法による測定結果とほとんど変わらなかった。
5). Measurement results The measurement results are shown in Table 1 below. The measurement result of the chlorite ion concentration by the iodine method was almost the same as the measurement result by the conventional ion chromatography method.
〔実施例〕温泉水中の次亜塩素酸イオン、二酸化塩素、及び亜塩素酸イオンの濃度測定
被検液として、次亜塩素酸ナトリウムと二酸化塩素を併用して殺菌処理を実施している温泉地の実温泉を使用し、この温泉水中の次亜塩素酸イオン、二酸化塩素、及び亜塩素酸イオンの濃度を測定した。
[Example] Concentration measurement of hypochlorite ion, chlorine dioxide, and chlorite ion in hot spring water Hot spring area where sodium hypochlorite and chlorine dioxide are used in combination as a test solution to perform sterilization treatment The concentration of hypochlorite ion, chlorine dioxide, and chlorite ion in this hot spring water was measured.
１．試薬及び基準液の調製
（試薬）
ヨウ素法に使用した試薬（硫酸、デンプン水溶液、ヨウ化カリウム溶液）は、上記参考例と同じものを使用した。
ＤＰＤ法に使用した試薬（ＤＰＤ試薬等）、及びＤＰＤ−グリシン法に使用した試薬（ＤＰＤ試薬、グリシン試薬）は、市販されている公知のものを使用した。
（基準液）
基準液１の調製：二酸化塩素水１０００ｐｐｍ〜３０００ｐｐｍの原水を１０００倍〜３０００倍に希釈して基準液１（二酸化塩素濃度：１．０００ｐｐｍ）を調製した。
基準液２の調製：１２％次亜塩素酸ナトリウム溶液（１．４４７ｇ）を水で希釈して１Ｌとし、さらにこの希釈液１ｍＬを水で１Ｌに希釈して基準液２（次亜塩素酸イオン濃度：１．０００ｐｐｍ）を調製した。
基準液３は、上記比較例の基準液（亜塩素酸イオン濃度：１．０００ｐｐｍ）と同じものを使用した。
1. Preparation of reagents and reference solutions (reagents)
The reagents used in the iodine method (sulfuric acid, starch aqueous solution, potassium iodide solution) were the same as those in the above Reference Example.
As the reagents used in the DPD method (DPD reagents and the like) and the reagents used in the DPD-glycine method (DPD reagent and glycine reagent), commercially available known ones were used.
(Reference solution)
Preparation of reference solution 1: A raw solution of 1000 ppm to 3000 ppm of chlorine dioxide water was diluted 1000 to 3000 times to prepare reference solution 1 (chlorine dioxide concentration: 1.000 ppm).
Preparation of Reference Solution 2: Dilute 12% sodium hypochlorite solution (1.447 g) with water to 1 L, and further dilute 1 mL of this diluted solution to 1 L with water to prepare Reference solution 2 (hypochlorite ion). Concentration: 1.000 ppm) was prepared.
The reference liquid 3 was the same as the reference liquid (chlorite ion concentration: 1.000 ppm) of the above comparative example.
２．測定器
比色計として、ＤＩＧＩＴＡＬ ＣＬ２ ＴＥＳＴＥＲ ＤＣＴ−１００（タクミナ社製）を使用した。
2. DIGITAL CL2 TESTER DCT-100 (manufactured by Takumina) was used as a colorimeter.
３．測定操作
上記温泉水に由来する６種類の試料（試料４〜９）を用意し、各試料について、上記実施形態の手順１〜６、及び手順１０を実施して、測定値１〜４を得た。
また、上記基準液１〜３について、上記実施形態の手順７〜９を実施して基準値１〜５を得た。
各試料について得られた測定値１、測定値３、測定値４、基準値１〜５、及び基準液３の亜塩素酸イオン濃度（１．０００ｐｐｍ）を、上記実施形態の手順１１及び手順１２の計算式に入力して各試料４〜９の亜塩素酸イオンの濃度を算出した（尚、試料４〜９については、公知のイオンクロマトグラフ法によっても亜塩素酸イオン濃度を測定した）。
さらに、各試料４〜９における測定値３、測定値４、基準値２、基準値４、基準液１の二酸化塩素濃度（１．０００ｐｐｍ）、及び基準液２の次亜塩素酸イオン濃度（１．０００ｐｐｍ）を、上記その他の実施形態の各計算式に入力して、各試料４〜９の二酸化塩素及び次亜塩素酸イオンの濃度を算出した。
3. Measurement operation Six types of samples (samples 4 to 9) derived from the hot spring water are prepared, and the measurement values 1 to 4 are obtained by performing the steps 1 to 6 and the procedure 10 of the above embodiment for each sample. It was.
Moreover, about the said reference | standard liquids 1-3, the procedure values 7-9 of the said embodiment were implemented and the reference values 1-5 were obtained.
The measured value 1, measured value 3, measured value 4, reference values 1 to 5, and chlorite ion concentration (1.000 ppm) of the reference solution 3 obtained for each sample were used as the procedures 11 and 12 of the above embodiment. The chlorite ion concentration of each of the samples 4 to 9 was calculated (the chlorite ion concentration was also measured by a known ion chromatographic method for the samples 4 to 9).
Furthermore, the measured value 3, measured value 4, reference value 2, reference value 4, reference sample 1 chlorine dioxide concentration (1.000 ppm), and reference solution 2 hypochlorite ion concentration (1) in each sample 4-9 .000 ppm) was input to each calculation formula of the above-mentioned other embodiments, and the concentrations of chlorine dioxide and hypochlorite ions in each sample 4 to 9 were calculated.
４．測定結果
測定結果を以下の表２及び表３に示す。表３に示すように、本発明の測定方法による亜塩素酸イオン濃度の測定結果は、従来のイオンクロマトグラフ法による測定結果とほとんど変わらなかった。即ち、本発明の測定方法によれば、被検液中に二酸化塩素や次亜塩素酸イオンが共存している場合においても、被検液中の亜塩素酸イオン濃度を正確に測定し得ることが示された。
4). Measurement results The measurement results are shown in Tables 2 and 3 below. As shown in Table 3, the measurement result of the chlorite ion concentration by the measurement method of the present invention was almost the same as the measurement result by the conventional ion chromatography method. That is, according to the measurement method of the present invention, even when chlorine dioxide and hypochlorite ions coexist in the test solution, the chlorite ion concentration in the test solution can be accurately measured. It has been shown.
Claims (1)
前記被検液に由来する第１被検液に対して、酸、デンプン、及びヨウ素化合物を添加して発色させて、その発色度を測定する第１工程；
前記被検液に由来する第２被検液に対して、ジエチル−ｐ−フェニレンジアミンを添加して発色させて、その発色度を測定する第２工程；
前記被検液に由来する第３被検液に対して、グリシン溶液を添加した後、ジエチル−ｐ−フェニレンジアミンを添加して発色させて、その発色度を測定する第３工程；
前記第２工程により得られた測定値から、前記第３工程により得られた測定値を差し引く第４工程；
前記第１工程により得られた測定値から、前記第３工程及び前記第４工程の測定値を基にして得られた値を差し引く第５工程；
を包含する亜塩素酸イオンの測定方法。 A method for measuring the concentration of chlorite ions in a test solution,
A first step in which acid, starch, and iodine compound are added to the first test solution derived from the test solution to develop color, and the degree of color development is measured;
A second step of measuring the degree of color development by adding diethyl-p-phenylenediamine to the second test liquid derived from the test liquid to cause color development;
A third step of adding a glycine solution to the third test solution derived from the test solution, then adding diethyl-p-phenylenediamine to cause color development, and measuring the degree of color development;
A fourth step of subtracting the measurement value obtained in the third step from the measurement value obtained in the second step;
A fifth step of subtracting a value obtained based on the measurement values of the third step and the fourth step from the measurement value obtained by the first step;
A method for measuring chlorite ions including
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