JP2014016277A - Chromium measurement reagent and chromium measurement method - Google Patents
Chromium measurement reagent and chromium measurement method Download PDFInfo
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Abstract
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本発明は、クロム測定試薬及びクロム測定方法に関する。さらに詳しくは、水中のクロムの自動分析計に、好適に使用可能なクロム測定試薬及びクロム測定方法に関する。 The present invention relates to a chromium measurement reagent and a chromium measurement method. More specifically, the present invention relates to a chromium measuring reagent and a chromium measuring method that can be suitably used for an automatic analyzer for chromium in water.
六価クロムは、酸性条件下でジフェニルカルバジドと反応して赤紫の錯体を生成することが知られている。例えば、ＪＩＳ Ｋ ０１０２では、クロム（六価クロム、全クロム）測定のためのジフェニルカルバジド吸光光度法が規定されている。このジフェニルカルバジド溶液は、時間の経過と共に溶媒中に溶け込んでいる溶存酸素によって酸化され、六価クロムと反応した際の発色強度（感度）が低下する。特に、ジフェニルカルバジド溶液を高温下で保管した場合には、顕著に感度が低下する。そのため、自動分析計等で長期間にわたり使用すると、所望の感度が得られなくなるという問題があった。
ジフェニルカルバジド溶液の感度低下を抑制するために、非特許文献１では、塩酸や硫酸を添加したり、アセトン溶媒を用いたりすることが開示されている。また、特許文献１では、アスコルビン酸等の酸化防止剤を加えて、ジフェニルカルバジドの酸化を抑制することが開示されている。
Hexavalent chromium is known to react with diphenylcarbazide under acidic conditions to form a red-violet complex. For example, JIS K 0102 defines a diphenylcarbazide absorptiometric method for measuring chromium (hexavalent chromium, total chromium). This diphenylcarbazide solution is oxidized by dissolved oxygen dissolved in the solvent with the passage of time, and the color intensity (sensitivity) when reacted with hexavalent chromium decreases. In particular, when the diphenylcarbazide solution is stored at a high temperature, the sensitivity is significantly reduced. For this reason, there has been a problem that a desired sensitivity cannot be obtained when used for a long period of time with an automatic analyzer or the like.
In order to suppress a decrease in sensitivity of the diphenylcarbazide solution, Non-Patent Document 1 discloses that hydrochloric acid or sulfuric acid is added or an acetone solvent is used. Patent Document 1 discloses that an antioxidant such as ascorbic acid is added to suppress oxidation of diphenylcarbazide.
非特許文献１のように塩酸や硫酸を添加したり、アセトン溶媒を用いたりすれば、ある程度の経時による感度低下抑制効果は得られる。しかし、自動分析計等において長期間にわたりクロムを測定するには不充分であった。
また、特許文献１のようにアスコルビン酸等の酸化防止剤を添加すると、経時による感度低下抑制効果は高いものの、溶液調製直後の初期の発色強度（初期感度）が低く、自動分析計等において精度良くクロムを測定するには不適当であった。アスコルビン酸等の酸化防止剤を添加すると初期感度が低下するのは、酸化防止剤が、ジフェニルカルバジドと競合的に、測定対象である六価クロムと反応してしまうためではないかと推測される。
本発明は、上記事情に鑑みてなされたものであって、経時による感度低下の充分な抑制が可能であるクロム測定試薬、また、初期感度が高いクロム測定試薬を提供することを課題とする。
また、経時による感度低下の少ないクロム測定方法、また、初期感度が高いクロム測定方法を提供することを課題とする。
If hydrochloric acid or sulfuric acid is added as in Non-Patent Document 1, or an acetone solvent is used, an effect of suppressing sensitivity reduction over time can be obtained. However, it was insufficient to measure chromium for a long period of time with an automatic analyzer or the like.
In addition, when an antioxidant such as ascorbic acid is added as in Patent Document 1, the effect of suppressing the decrease in sensitivity over time is high, but the initial color intensity (initial sensitivity) immediately after preparation of the solution is low, and the accuracy in an automatic analyzer or the like is low. It was unsuitable for measuring chromium well. It is speculated that the initial sensitivity decreases when an antioxidant such as ascorbic acid is added, because the antioxidant reacts with the hexavalent chromium to be measured competitively with diphenylcarbazide. .
This invention is made | formed in view of the said situation, Comprising: It aims at providing the chromium measuring reagent which can fully suppress the sensitivity fall with time, and the chromium measuring reagent with high initial sensitivity.
It is another object of the present invention to provide a chromium measuring method with little sensitivity deterioration with time and a chromium measuring method with high initial sensitivity.
上記の課題を達成するために、本発明は以下の態様を含む。
［１］溶媒と、該溶媒中に含有されるジフェニルカルバジド及び塩化ヒドロキシルアンモニウムを含むクロム測定試薬。
［２］前記溶媒が、水と有機溶媒を含む水性溶媒である［１］に記載のクロム測定試薬。
［３］塩化ヒドロキシルアンモニウムの含有量が、０．１〜１０ｇ／Ｌである［１］または［２］に記載のクロム測定試薬。
［４］試料液と［１］〜［３］の何れか一項に記載のクロム測定試薬とを、酸性条件下で反応させて吸光度を測定するクロム測定方法。
［５］試料液と［１］〜［３］の何れか一項に記載のクロム測定試薬と酸とを反応させて吸光度を測定するクロム測定方法。
In order to achieve the above object, the present invention includes the following aspects.
[1] A chromium measuring reagent containing a solvent, diphenylcarbazide and hydroxylammonium chloride contained in the solvent.
[2] The chromium measurement reagent according to [1], wherein the solvent is an aqueous solvent containing water and an organic solvent.
[3] The chromium measuring reagent according to [1] or [2], wherein the content of hydroxylammonium chloride is 0.1 to 10 g / L.
[4] A chromium measurement method for measuring absorbance by reacting a sample solution and the chromium measurement reagent according to any one of [1] to [3] under acidic conditions.
[5] A chromium measurement method for measuring absorbance by reacting a sample solution, the chromium measurement reagent according to any one of [1] to [3], and an acid.
本発明のクロム測定試薬は経時による感度低下が充分に抑制されている。また、本発明のクロム測定試薬は初期感度が高い。そのため、このクロム測定試薬を用いたクロム測定方法は、自動分析計等に好適に適用できる。 The chromium measurement reagent of the present invention sufficiently suppresses the decrease in sensitivity over time. The chromium measuring reagent of the present invention has a high initial sensitivity. Therefore, the chromium measuring method using this chromium measuring reagent can be suitably applied to an automatic analyzer or the like.
［クロム測定試薬］
本発明のクロム測定試薬は、溶媒と、該溶媒中に含有されるジフェニルカルバジド及び塩化ヒドロキシルアンモニウムを含む。
溶媒は水性溶媒、非水性溶媒のいずれでもよいが、水性溶媒であることが好ましい。本発明における水性溶媒とは、水と有機溶媒を含む溶媒である。
[Chrome measuring reagent]
The chromium measuring reagent of the present invention contains a solvent, diphenylcarbazide and hydroxylammonium chloride contained in the solvent.
The solvent may be either an aqueous solvent or a non-aqueous solvent, but is preferably an aqueous solvent. The aqueous solvent in the present invention is a solvent containing water and an organic solvent.
水性溶媒に含まれる有機溶媒は、ジフェニルカルバジドを溶解できるものであれば特に限定はない。例えば、エチルアルコール、イソプロピルアルコール等のアルコール類、アセトン等のケトン類が挙げられる。
中でも、樹脂やゴム製の配管部品，バルブ類に対し低攻撃性であることから、アルコール類が好ましく、低毒性であることから、エチルアルコールが特に好ましい。
水性溶媒に占める有機溶媒の割合は、２５〜７５容量％が好ましく、３５〜６５容量％がより好ましく、４５〜５５容量％が特に好ましい。
水性溶媒に占める有機溶媒の割合が好ましい下限値以上であることにより、ジフェニルカルバジドを溶解させやすい。また、水性溶媒に占める有機溶媒の割合が好ましい上限値以下であることにより、樹脂やゴム製の配管部品，バルブ類に対する攻撃性を低減できる。
非水性溶媒としては、アセトンとエタノールの混合溶媒、エタノール、イソプロピルアルコール等のアルコール類、アセトン、およびそれらの混合溶液等が挙げられる。
The organic solvent contained in the aqueous solvent is not particularly limited as long as it can dissolve diphenylcarbazide. Examples thereof include alcohols such as ethyl alcohol and isopropyl alcohol, and ketones such as acetone.
Of these, alcohols are preferred because of their low attack on resin and rubber piping parts and valves, and ethyl alcohol is particularly preferred because of their low toxicity.
The proportion of the organic solvent in the aqueous solvent is preferably 25 to 75% by volume, more preferably 35 to 65% by volume, and particularly preferably 45 to 55% by volume.
When the proportion of the organic solvent in the aqueous solvent is equal to or more than the preferred lower limit, diphenylcarbazide can be easily dissolved. Moreover, when the proportion of the organic solvent in the aqueous solvent is equal to or less than the preferable upper limit, the attacking property on the piping parts and valves made of resin or rubber can be reduced.
Examples of the non-aqueous solvent include a mixed solvent of acetone and ethanol, alcohols such as ethanol and isopropyl alcohol, acetone, and a mixed solution thereof.
クロム測定試薬中のジフェニルカルバジドの含有量は、０．５〜５ｇ／Ｌであることが好まししく、０．５〜３ｇ／Ｌであることがより好ましく、１〜２ｇ／Ｌであることが特に好ましい。
クロム測定試薬中のジフェニルカルバジドの含有量が好ましい下限値以上であることにより、経時による感度低下がより一層抑制されやすい。また、クロム測定試薬中のジフェニルカルバジドの含有量が好ましい上限値以下であることにより、経時によるジフェニルカルバジド結晶の析出を防止しやすい。
The content of diphenylcarbazide in the chromium measuring reagent is preferably 0.5-5 g / L, more preferably 0.5-3 g / L, and 1-2 g / L. Is particularly preferred.
When the content of diphenylcarbazide in the chromium measurement reagent is equal to or more than the preferable lower limit, a decrease in sensitivity over time can be further suppressed. Moreover, when the content of diphenylcarbazide in the chromium measuring reagent is not more than the preferred upper limit value, it is easy to prevent precipitation of diphenylcarbazide crystals over time.
クロム測定試薬中の塩化ヒドロキシルアンモニウムの含有量は、０．１〜１０ｇ／Ｌであることが好まししく、０．５〜５．０ｇ／Ｌであることがより好ましく、０．５〜１ｇ／Ｌであることが特に好ましい。
クロム測定試薬中の塩化ヒドロキシルアンモニウムの含有量が好ましい下限値以上であることにより、経時による感度低下がより一層抑制されやすい。また、クロム測定試薬中の塩化ヒドロキシルアンモニウムの含有量が好ましい上限値以下であることにより、高い初期感度を得やすい。また、温度変化による感度変化も抑制しやすい。
したがって、感度低下抑制効果を重視する場合は、塩化ヒドロキシルアンモニウムの含有量を高めにすればよく、高い初期感度及び温度変化による感度変化の抑制を重視する場合は、塩化ヒドロキシルアンモニウムの含有量を低めにすればよい。
特に、クロム測定試薬中の塩化ヒドロキシルアンモニウムの含有量が０．５〜１ｇ／Ｌの場合、経時による感度低下抑制効果と高い初期感度及び温度変化による感度変化の抑制を両立しやすい。
The content of hydroxylammonium chloride in the chromium measurement reagent is preferably 0.1 to 10 g / L, more preferably 0.5 to 5.0 g / L, and 0.5 to 1 g / L. L is particularly preferable.
When the content of hydroxylammonium chloride in the chromium measuring reagent is equal to or more than the preferred lower limit, the sensitivity deterioration with time is more easily suppressed. Further, when the content of hydroxylammonium chloride in the chromium measuring reagent is not more than the preferable upper limit value, high initial sensitivity can be easily obtained. In addition, it is easy to suppress sensitivity changes due to temperature changes.
Therefore, the content of hydroxylammonium chloride may be increased when emphasizing the effect of suppressing the decrease in sensitivity, and the content of hydroxylammonium chloride is decreased when emphasizing the high initial sensitivity and the suppression of sensitivity change due to temperature change. You can do it.
In particular, when the content of hydroxylammonium chloride in the chromium measurement reagent is 0.5 to 1 g / L, it is easy to achieve both the effect of suppressing the decrease in sensitivity over time, the high initial sensitivity, and the suppression of sensitivity change due to temperature changes.
クロム測定試薬中のジフェニルカルバジドに対する塩化ヒドロキシルアンモニウムの割合は、５〜５０質量％が好ましく、１０〜４０質量％がより好ましく、２０〜３０質量％が特に好ましい。
クロム測定試薬中のジフェニルカルバジドに対する塩化ヒドロキシルアンモニウムの割合が好ましい下限値以上であることにより、経時による感度低下がより一層抑制されやすい。また、クロム測定試薬中のジフェニルカルバジドに対する塩化ヒドロキシルアンモニウムの割合が好ましい上限値以下であることにより、高い初期感度を得やすい。また、温度変化による感度変化も抑制しやすい。
したがって、感度低下抑制効果を重視する場合は、塩化ヒドロキシルアンモニウムの割合を高めにすればよく、高い初期感度及び温度変化による感度変化の抑制を重視する場合は、塩化ヒドロキシルアンモニウムの割合を低めにすればよい。
特に、クロム測定試薬中のジフェニルカルバジドに対する塩化ヒドロキシルアンモニウムの割合が２０〜３０質量％の場合、経時による感度低下抑制効果と高い初期感度及び温度変化による感度変化の抑制を両立しやすい。
The ratio of hydroxylammonium chloride to diphenylcarbazide in the chromium measuring reagent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 20 to 30% by mass.
When the ratio of hydroxylammonium chloride to diphenylcarbazide in the chromium measurement reagent is equal to or more than the preferable lower limit value, a decrease in sensitivity over time can be further suppressed. Moreover, when the ratio of the hydroxylammonium chloride with respect to the diphenylcarbazide in a chromium measuring reagent is below a preferable upper limit, it is easy to obtain a high initial sensitivity. In addition, it is easy to suppress sensitivity changes due to temperature changes.
Therefore, when emphasizing the effect of suppressing sensitivity decrease, the proportion of hydroxylammonium chloride may be increased. When emphasizing high initial sensitivity and suppression of sensitivity change due to temperature change, the proportion of hydroxylammonium chloride should be decreased. That's fine.
In particular, when the ratio of hydroxylammonium chloride to diphenylcarbazide in the chromium measurement reagent is 20 to 30% by mass, it is easy to achieve both a sensitivity reduction suppressing effect with time and a high initial sensitivity and suppression of sensitivity change due to temperature change.
本発明のクロム測定試薬は、溶媒と、ジフェニルカルバジドと塩化ヒドロキシルアンモニウムに加えて、本発明の効果を阻害しない範囲で、他の成分を含んでいてもよい。
他の成分としては、例えば、硫酸、塩酸，リン酸等の無機酸、フタル酸等のカルボン酸、硫酸マグネシウム等の硫酸塩が挙げられる。
The chromium measuring reagent of the present invention may contain other components in addition to the solvent, diphenylcarbazide, and hydroxylammonium chloride as long as the effects of the present invention are not inhibited.
Examples of other components include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, carboxylic acids such as phthalic acid, and sulfates such as magnesium sulfate.
本発明のクロム測定試薬の製造方法に特に限定はないが、まず、ジフェニルカルバジドを有機溶媒に溶解してジフェニルカルバジドの有機溶媒溶液を得、この有機溶媒溶液に水及び塩化ヒドロキシルアンモニウムを加えて混合することが好ましい。ジフェニルカルバジドを有機溶媒に溶解する際には、４０〜７０℃、好ましくは５０〜６０℃に加熱することが好ましい。
塩化ヒドロキシルアンモニウムは、予め水に溶解してから有機溶媒溶液に加えても、粉末のまま水と共に有機溶媒溶液に加えてもよい。
The method for producing the chromium measuring reagent of the present invention is not particularly limited. First, diphenylcarbazide is dissolved in an organic solvent to obtain an organic solvent solution of diphenylcarbazide, and water and hydroxylammonium chloride are added to the organic solvent solution. It is preferable to mix them. When diphenylcarbazide is dissolved in an organic solvent, it is preferably heated to 40 to 70 ° C, preferably 50 to 60 ° C.
Hydroxyl ammonium chloride may be dissolved in water in advance and then added to the organic solvent solution, or may be added to the organic solvent solution together with water as a powder.
［クロム測定方法］
本発明のクロム測定方法は、試料液と本発明のクロム測定試薬とを、酸性条件下で反応させて吸光度を測定する方法である。反応時の反応系のｐＨは、０．５〜２が好ましく、１〜１．４がより好ましい。
反応時の反応系のｐＨを調整するための酸としては、硫酸、塩酸、リン酸が挙げられる。中でも硫酸が好ましい。
[Chromium measurement method]
The chromium measurement method of the present invention is a method for measuring absorbance by reacting a sample solution and the chromium measurement reagent of the present invention under acidic conditions. 0.5-2 are preferable and, as for pH of the reaction system at the time of reaction, 1-1.4 are more preferable.
Examples of the acid for adjusting the pH of the reaction system during the reaction include sulfuric acid, hydrochloric acid, and phosphoric acid. Of these, sulfuric acid is preferred.
反応時の反応系のｐＨを調整するための酸は、試料液および本発明のクロム測定試薬とは別に用意した酸溶液を、反応時に試料液および本発明のクロム測定試薬と混合してもよいし、予め試料液および本発明のクロム測定試薬の一方または両方に配合しておいてもよい。また、予め試料液および本発明のクロム測定試薬の一方または両方に酸を配合するとともに、測定時にさらに追加的に酸を混合してもよい。
中でも、別々に用意した、試料液と本発明のクロム測定試薬と酸とを、測定時に混合して反応させることが好ましい。
For the acid for adjusting the pH of the reaction system during the reaction, an acid solution prepared separately from the sample solution and the chromium measurement reagent of the present invention may be mixed with the sample solution and the chromium measurement reagent of the present invention during the reaction. In addition, it may be previously blended in one or both of the sample solution and the chromium measuring reagent of the present invention. In addition, an acid may be mixed in advance with one or both of the sample solution and the chromium measurement reagent of the present invention, and an acid may be further mixed during the measurement.
Especially, it is preferable to mix and react the sample solution prepared separately, the chromium measuring reagent of this invention, and an acid at the time of a measurement.
反応時の温度は、１０〜４０℃であることが好ましく、１５〜２５℃であることがより好ましい。反応時間は、２〜１５分が好ましく、３〜１０分がより好ましい。
吸光度測定の測定波長は、六価クロムとジフェニルカルバジドとが反応して得られる赤紫の錯体を検知できる波長であればよく、５００〜６００ｎｍの範囲の測定波長を選択できる。
The temperature during the reaction is preferably 10 to 40 ° C, and more preferably 15 to 25 ° C. The reaction time is preferably 2 to 15 minutes, more preferably 3 to 10 minutes.
The measurement wavelength of the absorbance measurement may be any wavelength that can detect a reddish purple complex obtained by reaction of hexavalent chromium with diphenylcarbazide, and a measurement wavelength in the range of 500 to 600 nm can be selected.
六価クロムだけでなく、三価クロムを含む全クロムを測定する場合は、試料液と本発明のクロム測定試薬とを、酸性条件下で反応させる前に、試料液中の三価クロムを酸化して六価クロムとする前処理を行う。
三価クロムの酸化は、硫酸酸性で過剰量の過マンガン酸カリウムと加熱することにより行う。過剰の過マンガン酸カリウムと一部生成する酸化マンガン（IV）は、尿素の存在下亜硝酸ナトリウムで還元して分解する。なお、亜硝酸ナトリムは、六価クロムと反応する前に、尿素と反応して分解する。
また，ペルオキソ二硫酸ナトリウム等の過硫酸塩を加えた後，加熱や紫外線を照射することで三価のクロムを酸化する方法もある。
When measuring not only hexavalent chromium but all chromium containing trivalent chromium, the trivalent chromium in the sample solution is oxidized before the sample solution and the chromium measuring reagent of the present invention are reacted under acidic conditions. Then, pretreatment to make hexavalent chromium is performed.
Trivalent chromium is oxidized by heating with an excess of potassium permanganate that is acidic with sulfuric acid. Excess potassium permanganate and partially formed manganese (IV) oxide are decomposed by reduction with sodium nitrite in the presence of urea. Note that sodium nitrite decomposes by reacting with urea before reacting with hexavalent chromium.
There is also a method in which trivalent chromium is oxidized by adding persulfate such as sodium peroxodisulfate and then heating or irradiating with ultraviolet rays.
本発明のクロム測定試薬は、例えば、廃木材等の固体表面に吹き付けて、固体表面に付着したクロムを検出するためにも使用できる。 The chromium measuring reagent of the present invention can be used, for example, by spraying on a solid surface such as waste wood and detecting chromium adhering to the solid surface.
以下、本発明の効果を明らかにするための実験例を示す。なお、以下の実験例で用いたＣｒ６＋１ｍｇ／Ｌ標準液は、関東化学製Ｃｒ１０００クロム標準液（二クロム酸カリウムをＣｒ６＋濃度として１０００ｍｇ／Ｌ含む硝酸０．０１ｍｏｌ／Ｌ溶液）を、水で１０００倍に希釈して調製した。 Examples of experiments for clarifying the effects of the present invention will be described below. The Cr 6+ 1 mg / L standard solution used in the following experimental examples is a Cr1000 chromium standard solution (0.01 mol / L nitric acid solution containing 1000 mg / L potassium dichromate as a Cr 6+ concentration) manufactured by Kanto Chemical. And diluted 1000 times.
［実験例１］
ジフェニルカルバジドの０．２ｇをエチルアルコールの５０ｍＬに加え加熱して溶解させてジフェニルカルバジドのアルコール溶液を得た。このアルコール溶液に、下記の添加剤と水を加えて、または水のみを加えて（添加剤なし）１００ｍＬとし、各測定試薬を得た。
また、ジフェニルカルバジドの０．２ｇをアセトンの５０ｍＬに加え加熱して溶解させてジフェニルカルバジドのアセトン溶液を得た。このアセトン溶液に水を加えて、１００ｍＬとし、アセトン５０％の測定試薬を得た。
[Experimental Example 1]
0.2 g of diphenylcarbazide was added to 50 mL of ethyl alcohol and dissolved by heating to obtain an alcohol solution of diphenylcarbazide. The following additives and water were added to this alcohol solution, or only water was added (no additive) to make 100 mL, and each measurement reagent was obtained.
Further, 0.2 g of diphenylcarbazide was added to 50 mL of acetone and dissolved by heating to obtain an acetone solution of diphenylcarbazide. Water was added to this acetone solution to make 100 mL, and a measuring reagent with 50% acetone was obtained.
（添加剤）
・塩化ヒドロキシルアンモニウムの０．１ｇ（測定試薬中の濃度：１ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．０５ｇ（測定試薬中の濃度：０．５ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．０１ｇ（測定試薬中の濃度：０．１ｇ／Ｌ）
・０．１ｍｏｌ／ＬのＨＣｌ溶液の２．５ｍＬ（測定試薬中の濃度：２．５ｍｍｏｌ／Ｌ）
・９９．７質量％酢酸溶液の１滴
・１ｍｏｌ／Ｌ硫酸の１ｍＬ（測定試薬中の濃度：１０ｍｍｏｌ／Ｌ）
・９６質量％濃硫酸の１滴
(Additive)
・ 0.1 g of hydroxylammonium chloride (concentration in measurement reagent: 1 g / L)
-0.05 g of hydroxylammonium chloride (concentration in measurement reagent: 0.5 g / L)
・ 0.01 g of hydroxylammonium chloride (concentration in measurement reagent: 0.1 g / L)
・ 2.5 mL of 0.1 mol / L HCl solution (concentration in measurement reagent: 2.5 mmol / L)
1 drop of 99.7% by mass acetic acid solution 1 mL of 1 mol / L sulfuric acid (concentration in measurement reagent: 10 mmol / L)
・ One drop of 96 mass% concentrated sulfuric acid
各測定試薬を容量１００ｍＬの褐色ガラス瓶に入れ、４０℃の環境下、約１ヶ月強保管した。
調製直後と、数日ないし１０日前後の間隔をおいた保管日数経過後において、褐色ガラス瓶内の各測定試薬の０．５ｍＬをその都度採取し、以下の手順でＣｒ６＋１ｍｇ／Ｌ標準液と反応させた。
すなわち、Ｃｒ６＋１ｍｇ／Ｌ標準液の５ｍＬに、硫酸（１＋１３）の０．５ｍＬと測定試薬の０．５ｍＬを加えて混合し、室温（約２５℃）にて５分放置した後に、５４０ｎｍの吸光度を測定し、下記式に基づき感度を求めた。結果を図１、図２に示す。なお、硫酸（１＋１３）は、濃硫酸の１体積を水の１３体積で希釈した硫酸溶液である。硫酸（１＋１３）の０．５ｍＬを加えることにより、この反応系のｐＨは約１である。
感度（％）
＝（所定の保管日数経過後の吸光度−調製直後の吸光度）／調製直後の吸光度×１００
Each measuring reagent was put in a brown glass bottle with a capacity of 100 mL and stored for about one month in a 40 ° C. environment.
Immediately after preparation and 0.5 days after storage for several days to around 10 days, 0.5 mL of each measurement reagent in the brown glass bottle is sampled each time, and Cr 6 + 1 mg / L standard solution and Reacted.
Specifically , 0.5 mL of sulfuric acid (1 + 13) and 0.5 mL of a measurement reagent were added to 5 mL of Cr 6+ 1 mg / L standard solution, mixed, and allowed to stand at room temperature (about 25 ° C.) for 5 minutes, and then 540 nm Absorbance was measured and sensitivity was determined based on the following formula. The results are shown in FIGS. The sulfuric acid (1 + 13) is a sulfuric acid solution obtained by diluting 1 volume of concentrated sulfuric acid with 13 volumes of water. The pH of the reaction is about 1 by adding 0.5 mL of sulfuric acid (1 + 13).
sensitivity(%)
= (Absorbance after elapse of predetermined storage days-Absorbance immediately after preparation) / Absorbance immediately after preparation × 100
図１に示すように、塩化ヒドロキシルアンモニウムを、測定試薬中の濃度が１ｇ／Ｌとなるように加えると２週間経過後の感度低下もわずか２．７％であり、他の種類の添加剤と比較して、極めて高い感度維持効果が得られた。
また、図２に示すように、塩化ヒドロキシルアンモニウムの添加量が多いほど、高い感度維持効果が得られた。特に、測定試薬中の塩化ヒドロキシルアンモニウム濃度が０．５ｇ／Ｌ以上となると、１週間経過後の感度低下が約３％であり、２週間経過後の感度低下は６．７％であり、自動分析計での長期使用に充分耐え得るものであった。
As shown in FIG. 1, when hydroxylammonium chloride was added so that the concentration in the measurement reagent was 1 g / L, the sensitivity decrease after 2 weeks was only 2.7%. In comparison, an extremely high sensitivity maintaining effect was obtained.
Moreover, as shown in FIG. 2, the higher the amount of hydroxylammonium chloride added, the higher the sensitivity maintaining effect. In particular, when the concentration of hydroxylammonium chloride in the measurement reagent is 0.5 g / L or more, the decrease in sensitivity after 1 week is about 3%, and the decrease in sensitivity after 2 weeks is 6.7%. It was able to withstand long-term use with an analyzer.
［実験例２］
ジフェニルカルバジドの０．２ｇをエチルアルコールの５０ｍＬに加え加熱して溶解させてジフェニルカルバジドのアルコール溶液を得た。このアルコール溶液に、下記の添加剤と水を加えて、または水のみを加えて（添加剤なし）１００ｍＬとし、各測定試薬を得た。
・塩化ヒドロキシルアンモニウムの０．０１ｇ（測定試薬中の濃度：０．１ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．０５ｇ（測定試薬中の濃度：０．５ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．１ｇ（測定試薬中の濃度：１ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの１．１ｇ（測定試薬中の濃度：１０ｇ／Ｌ）
・９９質量以上％のＬ（＋）−アスコルビン酸の０．２ｇ（測定試薬中の濃度：２ｇ／Ｌ）
・９９．７質量％酢酸溶液の１滴
・０．０１ｍｏｌ／ＬのＨＣｌ溶液の０．５ｍＬ（測定試薬中の濃度：０．０５ｍｍｏｌ／Ｌ）
[Experiment 2]
0.2 g of diphenylcarbazide was added to 50 mL of ethyl alcohol and dissolved by heating to obtain an alcohol solution of diphenylcarbazide. The following additives and water were added to this alcohol solution, or only water was added (no additive) to make 100 mL, and each measurement reagent was obtained.
・ 0.01 g of hydroxylammonium chloride (concentration in measurement reagent: 0.1 g / L)
-0.05 g of hydroxylammonium chloride (concentration in measurement reagent: 0.5 g / L)
・ 0.1 g of hydroxylammonium chloride (concentration in measurement reagent: 1 g / L)
-1.1 g of hydroxylammonium chloride (concentration in measurement reagent: 10 g / L)
-0.2 g of 99% by mass or more of L (+)-ascorbic acid (concentration in measurement reagent: 2 g / L)
-1 drop of 99.7 mass% acetic acid solution-0.5 mL of 0.01 mol / L HCl solution (concentration in measurement reagent: 0.05 mmol / L)
Ｃｒ６＋１ｍｇ／Ｌ標準液の５ｍＬに、硫酸（１＋１３）の０．５ｍＬと調製直後の各測定試薬の０．５ｍＬを加えて混合し、室温（約２５℃）にて５分放置した後に、５４０ｎｍの吸光度を測定した。結果を表１に示す。
表１に示すように、塩化ヒドロキシルアンモニウムは、アスコルビン酸と同様に還元剤であるにも関わらず、アスコルビン酸より、高い初期感度が得られた。また、塩化ヒドロキシルアンモニウムの添加量が少ないほど、高い初期感度が得られた。特に、測定試薬中の塩化ヒドロキシルアンモニウム濃度が１ｇ／Ｌ以下では、還元作用を有しない酢酸や塩酸に匹敵する初期感度が得られ、自動分析計での高い精度の測定を可能とするものであった。
To 5 mL of Cr 6+ 1 mg / L standard solution, 0.5 mL of sulfuric acid (1 + 13) and 0.5 mL of each measurement reagent immediately after preparation were added and mixed, and allowed to stand at room temperature (about 25 ° C.) for 5 minutes. Absorbance at 540 nm was measured. The results are shown in Table 1.
As shown in Table 1, although hydroxylammonium chloride was a reducing agent like ascorbic acid, higher initial sensitivity was obtained than ascorbic acid. Moreover, the higher initial sensitivity was obtained, so that the addition amount of hydroxylammonium chloride was small. In particular, when the concentration of hydroxylammonium chloride in the measurement reagent is 1 g / L or less, initial sensitivity comparable to acetic acid and hydrochloric acid having no reducing action can be obtained, and high-accuracy measurement with an automatic analyzer is possible. It was.
［実験例３］
ジフェニルカルバジドの０．２ｇをエチルアルコールの５０ｍＬに加え加熱して溶解させてジフェニルカルバジドのアルコール溶液を得た。このアルコール溶液に、下記の添加剤と水を加えて、または水のみを加えて（塩化ヒドロキシルアンモニウムの添加量ゼロ）１００ｍＬとし、各測定試薬を得た。
・塩化ヒドロキシルアンモニウムの０．０１ｇ（測定試薬中の濃度：０．１ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．０５ｇ（測定試薬中の濃度：０．５ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの０．１ｇ（測定試薬中の濃度：１ｇ／Ｌ）
・塩化ヒドロキシルアンモニウムの１．１ｇ（測定試薬中の濃度：１０ｇ／Ｌ）
[Experiment 3]
0.2 g of diphenylcarbazide was added to 50 mL of ethyl alcohol and dissolved by heating to obtain an alcohol solution of diphenylcarbazide. The following additives and water were added to this alcohol solution, or only water was added (the amount of hydroxylammonium chloride added was zero) to 100 mL to obtain each measurement reagent.
・ 0.01 g of hydroxylammonium chloride (concentration in measurement reagent: 0.1 g / L)
-0.05 g of hydroxylammonium chloride (concentration in measurement reagent: 0.5 g / L)
・ 0.1 g of hydroxylammonium chloride (concentration in measurement reagent: 1 g / L)
-1.1 g of hydroxylammonium chloride (concentration in measurement reagent: 10 g / L)
Ｃｒ６＋１ｍｇ／Ｌ標準液の５ｍＬに、硫酸（１＋１３）の０．５ｍＬと調製直後の各測定試薬の０．５ｍＬを加えて混合し、１０℃にて５分放置した後に、５４０ｎｍの吸光度を測定し、１０℃初期感度を得た。
Ｃｒ６＋１ｍｇ／Ｌ標準液の５ｍＬに、硫酸（１＋１３）の０．５ｍＬと調製直後の各測定試薬の０．５ｍＬを加えて混合し、４５℃にて５分放置した後に、５４０ｎｍの吸光度を測定し、４５℃初期感度を得た。
そして、１０℃初期感度と４５℃初期感度から、下記式に基づき感度変化率を求めた。結果を表２に示す。
感度変化率（％）＝（４５℃初期感度−１０℃初期感度）／１０℃初期感度×１００
To 5 mL of Cr 6+ 1 mg / L standard solution, add 0.5 mL of sulfuric acid (1 + 13) and 0.5 mL of each measurement reagent immediately after preparation, mix and leave at 10 ° C. for 5 minutes, and then absorb the absorbance at 540 nm. Measurement was performed to obtain an initial sensitivity of 10 ° C.
Add 5 mL of sulfuric acid (1 + 13) and 0.5 mL of each measurement reagent immediately after preparation to 5 mL of Cr 6+ 1 mg / L standard solution, mix and leave at 45 ° C. for 5 minutes, and then absorb the absorbance at 540 nm. The initial sensitivity was measured at 45 ° C.
Then, from the initial sensitivity at 10 ° C. and the initial sensitivity at 45 ° C., the rate of change in sensitivity was determined based on the following formula. The results are shown in Table 2.
Sensitivity change rate (%) = (45 ° C. initial sensitivity−10 ° C. initial sensitivity) / 10 ° C. initial sensitivity × 100
表２に示すように、塩化ヒドロキシルアンモニウムの添加量が少ないほど、感度変化率が低い傾向にあった。特に、測定試薬中の塩化ヒドロキシルアンモニウム濃度が１ｇ／Ｌ以下では、１０℃から４５℃まで大幅に温度が変化しても感度変化率は１０％未満に留まり、自動分析計の使用環境温度を厳密に調整しなくても、実用上充分な精度が得られるものであった。 As shown in Table 2, the smaller the amount of hydroxylammonium chloride added, the lower the sensitivity change rate. In particular, when the concentration of hydroxylammonium chloride in the measurement reagent is 1 g / L or less, the rate of change in sensitivity remains below 10% even when the temperature changes significantly from 10 ° C to 45 ° C, and the operating environment temperature of the automatic analyzer is strict. Even if it was not adjusted to a sufficient level, practically sufficient accuracy could be obtained.
本発明のクロム測定試薬及びクロム測定方法は、各種工場排水、河川水等のクロムの測定、特に、自動分析計による測定に適している。
本発明のクロム測定試薬及びクロム測定方法は、水中のクロム測定に限られず、例えば、建築廃材に付着したクロムの検出等にも使用できる。
The chromium measuring reagent and chromium measuring method of the present invention are suitable for the measurement of chromium in various factory effluents, river water, etc., particularly for the measurement by an automatic analyzer.
The chromium measuring reagent and the chromium measuring method of the present invention are not limited to the measurement of chromium in water, and can be used, for example, for detecting chromium adhering to building waste materials.
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