CN101275914A - Method of determining chelating agent and determination kit for chelating agent - Google Patents
Method of determining chelating agent and determination kit for chelating agent Download PDFInfo
- Publication number
- CN101275914A CN101275914A CNA2007100918456A CN200710091845A CN101275914A CN 101275914 A CN101275914 A CN 101275914A CN A2007100918456 A CNA2007100918456 A CN A2007100918456A CN 200710091845 A CN200710091845 A CN 200710091845A CN 101275914 A CN101275914 A CN 101275914A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- reagent solution
- sample water
- sequestrant
- agent
- 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
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S435/00—Chemistry: molecular biology and microbiology
- Y10S435/975—Kit
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The purpose of the invention is to simply know the concentration of a water treatment agent on the spot where a heat device is installed. A method for determining chelating agent includes a step of collecting sample water, a step of respectively adding a first chemical solution containing a metal indicator and a second chemical solution containing a pH controller to the collected sample water, a step of dripping a third chemical solution, which contains a metal salt for discoloring the metal indicator, on the sample water to which the first chemical solution and the second chemical solution are added and counting a dripping number until the sample water is discolored and a step of specifying the concentration of the chelating agent in the sample water on the basis of the dripping number of the third chemical solution. The measuring kit includes a first container in which the first chemical solution containing the metal indicator is housed, a second container in which the second chemical solution containing the pH controller is housed and a third container in which the third solution containing the metal salt for discoloring the metal indicator.
Description
Technical field
The present invention relates to the assay method of sequestrant and the mensuration kit of sequestrant, particularly be used for determining easily being added with the assay method of the contained sequestrant concentration of the water of water treatment agent and measure kit.
Background technology
In heat exchangers such as boiler or cooling tower,, in make-up water, add water treatment agent usually in order to suppress moisture to the corrosion of heat-transfer area or the generation of incrustation scale.In recent years, as patent documentation 1 is disclosed, in above-mentioned boiler, use the water treatment agent that constitutes, contains silicon dioxide, alkaline agent and scale inhibitor by food additives.Here, the purpose that cooperates above-mentioned silicon dioxide is to form tunicle on above-mentioned heat-transfer area, prevents the corrosion of moisture.In addition, above-mentioned alkaline agent is typical alkali-metal oxyhydroxide, and the purpose of its cooperation is that moisture is adjusted to the pH zone (pH 11-12) that above-mentioned heat-transfer area is difficult to be corroded.Above-mentioned scale inhibitor is to promote composition with incrustation scale in the make-up water---hardness components (calcium ion and magnesium ion), copper ion, zinc ion and ferric ion etc. form the sequestrant of complex compound, and the purpose of its cooperation is to be suppressed at the incrustation scale of looking unfamiliar into that above-mentioned heat-transfer area contacts with moisture.
The quantity delivered of above-mentioned water treatment agent can be set the water treatment agent concentration that makes in the above-mentioned heat exchanger for according to the water quality of make-up water or the operating condition of above-mentioned heat exchanger (concentration rate in for example above-mentioned boiler) etc. and be set in the specialized range.In order to bring into play the effect of above-mentioned water treatment agent to greatest extent, it is very important within the specific limits that water treatment agent concentration is kept, and when water treatment agent concentration is not enough or when superfluous, must promptly readjust the supply of above-mentioned water treatment agent.For this reason, maintenance management person or user must be provided with the on-the-spot water treatment agent of the understanding regularly concentration of above-mentioned heat exchanger.
Patent documentation 1:JP2003-159597A
Summary of the invention
But, need carry out respectively the whole compositions as above-mentioned water treatment agent supply quantitatively for understanding water treatment agent concentration, this needs a lot of operations and work.For example if the water treatment agent shown in the patent documentation 1, above-mentioned special component as the water treatment agent supply is carried out when quantitative, because silicon dioxide forms tunicle on above-mentioned heat-transfer area, therefore concentration and the inconsistent problem of being calculated by supply of actual concentrations arranged.And, also generate during the alkali composition thermal decompositions such as sodium bicarbonate of alkali-metal oxyhydroxide in make-up water, therefore in the particularly above-mentioned boiler, inconsistent by concentration and actual concentrations that supply is calculated.For the foregoing reasons, in fact can't at above-mentioned heat exchanger the on-the-spot water treatment agent concentration of understanding be set easily.
The present invention is directed to the problems referred to above and establish, its purpose is can understand water treatment agent concentration easily at the scene that heat exchanger is set.
The present invention can realize above-mentioned purpose.First content of the present invention relates to the assay method of sequestrant concentration in the sample water, and this method comprises following operation: the operation of gathering sample water; In the sample water of gathering, add first reagent solution that contains metal indicator and the operation that contains second reagent solution of pH regulator agent respectively; In the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip the 3rd reagent solution that contains the slaine that makes above-mentioned metal indicator variable color, count up to the operation of dripping number of sample water variable color; The operation that number is determined sequestrant concentration in the sample water of dripping based on above-mentioned the 3rd reagent solution.
According to first content, in the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution, the preferential special metal ion forming complex with from above-mentioned slaine of then above-mentioned sequestrant.The total amount of above-mentioned sequestrant and above-mentioned special metal ion forming complex, then above-mentioned metal indicator and remaining above-mentioned specific ion form complex compound, the variable color of sample water.The supply of above-mentioned special metal ion is corresponding with the amount of above-mentioned sequestrant before the variable color of sample water, therefore according to the number that drips of above-mentioned the 3rd reagent solution, can determine the concentration of above-mentioned sequestrant.Therefore, adopt this assay method, can understand water treatment agent concentration in the heat exchanger easily with the above-mentioned sequestrant that contains in the water treatment agent as index.
Second content of the present invention is included in first content, further adds the operation of screening agent in the sample water of being gathered.
According to second content, in the presence of above-mentioned screening agent, drip the 3rd reagent solution, then ferrous ion or the preferential and above-mentioned screening agent of copper ion with above-mentioned sequestrant complexing forms complex compound.Therefore, the total amount of above-mentioned sequestrant and above-mentioned special metal ion form complex compound rapidly, can foreshorten to the required reaction time of sample water variable color.Therefore, adopt this assay method, with the above-mentioned sequestrant that contains in the water treatment agent as index, can be rapidly and understand water treatment agent concentration in the above-mentioned heat exchanger exactly.
The 3rd content of the present invention is in second content, comprises the operation of further adding reductive agent in the sample water of gathering.
According to the 3rd content, add above-mentioned reductive agent, then the ferric ion in the sample water is reduced to ferrous ion.This ferrous ion is sealed by above-mentioned screening agent.Therefore, can prevent that above-mentioned metal indicator and ferric ion from forming complex compound and colour developing, guarantees the normal tone of sample water.Therefore, adopt this assay method, as index, can understand water treatment agent concentration in the heat exchanger more accurately with the above-mentioned sequestrant that contains in the water treatment agent.
The 4th content of the present invention is the assay method of sequestrant concentration in the sample water, and this method comprises following operation: the operation of gathering sample water; In the sample water of gathering, add first reagent solution that contains metal indicator and the operation that contains second reagent solution of pH regulator agent respectively; In the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip the 3rd reagent solution that contains the slaine that makes above-mentioned metal indicator variable color, count up to the required operation of dripping number of sample water variable color; The operation that number is determined sequestrant concentration in the sample water of dripping according to above-mentioned the 3rd reagent solution; Above-mentioned sequestrant is ethylenediamine tetraacetic acid and salt thereof, and above-mentioned metal indicator, above-mentioned pH regulator agent and above-mentioned slaine are respectively xylenol orange, nitric acid and bismuth nitrate.
According to the 4th content, in the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution, then ethylenediamine tetraacetic acid (EDTA) bismuth ion preferential and from bismuth nitrate forms complex compound.EDTA total amount and bismuth ion form complex compound, and then xylenol orange and remaining bismuth ion form complex compound, the variable color of sample water.Supply to the bismuth ion of sample water variable color is corresponding with the amount of EDTA, therefore, and according to the concentration that number can be determined EDTA of dripping of above-mentioned the 3rd reagent solution.Therefore, use this assay method, as index, can understand the water treatment agent concentration in the heat exchanger easily with the EDTA that contains in the water treatment agent.
The 5th content of the present invention is to comprise the operation of further adding screening agent in the sample water of gathering in the 4th content, and this screening agent is the o-phenanthroline.
According to the 5th content, in the presence of the o-phenanthroline, drip above-mentioned the 3rd reagent solution, then will with the ferrous ion of EDTA complexing or copper ion preferential with o-phenanthroline formation complex compound.Therefore, the total amount of EDTA can form complex compound rapidly with bismuth ion, can foreshorten to the required reaction time of sample water variable color.Therefore, adopt this assay method, with the EDTA that contains in the water treatment agent as index, can be rapidly and understand water treatment agent concentration in the heat exchanger exactly.
The 6th content of the present invention is to comprise the operation of further adding reductive agent in the sample water of gathering in the 5th content, and wherein said reductive agent is ascorbic acid and alkali metal salt thereof.
According to the 6th content, add ascorbic acid or its alkali metal salt then the ferric ion in the sample water be reduced to ferrous ion.This ferrous ion is sealed by the o-phenanthroline.Therefore can prevent that xylenol orange and ferric ion from forming complex compound and colour developing, can guarantee the normal tone of sample water.Therefore, adopting this assay method, is index with the EDTA that contains in the water treatment agent, can understand water treatment agent concentration in the heat exchanger more accurately.
The 7th content of the present invention is the mensuration kit that sequestrant concentration in the sample water is carried out quantitative sequestrant, and this kit possesses first container that first reagent solution is housed, this first reagent solution containing metal indicator; Second container of second reagent solution is housed, and this second reagent solution contains the pH regulator agent; The 3rd container of the 3rd reagent solution is housed, and the 3rd reagent solution contains the slaine that makes above-mentioned metal indicator variable color.
According to the 7th content, in sample water, add above-mentioned first reagent solution by above-mentioned first container, simultaneously by adding above-mentioned second reagent solution in above-mentioned second container, drip above-mentioned the 3rd reagent solution by the 3rd container then, then above-mentioned sequestrant with preferentially form complex compound from the special metal ion of above-mentioned slaine.The total amount of above-mentioned sequestrant and above-mentioned special metal ion forming complex, then above-mentioned metal indicator and remaining above-mentioned special metal ion forming complex, the variable color of sample water.Supply to the special metal ion of sample water variable color is corresponding with the amount of above-mentioned sequestrant, therefore according to the concentration that number can be determined above-mentioned sequestrant of dripping of above-mentioned the 3rd reagent solution.Therefore, adopt this mensuration kit, as index, can easily understand the water treatment agent concentration in the heat exchanger with the above-mentioned sequestrant that contains in the water treatment agent.
The 8th content of the present invention is in the 7th content, and above-mentioned first reagent solution or above-mentioned second reagent solution further contain screening agent.
According to the 8th content, in sample water, add above-mentioned screening agent by above-mentioned first reagent solution or above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution then, then ferrous ion or the preferential and above-mentioned screening agent of copper ion with above-mentioned sequestrant complexing forms complex compound.Therefore, above-mentioned sequestrant total amount and above-mentioned special metal ion form complex compound rapidly, can foreshorten to the required reaction time of sample water variable color.Therefore, use this mensuration kit, with the above-mentioned sequestrant that contains in the water treatment agent as index, can be rapidly and understand water treatment agent concentration in the heat exchanger exactly.
The 9th content of the present invention is that above-mentioned first reagent solution further contains reductive agent in the 8th content.
According to the 9th content, add above-mentioned reductive agent by above-mentioned first reagent solution, then the ferric ion in the sample water is reduced to ferrous ion.This ferrous ion is sealed by above-mentioned screening agent.Therefore, can prevent that above-mentioned metal indicator and ferric ion from forming complex compound and colour developing, can guarantee the normal tone of sample water.Therefore, adopt this mensuration kit, as index, can understand the water treatment agent concentration in the heat exchanger more accurately with the above-mentioned sequestrant that contains in the water treatment agent.
The of the present invention ten content is to possess the 4th container in the 8th content, and the 4th container is equipped with powder reducing agent.
According to the tenth content, add pulverous above-mentioned reductive agent by above-mentioned the 4th container, then the ferric ion in the sample water is reduced to ferrous ion.This ferrous ion is sealed by above-mentioned screening agent.Therefore can prevent that above-mentioned metal indicator and ferric ion from forming complex compound and colour developing, can guarantee the normal tonal variation of sample water.Therefore, adopt this mensuration kit, as index, can understand the water treatment agent concentration in the heat exchanger more accurately with the above-mentioned sequestrant that contains in the water treatment agent.
According to the present invention, can understand water treatment agent concentration easily at the scene that is provided with heat exchanger.The result can judge at the scene whether the water treatment agent supply is suitable in the heat exchanger, can make the maintenance management of water treatment more efficient.
The accompanying drawing summary
Fig. 1 is the correlogram of the EDTA-2Na quantitative values of the EDTA-2Na quantitative values of expression HPLC method and simple and easy titrimetry.
Embodiment
Below, describe embodiment of the present invention in detail.It is the management of the heat exchanger water treatment agent supply of representative that the assay method of sequestrant of the present invention and mensuration kit are used for boiler or cooling tower etc.Specifically, as tracer, determine the water treatment agent concentration in the above-mentioned heat exchanger with the above-mentioned sequestrant that cooperates in the above-mentioned water treatment agent, suitably whether supply that to judge above-mentioned water treatment agent according to this water treatment agent concentration.
In the above-mentioned water treatment agent, above-mentioned sequestrant is that the incrustation scale that is used for sealing water promotes that composition---hardness components (calcium ion or magnesium ion), copper ion, zinc ion and ferric ion etc., the generation that suppresses the incrustation scale on the above-mentioned heat exchanger heat-transfer area cooperates.Described sequestrant for example can use the amino carboxylic acid based compound of organic system and the polyphosphoric acid based compound of tricarboxylic acids based compound and inorganic system etc.
The object lesson of above-mentioned amino carboxylic acid based compound has: ethylenediamine tetraacetic acid (EDTA) and salt thereof, nitrilotriacetic acid (NTA) and salt thereof, hydroxyethylethylene diamine tri-acetic acid (HEDTA) and salt thereof, anti-form-1,2-diamino-cyclohexane tetraacethyl (CyDTA) and salt thereof etc.In addition, the object lesson of above-mentioned tricarboxylic acids based compound has citric acid and salt thereof etc.The object lesson of above-mentioned polyphosphoric acid based compound has hydroxy ethylene diphosphonic acid (HEDT) and salt thereof etc.In these compounds, the alkali metal salt of ethylenediamine tetraacetic acid is the compound that does not promote to generate incrustation scale on above-mentioned heat-transfer area, therefore preferred the employing.And in the alkali metal salt of ethylenediamine tetraacetic acid, disodium EDTA is the compound that can be used as the safety of food additives use, therefore especially preferably adopts.
The said determination kit be used for by titrimetry to the above-mentioned sequestrant of sample water for example the concentration of EDTA carry out quantitatively.The said determination kit possesses first container that first reagent solution is housed, and wherein first reagent solution contains metal indicator; Second container of second reagent solution is housed, and wherein second reagent solution contains the pH regulator agent; The 3rd container of the 3rd reagent solution is housed, and wherein the 3rd reagent solution contains the slaine that makes above-mentioned metal indicator variable color.
Above-mentioned first container, above-mentioned second container and above-mentioned the 3rd container are the container classes that stores reagent solution, can drip reagent solution simultaneously in sample water, for example can utilize the dropping bottle of band nozzle, and its structure is on resinous bottle nozzle to be installed.The bottle of the form of the reagent solution that the dropping bottle of this band nozzle is the bottle portion of pushing above-mentioned bottle in use, drip ormal weight.In addition, above-mentioned first container, above-mentioned second container and above-mentioned the 3rd container can utilize the dropping bottle of band dropper, and its structure is to cover the installation dropper at bottle.The dropping bottle of this band dropper is drawn the reagent solution in the above-mentioned bottle in use by above-mentioned dropper, drip the bottle of the form of ormal weight reagent solution then.And above-mentioned first container, above-mentioned second container and above-mentioned the 3rd container also can use the band dropper container that dropper is arranged that separate with bottle, subsidiary.The container of this band dropper is in use the reagent solution in the above-mentioned bottle to be drawn by above-mentioned dropper, drips the form of the reagent solution of ormal weight then.
Above-mentioned first reagent solution, above-mentioned second reagent solution and above-mentioned the 3rd reagent solution are polluted or rotten angle is considered, above-mentioned bottle is preferably the insoluble material (for example tygon or glass etc.) that goes out impurity, simultaneously can shading.Consider that from the easy degree of operation and the easy degree of carrying the capacity of above-mentioned bottle preferably sets the scope at 25-100mL.
Then, above-mentioned first reagent solution, above-mentioned second reagent solution and above-mentioned the 3rd reagent solution are described.At first above-mentioned first reagent solution is described.The above-mentioned metal indicator that contains in above-mentioned first reagent solution be with above-mentioned the 3rd reagent solution in the above-mentioned reacting metal salt that contains and the pigment of variable color be the chelating material, be used to detect the terminal point of titration operation.In the titration operation of above-mentioned sequestrant as quantitative object, constitute above-mentioned slaine metallic ion (following for sample water in the metallic ion difference that contains, be called " special metal ion ") must preferentially form complex compound with above-mentioned sequestrant.Therefore, above-mentioned metal indicator is selected from the chelating material littler than above-mentioned sequestrant with the degree of stability constant of above-mentioned special metal ion.For example with EDTA during as quantitative object, described chelating material can use xylenol orange (chemical name: 3,3 '-two [N, N-two (ethyloic) amino methyl]-o-cresolsulfon-phthalein, disodium salt) or methylthymol blue (chemical name: 3,3 '-two [N, N-two (ethyloic) amino methyl] thymolsulfonphthalein, disodium salt).
As described later, the operation that when adding to above-mentioned first reagent solution in the sample water, will supply the above-mentioned metal indicator of ormal weight, therefore therefore the content of the above-mentioned metal indicator in above-mentioned first reagent solution be not particularly limited.Usually, consider, can suitably be set in the scope of 0.1-0.6 weight % from the angle of dissolubility and economy.
In order to seal ferrous ion and the copper ion in the sample water, can contain screening agent in above-mentioned first reagent solution.From the ferrous ion of make-up water or pipeline material etc. and copper ion usually with the strong complexing of above-mentioned sequestrant, therefore be difficult to take place the displacement with above-mentioned special metal ion, terminal point determining needs the long period during titration operation.On the other hand, contain above-mentioned screening agent in above-mentioned first reagent solution, then the preferential and above-mentioned screening agent of ferrous ion and copper ion forms complex compound, therefore, the total amount of above-mentioned sequestrant can form complex compound rapidly with above-mentioned special metal ion, can foreshorten to the needed reaction time of sample water variable color.Here, to be selected from degree of stability constant with ferrous ion and copper ion bigger and do not hinder the chelating material of the identification of above-mentioned metal indicator tonal variation when sealing ferrous ion and copper ion than above-mentioned sequestrant for above-mentioned screening agent.When being quantitative object with EDTA, described chelating material can utilize o-phenanthroline etc.
As described later, when adding to above-mentioned first reagent solution in the sample water, supply with the operation of the above-mentioned screening agent of ormal weight, therefore the content of the above-mentioned screening agent in above-mentioned first reagent solution is not particularly limited.Usually consider from dissolubility and economy angle, can in the scope of 0.5-5 weight %, suitably set.
In order to prevent that the ferric ion in above-mentioned metal indicator and the sample water from forming complex compound and variable color, can contain reductive agent in above-mentioned first reagent solution.For example, the xylenol orange in the acid solution is yellow at pH6 or when following, but then becomes blueness with the ferric ion complexing.Therefore, normal tonal variation not taking place in the titration operation, can not carry out the quantitative of above-mentioned sequestrant.On the other hand, ferric ion is reduced to ferrous ion, then xylenol orange shows original tone.Here, above-mentioned reductive agent is selected to have ferric ion is reduced to the effect of ferrous ion and muddiness, precipitation and painted reducing substances do not take place in sample water.Described reducing substances for example can use ascorbic acid and alkali metal salt thereof, alkali-metal sulphite, alkali-metal hydrosulfite and oxammonium hydrochloride etc.
As described later, will supply with the operation of the above-mentioned reductive agent of ormal weight when adding to above-mentioned first reagent solution in the sample water, therefore the content for above-mentioned reductive agent in above-mentioned first reagent solution is not particularly limited.Usually, consider, can in the scope of 0.1-10 weight %, suitably set from dissolubility and economy angle.
Above-mentioned first reagent solution can be by being dissolved in above-mentioned metal indicator and other additive (above-mentioned screening agent and above-mentioned reductive agent) as preparing in the water of solvent or the alcohol equably.For example, when being quantitative object with EDTA, above-mentioned first reagent solution can be prepared as follows: xylenol orange is dissolved in the water, adds the o-phenanthroline and the mixing that are dissolved in the alcohol in this solution, add pulverous ascorbic acid and mixing again.
Then above-mentioned second reagent solution is described.The above-mentioned pH regulator agent that contains in above-mentioned second reagent solution is used for sample water is adjusted to the acidic region that above-mentioned metal indicator can sharp variable color.Above-mentioned pH regulator agent can utilize usually contain acid or with the buffering agent of acid and salt thereof.Here, utilizable acid is organic acids such as mineral acids such as nitric acid, hydrochloric acid and sulfuric acid and acetate.In addition, the salt of available acid here is the alkali metal salt of nitric acid, hydrochloric acid, sulfuric acid and acetate etc.Sour or sour salt can be with any two kinds or above being used in combination.
As described later, the operation of pH in specialized range of the sample water after when adding to above-mentioned second reagent solution in the sample water, will making interpolation, therefore the content for above-mentioned pH regulator agent in above-mentioned second reagent solution is not particularly limited.Usually consider that from the angle of guaranteeing safety in utilization preferably its content can not become Toxic.In addition, when above-mentioned water treatment agent contained alkali-metal oxyhydroxide, sample water presented the alkalescence zone, therefore preferably contained the acid of the amount that is adjustable to neutralization and acidic region as above-mentioned pH regulator agent.
In order to seal ferrous ion and the copper ion in the sample water, can contain above-mentioned screening agent in above-mentioned second reagent solution.Above-mentioned screening agent can be contained in above-mentioned first reagent solution and above-mentioned second reagent solution among either party usually.As described later, will supply with the operation of the above-mentioned screening agent of ormal weight when adding to above-mentioned second reagent solution in the sample water, therefore the content of the above-mentioned screening agent in above-mentioned second reagent solution is not particularly limited.Usually consider from the angle of dissolubility and economy, can in the scope of 0.5-5 weight %, suitably set.
Above-mentioned second reagent solution can be by preparing above-mentioned pH regulator agent and other additive (above-mentioned screening agent) uniform dissolution in as the water of solvent or alcohol.For example, can be prepared as follows as above-mentioned second reagent solution of quantitative object: nitric acid dissolve in water, is added the o-phenanthroline and the mixing that are dissolved in the alcohol in this solution with EDTA.
Then above-mentioned the 3rd reagent solution is described.The above-mentioned slaine that contains in above-mentioned the 3rd reagent solution is used for to the above-mentioned special metal ion of sample water supply that is added with above-mentioned first reagent solution and above-mentioned second reagent solution.Above-mentioned slaine is selected from the inorganic salts of the polyvalent metal that can supply with above-mentioned special metal ion, and wherein said above-mentioned special metal ion can make above-mentioned metal indicator be changed to the tone of regulation after preferential and above-mentioned sequestrant forms complex compound.When for example its above-mentioned metal indicator was xylenol orange, the inorganic salts of described polyvalent metal can utilize bismuth nitrate.Here, the sample water that has added xylenol orange is at pH 6 or following xylenol orange and bismuth ion complexing then are changed to redness for yellow, so according to the terminal point of this tonal variation decidable titration operation.In addition, when the o-phenanthroline (being above-mentioned screening agent) of ferrous ion and copper ion is sealed in coexistence in the sample water, sample water is not yellow and present orangely, and xylenol orange and bismuth ion complexing then are changed to redness, so according to the terminal point of this tonal variation decidable titration operation.
The content of above-mentioned slaine can be set according to the capacity of decomposition of above-mentioned sequestrant quantitative values in above-mentioned the 3rd reagent solution.That is, regulate the content of above-mentioned slaine in advance, the above-mentioned slaine that contains in above-mentioned second reagent solution of being discharged by said nozzle or above-mentioned dropper and the above-mentioned sequestrant of ormal weight are reacted.For example, above-mentioned the 3rd reagent solution that is 10mL at sample water, is discharged by said nozzle or above-mentioned dropper is under the condition of 0.035g, with every capacity of decomposition that is equivalent to 0.05mg the EDTA of the free state that contains in the sample water and complex status is carried out when quantitative with the form of EDTA-2Na, the content of bismuth nitrate is set at 0.168 weight %.
For the discharge rate that makes a said nozzle or above-mentioned dropper is certain, can contain surface tension reducing agent in above-mentioned the 3rd reagent solution.For example, when the bottle part of the drop bottle of slowly pushing and push fast above-mentioned band nozzle, the discharge rate of above-mentioned the 3rd reagent solution is many when slowly pushing.And contain above-mentioned surface tension reducing agent in above-mentioned the 3rd reagent solution, and the surface tension of said nozzle elder generation end is reduced, every discharge rate is fixed.Here, above-mentioned surface tension reducing agent has the effect of the surface tension reduction of the aqueous solution of making, and can be selected from and the nonreactive material of above-mentioned slaine.Described material can use alcoholic compound and nonionic surfactant.Preferred above-mentioned alcoholic compound for example has glycolss such as ethylene glycol and propylene glycol.Preferred above-mentioned nonionic surfactant for example has polyoxyethylene alkyl ether class and polyalkylene alkyl ether.
Be controlled at soil 5% or following angle consideration from the change with each discharge rate, the content of above-mentioned surface tension reducing agent is preferably set in the scope of 20-40 weight % in above-mentioned the 3rd reagent solution.
Above-mentioned the 3rd reagent solution can be by being dissolved in above-mentioned slaine and other additive (above-mentioned surface tension reducing agent) as preparing in the water of solvent or the diluted acid equably.For example can be prepared as follows as above-mentioned the 3rd reagent solution of quantitative object: bismuth nitrate is dissolved in rare nitric acid, dissolves propylene glycol etc. as required with EDTA.
The said determination kit also can be following formation: do not contain above-mentioned reductive agent in above-mentioned first reagent solution, also possess the 4th container that Powdered above-mentioned reductive agent is housed when possessing above-mentioned first container, above-mentioned second container and above-mentioned the 3rd container.According to the difference of the kind of above-mentioned reductive agent, have in time oxidized character easily when having some in aqueous solution, to preserve, for example can stand 1-3 month short-term and preserve, but may not tolerate the long preservation in 1 year.When utilizing the above-mentioned reductive agent of described character, can carry out long preservation with Powdered directly being contained in above-mentioned the 4th container.
Above-mentioned the 4th container is so long as can prevent that the container of the form of air oxidation from getting final product, and is not particularly limited all and can uses kind by airtight bolt.In addition, consider that from the easy degree of operation and the easy degree angle of carrying the capacity of above-mentioned the 4th container preferably sets the scope at 25-100mL.The more preferably subsidiary Metering spoon of above-mentioned the 4th container.Subsidiary above-mentioned weighing spoon then can add in the sample water behind a certain amount of above-mentioned reductive agent of weighing, and operability is improved.
Then, the assay method for the above-mentioned sequestrant that uses the said determination kit describes.At first, get the part of the water that above-mentioned heat exchanger inside retains as sample water.When above-mentioned heat exchanger is boiler, the part of this sample water collection boiler water from discharger (Block ロ one device) waits.When above-mentioned heat exchanger was cooling tower, this sample water was gathered the part of recirculated water from heat abstractor etc.Here, when the sample water of collection surpasses 40 ℃, consider, preferably sample is water-cooled to 40 ℃ or following from the safety perspective of guaranteeing titration operation.In addition, when the sample water of collection had muddiness, the angle of sample water colour modulationization was considered from accurate identification titration operation, preferably sample water is filtered.The sample water of gathering is used for titration operation, therefore gets ormal weight (for example 10-50mL) with graduated cylinder in advance, transfers in the beaker then.
Then, in the sample water of gathering, add above-mentioned first reagent solution, evenly mix.Adjusting is from the number that drips of above-mentioned first container, and the addition that makes above-mentioned first reagent solution is normally to adding above-mentioned metal indicator of 0.0001-0.003 weight portion and the above-mentioned reductive agent of 0.001-0.5 weight portion respectively in the 100 weight portion sample water.In sample water, add above-mentioned second reagent solution, evenly mix.Adjusting is from the number that drips of above-mentioned second container, the addition that makes above-mentioned second reagent solution satisfies usually and adds the agent of following amount pH regulator: the pH that makes sample water is 6 or following amount, more preferably makes the amount of pH value at the pH 1-3 that not influenced by bivalent metal ion or rare-earth metal ion.And, when above-mentioned first reagent solution or above-mentioned second reagent solution contain above-mentioned screening agent, regulate the number that drips from above-mentioned first container or above-mentioned second container, the addition that makes above-mentioned screening agent is the 0.005-0.5 weight portion.The interpolation of above-mentioned first reagent solution and above-mentioned second reagent solution is not particularly limited in proper order, both can be added simultaneously.
Wherein, when the addition of above-mentioned metal indicator was lower than 0.0001 weight portion, sample water painted shallow was difficult to discern near the tonal variation the titration operation terminal point.And the addition of above-mentioned metal indicator is when surpassing 0.003 weight portion, sample water color depth, be difficult to discern near the tonal variation the titration operation terminal point.In addition, when the addition of above-mentioned reductive agent is lower than 0.001 weight portion, possibly can't go back the whole of ferric ion contained in the original sample water.And the addition of above-mentioned reductive agent is when surpassing 0.5 weight portion, and the above-mentioned reductive agent of overage also can't be used as the reduced iron ion, and is uneconomical on cost.The pH of sample water surpasses at 6 o'clock, and above-mentioned metal indicator possibly can't show the tone of regulation.And, when the addition of above-mentioned screening agent is lower than 0.005 weight portion, can't cover the whole of contained ferrous ion and copper ion in the sample water, possibly can't obtain quantitative values accurately.And the addition of above-mentioned screening agent is when surpassing 0.5 weight portion, and the above-mentioned screening agent of overage can not be used for the sealing of ferrous ion and copper ion, so uneconomical on the cost.
Add in the operation of above-mentioned first reagent solution,, then before will adding above-mentioned first reagent solution, in sample water, add pulverous above-mentioned reductive agent usually, evenly mix by above-mentioned the 4th container if above-mentioned first reagent solution does not contain above-mentioned reductive agent.At this moment, same when containing above-mentioned reductive agent in the addition of above-mentioned reductive agent and above-mentioned first reagent solution, be the 0.001-0.5 weight portion with respect to 100 weight portion sample water.
Add above-mentioned first reagent solution that contains above-mentioned reductive agent in sample water, perhaps add pulverous above-mentioned reductive agent, then the ferric ion in the sample water is reduced to ferrous ion.Preferential and the above-mentioned screening agent of this ferrous ion forms complex compound.Therefore, can prevent above-mentioned metal indicator for example xylenol orange and ferric ion form complex compound and variable color take place, can guarantee the normal tone of sample water.
Then, in the sample water that has added above-mentioned first reagent solution and above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution, count up to the number that drips of sample water variable color by above-mentioned the 3rd container.At this moment, on one side beaker vibration mixing is dripped above-mentioned the 3rd reagent solution on one side, sample water is evenly mixed with above-mentioned the 3rd reagent solution.
In the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution, the preferential and above-mentioned special metal ion forming complex of then above-mentioned sequestrant.The total amount of above-mentioned sequestrant and above-mentioned special metal ion forming complex, then above-mentioned metal indicator and remaining above-mentioned special metal ion forming complex, the variable color of sample water.For example, when above-mentioned sequestrant is EDTA and alkali metal salt thereof, in the sample water that has added above-mentioned first reagent solution and above-mentioned second reagent solution, drip above-mentioned the 3rd reagent solution, then preferential the and bismuth ion formation complex compound of EDTA.The total amount of EDTA and bismuth ion form complex compound, and then xylenol orange and remaining bismuth ion form complex compound, and sample water becomes redness by yellow (the o-phenanthroline that combines with ferrous ion is orange when existing jointly).
Drip above-mentioned the 3rd reagent solution in the presence of above-mentioned screening agent, then ferrous ion or the preferential and above-mentioned screening agent of copper ion with above-mentioned sequestrant complexing forms complex compound.For this reason, the total amount of above-mentioned sequestrant and above-mentioned special metal ion form complex compound rapidly, can foreshorten to the needed reaction time of sample water variable color.
Then, according to the concentration that number is determined above-mentioned sequestrant in the sample water of dripping to required above-mentioned the 3rd reagent solution of titration operation terminal point.As previously mentioned, above-mentioned the 3rd reagent solution is prepared into the above-mentioned sequestrant reaction of above-mentioned slaine contained in one and ormal weight, therefore by the amount of the above-mentioned sequestrant of the correspondence of each above-mentioned the 3rd reagent solution, above-mentioned the 3rd reagent solution drip the number and the sample water yield, can calculate the above-mentioned sequestrant concentration in the sample water.
But, in above-mentioned heat exchanger, above-mentioned sequestrant is dissolved in the water with free state or with the state of formation complex compounds such as hardness components.Common concentration rate in order to keep stipulating, the water that remains in above-mentioned heat exchanger inside will intermittently be discharged to the outside, perhaps regularly supply with make-up water, therefore above-mentioned sequestrant can not form crystal above solubleness in water, or precipitate on the heat-transfer area, therefore, above-mentioned sequestrant concentration and water treatment agent concentration in the above-mentioned heat exchanger have correlativity, can determine water treatment agent concentration easily by the proportioning of above-mentioned sequestrant in the concentration of above-mentioned sequestrant and the above-mentioned water treatment agent.Therefore, can judge according to this water treatment agent concentration whether the supply of above-mentioned water treatment agent is appropriate.
As described above, in embodiment of the present invention, promptly can understand water treatment agent concentration easily at the scene that heat exchanger is set.As a result, can judge whether the water treatment agent quantity delivered is suitable in the heat exchanger, can make the relevant maintenance management of water treatment more efficient then and there.
Embodiment
(preparation of first reagent solution)
Use xylenol orange as metal indicator, o-phenanthroline as screening agent, distilled water and ethanol as solvent, these compositions are mixed according to the content shown in the table 1, prepare first reagent solution.After the preparation, pack into drop bottle (the capacity 100mL of band nozzle of tygon system of this first reagent solution; Hereinafter referred to as " first container ") in.Use the dripping quantity of every of above-mentioned first reagent solution of above-mentioned first container to be 0.035g (mean value).
Table 1
| Composition | Content (weight %) |
| Xylenol orange | 0.3 |
| The o-phenanthroline | 2 |
| Distilled water | 77.7 |
| |
20 |
(preparation of second reagent solution)
Use 10% aqueous solution of nitric acid as the pH regulator agent, make second reagent solution.Pack into drop bottle (the capacity 100mL of band nozzle of tygon system of this second reagent solution; Hereinafter referred to as " second container ").Use the dripping quantity of every of above-mentioned second reagent solution of above-mentioned second container to be 0.035g (mean value).
(preparation of the 3rd reagent solution)
Use the bismuth nitrate pentahydrate as slaine, 0.5mol/L aqueous solution of nitric acid as solvent, their each composition is mixed according to the content shown in the table 2, prepare the 3rd reagent solution.After the preparation, pack into drop bottle (the capacity 100mL of band nozzle of tygon system of the 3rd reagent solution; Hereinafter referred to as " the 3rd container ").Use the dripping quantity of every of above-mentioned the 3rd reagent solution of above-mentioned the 3rd container to be 0.035g (mean value), each drips above-mentioned the 3rd reagent solution, and it is equivalent to 0.05mgEDTA-2Na.
Table 2
| Composition | Content (weight %) |
| The bismuth nitrate pentahydrate | 0.21 |
| 0.5mol/L aqueous solution of nitric acid | 99.79 |
(collection of sample water)
Randomly draw 67 from being combined with the tubular boiler of disodium ethylene diamine tetraacetate (EDTA-2Na) as the water treatment agent of scale inhibitor of the whole nation from supply, on-stream by continuous discharger collection sample water.Except that EDTA-2Na, also be combined with alkali-metal oxyhydroxide as corrosion inhibitor in the above-mentioned water treatment agent, the pH of the sample water of collection is the scope of 10.5-12.After each sample is water-cooled to room temperature, measure 10mL, be respectively charged in the beaker, prepare the first fen water of materialsing of 67 samples with graduated cylinder.Use graduated cylinder, get 5mL respectively by each sample water and pour beaker into, prepare the second fen water of materialsing of 67 samples.
(by simple and easy titration measuring EDTA)
Added the Powdered ascorbic acid of 20mg in the water of materialsing as reductive agent to first minute, uniform dissolution.In the first fen water of materialsing that is added with above-mentioned reductive agent, add above-mentioned first reagent solution by above-mentioned first container, then add 5 above-mentioned second reagent solutions, evenly mix, the preparation test water by above-mentioned second container.Then, drip above-mentioned the 3rd reagent solution by above-mentioned the 3rd container in test water, the counting test water is dripped number by orange when becoming redness.The branch amount of getting of dripping number and sample water that is equivalent to the amount of EDTA-2Na, above-mentioned the 3rd reagent solution by above-mentioned every the 3rd reagent solution is calculated the concentration of EDTA-2Na in the sample water then.More than in the operation, it is 1-3 minute that each sample is measured required time.
(high effective liquid chromatography for measuring EDTA)
For the EDTA quantitative values with simple and easy titrimetry compares,, implement the mensuration of EDTA by high performance liquid chromatography (HPLC method) to the second fen water of materialsing.At first, with commercially available 0.01mol/L disodium ethylene diamine tetraacetate (EDTA-2Na) aqueous solution distilled water diluting, prepare the standard solution of 0mg/L, 10mg/L, 20mg/L, 40mg/L and 80mg/L respectively.In addition, the 0.27g ferric chloride hexahydrate is dissolved in the hydrochloric acid of 0.01N, making total amount is 100mL, the ferric chloride solution of preparation 0.01mol/L.
In each standard solution of 5mL, add 5mL 0.01mol/L ferric chloride solution respectively,, carry out high-performance liquid chromatogram determination for 10 each solution of μ L then with the membrane filter filtration of 0.2 μ m.Height and concentration by each peak of gained are made calibration curve.Wherein, the condition of high performance liquid chromatography is as follows.
-column dimension: internal diameter 4.6mm, length 150mm
-stationary phase: porasil is carried out octadecyl chemical modification gained
-mobile phase: in 0.01mol/L 4-n-butyl ammonium hydroxide solution, add acetate, be adjusted to pH 3.0 gained
-mobile phase flow velocity: 1mL/ minute
The selection wavelength of-detecting device: 255nm
Then, added the ferric chloride solution of 5mL 0.01mol/L in the water of materialsing to second minute,, get 10 each solution of μ L then, under the condition identical, carry out high-performance liquid chromatogram determination, the instrumentation peak heights with standard solution with the membrane filter filtration of 0.2 μ m.Calculate the concentration of EDTA-2Na in the sample water according to the calibration curve of making in advance.More than in the operation, it is 25 minutes that each sample is measured required time.
(evaluation)
For each sample water, the point diagram of legal value of HPLC and simple and easy titrimetry quantitative values as shown in Figure 1.According to Fig. 1, the quantitative values of the quantitative values of simple and easy titrimetry and HPLC method produces the difference about positive 5mg/L.This is because the capacity of decomposition of the quantitative values of simple and easy titrimetry is set at 5mg/L.The quantitative values of the quantitative values of simple and easy titrimetry and HPLC method shows roughly linear correlativity, hence one can see that its reliability height.In addition, simple and easy titrimetry need not to use special instrument, and can measure at short notice, therefore can be used for on-the-spot mensuration.
Claims (10)
1. the assay method of sequestrant, this method is the assay method of sequestrant concentration in the sample water, comprises following operation:
Gather the operation of sample water;
In the sample water of gathering, add first reagent solution that contains metal indicator and the operation that contains second reagent solution of pH regulator agent respectively;
In the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip the 3rd reagent solution that contains the slaine that makes above-mentioned metal indicator variable color, count up to the required operation of dripping number of sample water variable color;
The operation that number is determined sequestrant concentration in the sample water of dripping based on above-mentioned the 3rd reagent solution.
2. the assay method of the sequestrant of claim 1, this method comprise the operation of further adding screening agent in the sample water of being gathered.
3. the assay method of the sequestrant of claim 2, this method comprise the operation of further adding reductive agent in the sample water of gathering.
4. the assay method of sequestrant, this method is the assay method of sequestrant concentration in the sample water, comprises following operation:
Gather the operation of sample water;
In the sample water of gathering, add first reagent solution that contains metal indicator and the operation that contains second reagent solution of pH regulator agent respectively;
In the sample water that is added with above-mentioned first reagent solution and above-mentioned second reagent solution, drip the 3rd reagent solution that contains the slaine that makes above-mentioned metal indicator variable color, count up to the required operation of dripping number of sample water variable color;
According to the operation that number is determined sequestrant concentration in the sample water of dripping of above-mentioned the 3rd reagent solution,
Above-mentioned sequestrant is ethylenediamine tetraacetic acid and salt thereof,
Above-mentioned metal indicator, above-mentioned pH regulator agent and above-mentioned slaine are respectively xylenol orange, nitric acid and bismuth nitrate.
5. the assay method of the sequestrant of claim 4, this method comprise the operation of further adding screening agent in the sample water of gathering, and wherein said screening agent is the o-phenanthroline.
6. the assay method of the sequestrant of claim 5, this method comprise the operation of further adding reductive agent in the sample water of gathering, and wherein said reductive agent is ascorbic acid and alkali metal salt thereof.
7. the mensuration kit of sequestrant, this kit is the mensuration kit that sequestrant concentration in the sample water is carried out quantitative sequestrant, this kit possesses:
First container of first reagent solution is housed, this first reagent solution containing metal indicator;
Second container of second reagent solution is housed, and this second reagent solution contains the pH regulator agent;
The 3rd container of the 3rd reagent solution is housed, and the 3rd reagent solution contains the slaine that makes above-mentioned metal indicator variable color.
8. the sequestrant of claim 7 is measured kit, and wherein, above-mentioned first reagent solution or above-mentioned second reagent solution further contain screening agent.
9. the sequestrant of claim 8 is measured kit, and wherein, above-mentioned first reagent solution further contains reductive agent.
10. the sequestrant of claim 8 is measured kit, and this kit possesses the 4th container, and the 4th container is equipped with powder reducing agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006086834 | 2006-03-28 | ||
| JP2006-086834 | 2006-03-28 | ||
| JP2006086834A JP2007263632A (en) | 2006-03-28 | 2006-03-28 | Method and kit for measuring chelating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101275914A true CN101275914A (en) | 2008-10-01 |
| CN100592077C CN100592077C (en) | 2010-02-24 |
Family
ID=38561906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710091845A Expired - Fee Related CN100592077C (en) | 2006-03-28 | 2007-03-28 | Method of determining chelating agent and determination kit for chelating agent |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2007263632A (en) |
| KR (1) | KR101100556B1 (en) |
| CN (1) | CN100592077C (en) |
| CA (1) | CA2582890A1 (en) |
| TW (1) | TW200745546A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104034726A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for determining bismuth content and vanadium content of bismuth vanadate |
| CN113970615A (en) * | 2021-11-09 | 2022-01-25 | 浙江盛远环境检测科技有限公司 | Device and method for detecting effective content of heavy metal chelating agent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6644552B2 (en) * | 2016-01-07 | 2020-02-12 | 株式会社ニイタカ | Determination method of chelating agent |
| KR102133667B1 (en) * | 2019-02-12 | 2020-07-13 | 가천대학교 산학협력단 | Sensitive detecting method for detergent component etidronic acid utilizing phase transformation of copper compound |
| KR102139002B1 (en) * | 2019-02-27 | 2020-07-28 | 가천대학교 산학협력단 | Fast and sensitive detecting method for detergent component etidronic acid utilizing copper compound |
| CN112414954B (en) * | 2020-12-03 | 2023-12-08 | 广东湛丰精细化工有限公司 | Iron ion chelating ability testing method suitable for actual production conditions of printing and dyeing mill |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61153565A (en) * | 1984-12-26 | 1986-07-12 | Kao Corp | Quantitative determination of iron in water and reagent for quantitative determination to be used therefor |
| JPS6440614A (en) * | 1987-08-03 | 1989-02-10 | Kuraray Co | Deodorizing polyester fiber |
| IT1219848B (en) * | 1988-03-03 | 1990-05-24 | Miles Italiana | COMPOUND INDICATORS, METHOD FOR THEIR PREPARATION AND USE IN A STEEL SYSTEM ASSAY SYSTEM |
| JP2595835B2 (en) * | 1991-05-31 | 1997-04-02 | 日立化成工業株式会社 | Measurement method of chelating agent concentration, hydroxide ion concentration and reducing agent concentration in chemical copper plating solution |
| JP3134973B2 (en) * | 1993-03-26 | 2001-02-13 | 日本碍子株式会社 | Iron ion valence analysis method |
| GB9719142D0 (en) * | 1997-09-09 | 1997-11-12 | Glaxo Group Ltd | Analytical method and apparatus therefor |
| CN1079380C (en) * | 1998-09-08 | 2002-02-20 | 新疆工学院 | Water-treating chemical and its application method |
| JP2000162128A (en) * | 1998-11-30 | 2000-06-16 | Nippon Shokubai Co Ltd | Discrimination of polymer compound by metal affinity |
| JP4066580B2 (en) | 1999-11-29 | 2008-03-26 | 三浦工業株式会社 | Method for measuring the concentration of residual dispersant |
| JP2001296305A (en) * | 2000-04-18 | 2001-10-26 | Ebara Udylite Kk | Sample solution automatic analyzing device and method |
| JP3941498B2 (en) * | 2001-12-25 | 2007-07-04 | 三浦工業株式会社 | Method for measuring concentration of components contained in liquid |
| JP4222327B2 (en) * | 2004-03-30 | 2009-02-12 | 三浦工業株式会社 | Reagent for hardness measurement |
-
2006
- 2006-03-28 JP JP2006086834A patent/JP2007263632A/en active Pending
-
2007
- 2007-03-05 TW TW096107486A patent/TW200745546A/en unknown
- 2007-03-27 CA CA002582890A patent/CA2582890A1/en not_active Abandoned
- 2007-03-27 KR KR1020070029574A patent/KR101100556B1/en not_active IP Right Cessation
- 2007-03-28 CN CN200710091845A patent/CN100592077C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104034726A (en) * | 2013-03-06 | 2014-09-10 | 广东先导稀材股份有限公司 | Method for determining bismuth content and vanadium content of bismuth vanadate |
| CN113970615A (en) * | 2021-11-09 | 2022-01-25 | 浙江盛远环境检测科技有限公司 | Device and method for detecting effective content of heavy metal chelating agent |
| CN113970615B (en) * | 2021-11-09 | 2022-09-27 | 浙江盛远环境检测科技有限公司 | Device and method for detecting effective content of heavy metal chelating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007263632A (en) | 2007-10-11 |
| TW200745546A (en) | 2007-12-16 |
| CN100592077C (en) | 2010-02-24 |
| KR101100556B1 (en) | 2011-12-29 |
| KR20070097338A (en) | 2007-10-04 |
| CA2582890A1 (en) | 2007-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100592077C (en) | Method of determining chelating agent and determination kit for chelating agent | |
| JP2954964B2 (en) | Transition metals as treatment chemical tracers | |
| Scaringelli et al. | Spectrophotometric determination of atmospheric sulfur dioxide | |
| CA2502534A1 (en) | Hardness measurement reagent | |
| JP4905768B2 (en) | Management method of water treatment agent supply | |
| AU742188B2 (en) | Method for measuring the level of carboxylate anion in engine coolant and test kit for carrying out the method | |
| KR20060044816A (en) | Hardness measurement reagent | |
| US20070231920A1 (en) | Method of determining chelating agent and determination kit for chelating agent | |
| KR101171802B1 (en) | Pyrene derivatives having mercury ion selectivity, and fluorescent chemodosimeter using the same | |
| Walinga et al. | Digestion in tubes with H2SO4-salicylic acid-H2O2 and selenium and determination of Ca, K, Mg, N, Na, P, Zn | |
| CN1563945B (en) | Total iron assaying liquid and color comparison tube | |
| Schilt et al. | Spectrophotometric determination of copper in alkali metals and hydroxides with 4, 4'-dihydroxy-2, 2'-biquinoline | |
| Jones et al. | Analytical problems arising from the use of bromide and rhodamine WT as co-tracers in streams | |
| Rahman | Quenchofluorimetric determination of mercury trace with murexide | |
| CN101576480B (en) | Method for measuring contents of cationic surface active substances by bromothymol blue spectrometry | |
| Ericsson et al. | Oskarshamn Site Investigation: Surface Water Sampling at Simpevarp 2002-2003 | |
| US20240053305A1 (en) | Rapid method for different types of biocide residual with analysis procedure | |
| Ali | Ternary complexes of copper (II) and their use in the spectrophotometric determination of copper in alloys and rocks | |
| WO2010036620A2 (en) | Method and composition for determining hardness in wellbore fluid filtrate | |
| USRE33349E (en) | Controlling sulfide scavenger content of drilling fluid | |
| JPH0894520A (en) | Measuring method for cooling water system water treatment agent concentration and retaining water quantity by means of fluorescent material | |
| CN2695953Y (en) | Total iron colorimetric investigating pipe | |
| Nan | Selective spectrophotometric determination of aluminium in the presence of beryllium and lanthanide cations | |
| Pavon et al. | Fluorimetric determination of trace amounts of yttrium with salicylaldehyde carbohydrazone | |
| Ružička | Application of Titanometry to Titrations in Alkaline Medium. I. Determination of Bichromate and Cyanoferrate (III) Ions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100224 Termination date: 20140328 |