CN107036991A - A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS - Google Patents

A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS Download PDF

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Publication number
CN107036991A
CN107036991A CN201710179130.XA CN201710179130A CN107036991A CN 107036991 A CN107036991 A CN 107036991A CN 201710179130 A CN201710179130 A CN 201710179130A CN 107036991 A CN107036991 A CN 107036991A
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chlorine dioxide
abts
chlorite
concentration
analysis method
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方晶云
华哲超
张金松
吴梓昊
侯少东
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National Sun Yat Sen University
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National Sun Yat Sen University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light

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  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The present invention provides a kind of chlorine dioxide and chlorite rapid analysis method based on ABTS, and this method, which is crossed, takes water sample to be measured, and regulation pH value is 6.5, adds ABTS solution, determines absorbance of the solution under 405nm wavelength, calculates the concentration for obtaining chlorine dioxide;Chlorine dioxide in logical nitrogen stripping water sample, then adds acid for adjusting pH value to be 2, adds ABTS solution, determines absorbance of the solution under 405nm wavelength, calculates the concentration for obtaining chlorine dioxide.This method can be quick, accurate, economical, simple to operate carry out water quality chlorine dioxide and chloritic analysis.

Description

A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS
Technical field
The present invention relates to disinfectant field in analyzing water body, more particularly, to a kind of chlorine dioxide based on ABTS and Chlorite rapid analysis method.
Background technology
Chlorine dioxide is generally acknowledged efficient, wide spectrum of new generation, the sterilization of safety, antistaling agent in the world, is chlorhexidine-containing disinfectant Preferable substitute, is widely used all over the world.Meanwhile, disinfection by chlorine dioxide is nearly free from haloform, halogen The DBPs such as acetic acid.And chlorite is the common accessory substance that disinfection by chlorine dioxide is produced, chlorine dioxide self property Also it is unstable, easily it is decomposed into chlorite etc..What China promulgated for 2006《Standards for drinking water quality》Provide titanium dioxide Limit value concentration is 0.1-0.8mg/L in the output water of chlorine, when using disinfection by chlorine dioxide, limit of the chlorite in drinking water It is worth for 0.7mg/L.Therefore, it is necessary to chlorine dioxide and chloritic in periodic monitoring water when being carried out disinfection using chlorine dioxide Concentration, to ensure water quality safety.
At present in Chinese GB5750-2006《Drinking water standard detection method》With U.S. APHA《Standard Methods for the Examination of Water and Wastewater》In, the chlorine dioxide in drinking water is commonly used Assay method be N, N- diethyl p-phenylenediamines ferrous ammonium sulfate titration (DPD-FAS methods) and iodimetric titration;Chlorite exists Detection method be iodimetric titration and the chromatography of ions.Instrument needed for the chromatography of ions --- ion chromatograph is expensive, typically Water factory does not have fund outfit, and comparatively DPD-FAS methods and instrument price required for iodimetric titration are relatively inexpensive but required when determining Reagent is more and inconvenient on-site measurement.Also, many water factories are when using chlorine dioxide as disinfectant, by titanium dioxide Chlorine and free chlorine are used in combination, and when using iodometric determination chlorite, chlorate and free chlorine can be produced to measurement result Raw influence.
The content of the invention
It is fast that the present invention provides a kind of quick, accurate, economical, simple to operate chlorine dioxide and chlorite based on ABTS Fast analysis method.
In order to reach above-mentioned technique effect, technical scheme is as follows:
A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS, including chlorine dioxide analysis method and Chloritic analysis method;
The analysis method of the chlorine dioxide is:
Water sample to be measured is taken, regulation pH value is 6.5, adds ABTS solution, determine absorbance of the solution under 405nm wavelength A1, then pass through formula:Chlorine dioxide concentration=2.37A1/b×V2/V1Calculate the concentration of chlorine dioxide;
The chloritic analysis method:
Water sample to be measured is taken, then the chlorine dioxide led in nitrogen stripping water sample adds acid for adjusting pH value to be 2, add ABTS molten Liquid, determines absorbance A of the solution under 405nm wavelength2, chlorite concentration=0.53A2/b×V2/V1, wherein, A1For pH The absorbance measured under the conditions of 6.5;A2For the absorbance measured under the conditions of pH 2.0;B is cuvette light path;V1For institute's water sampling Volume;V2To add the cumulative volume after various reagents.
In the present invention, ABTS is a kind of substrate of catalase, and its oxidation-reduction potential is 0.68V, easily with oxidation Electro transfer, the green free radical ABTS of generation occur for agent reaction·+。ABTS·+Stability is strong, and half-life period is 47 at ambient temperature Hour, at 4 DEG C, half-life period is 357 hours, therefore, at ambient temperature the attenuation rate in 5 hours<5%, 24 hours at 4 DEG C Interior attenuation rate<3%.Also, ABTS·+Absorbance when 405nm molar absorption coefficient is in pH 6.5 and pH 2 is respectively 28500M-1cm-1And 31600M-1cm-1.It therefore, it can according to reacted ABTS·+Absorbance, and oxidant and ABTS it is anti- The quantitative relationship answered, directly calculates the concentration of oxidant, without bioassay standard curve.
In pH 6.5, ABTS only generates ABTS free radicals (ABTS with chlorine dioxide reaction·+), and chlorite and chlorine Hydrochlorate does not react (formula 1) with ABTS;In pH 2, chlorite and chlorine dioxide can be with ABTS reaction generations ABTS·+, and Chlorate does not react with ABTS.
ClO2+ABTS→ClO2 -+ABTS·+ (1)
ClO2 -+4ABTS+4H+→Cl-+4ABTS·++2H2O (2)
Around this principle, in pH=2, with nitrogen stripping chlorine dioxide, the chlorite in water can be carried out single Solely determine.Chlorine dioxide and chlorite react the ABTS of generation with ABTS·+For green, pass through ultraviolet-uisible spectrophotometer The absorbance that it is determined in 405nm determines concentration.
Further, pH is adjusted to 6.5 using phosphate buffer solution, and makes phosphate concn be 12mM;Using sulfuric acid, One or more in nitric acid, hydrochloric acid, phosphoric acid adjust chloritic pH to 2 to be determined.
Further, absorbance A is determined1Process it is as follows:
Water sample 21mL to be measured is taken, the phosphate buffer solutions of pH 6.5 that 3mL concentration is 0.1M are added, adding 1mL concentration is 1g/L ABTS solution, then absorbance of the determination sample under 405nm wavelength.
Further, absorbance A is determined2Process it is as follows:
Water sample 21mL to be measured is taken, the nitrogen 3min that flow velocity is 20ml/min is passed through, the salt that 3mL equivalent concentration is 0.3M is added Acid solution, adds the ABTS solution that 1mL concentration is 1g/L, then absorbance of the determination sample under 405nm wavelength.
Further, when there is free chlorine simultaneously in water sample to be measured, 5g/L glycine 0.2mL is added, to eliminate certainly The influence determined by chlorine to chlorine dioxide and chlorite.
Further, the concentration range that this method determines chlorine dioxide in water is 0.15-2.65mg/L, chloritic dense Degree scope is 0.07-0.7mg/L;If chlorine dioxide and chlorite are more than this concentration range in water sample to be measured, pure water need to be used It is diluted to the concentration range.
The chlorine dioxide and chloritic concentration in water sample are determined, is calculated by below equation:
Chlorine dioxide concentration (mg/L)=A1/(28500×b)×67.5×1000×V2/V1
=2.37A1/b×V2/V1 (3)
Chlorite concentration (mg/L)=A/ (31600 × b)/4 × 67.5 × 1000 × V2/V1
=0.53A2/b×V2/V1 (4)
Wherein, A1For the absorbance measured under the conditions of pH 6.5;A2For the absorbance measured under the conditions of pH 2;B is cuvette Light path (cm);V1For the volume (mL) of institute's water sampling;V2To add the cumulative volume (mL) after various reagents.
Compared with prior art, the beneficial effect of technical solution of the present invention is:
The present invention is by taking water sample to be measured, and regulation pH value is 6.5, adds ABTS solution, determines solution under 405nm wavelength Absorbance, the concentration of chlorine dioxide is obtained by standard curve;Chlorine dioxide in logical nitrogen stripping water sample, then acid adding adjust It is 2 to save pH value, adds ABTS solution, determines absorbance of the solution under 405nm wavelength, chlorine dioxide is obtained by standard curve Concentration.This method can be quick, accurate, economical, simple to operate carry out water quality chlorine dioxide and chloritic analysis.
Brief description of the drawings
Fig. 1 is that and chlorite and chlorate are to dioxy in 6.5 times chlorine dioxide standard curves of pH based on ABTS methods Change the interference of chlorine measurement;
Fig. 2 is that chlorite measure is done in 2 times chlorite standard curves of pH, and chlorate based on ABTS methods Disturb.
Embodiment
Accompanying drawing being given for example only property explanation, it is impossible to be interpreted as the limitation to this patent;
In order to more preferably illustrate the present embodiment, some parts of accompanying drawing have omission, zoomed in or out, and do not represent actual product Size;
To those skilled in the art, it is to be appreciated that some known features and its explanation, which may be omitted, in accompanying drawing 's.
Technical scheme is described further with reference to the accompanying drawings and examples.
The present invention proposes that one kind joins the two of nitrogen-two (3- ethyls-benzothiazole -6- sulfonic acid) di-ammonium salts (ABTS) based on 2,2- Chlorine monoxid and chlorite rapid analysis method.
ABTS is a kind of substrate of catalase, and its oxidation-reduction potential is 0.68V, is easily occurred with oxidant reaction Electro transfer, the green free radical ABTS of generation·+。ABTS·+Stability is strong, and half-life period is 47 hours at ambient temperature, at 4 DEG C When half-life period be 357 hours, therefore, the attenuation rate in 5 hours at ambient temperature<5%, attenuation rate at 4 DEG C in 24 hours< 3%.Also, ABTS·+Absorbance when 405nm molar absorption coefficient is in pH 6.5 and pH 2 is respectively 28500M-1cm-1 And 31600M-1cm-1.It therefore, it can according to reacted ABTS·+Absorbance, and the quantitative pass that oxidant reacts with ABTS System, directly calculates the concentration of oxidant, without bioassay standard curve.
Chlorine dioxide is surveyed in 6.5 times chlorine dioxide standard curves of pH, and chlorite and chlorate based on ABTS methods Fixed interference is as shown in Figure 1;Chlorite is determined in 2 times chlorite standard curves of pH, and chlorate based on ABTS methods Interference it is as shown in Figure 2.
The technical scheme is that:
A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS, comprising:(1) the analysis side of chlorine dioxide Method:Water sample to be measured is taken, regulation pH value is 6.5, adds ABTS solution, determine absorbance of the solution under 405nm wavelength, pass through mark Directrix curve obtains the concentration of chlorine dioxide;(2) chloritic analysis method:Water sample to be measured is taken, is led in nitrogen stripping water sample Chlorine dioxide, then adds acid for adjusting pH value to be 2, adds ABTS solution, determines absorbance of the solution under 405nm wavelength, passes through Standard curve obtains the concentration of chlorine dioxide.
Using phosphate buffer solution regulation pH to 6.5 (phosphate concn=12mM);Using sulfuric acid, nitric acid, hydrochloric acid, phosphorus One or more of regulations in acid determine chloritic pH to 2.
The present invention principle be:In pH 6.5, ABTS only generates ABTS free radicals (ABTS with chlorine dioxide reaction·+), And chlorite and chlorate do not react (formula 1) with ABTS;In pH 2, chlorite and chlorine dioxide can react with ABTS Generate ABTS·+, and chlorate does not react with ABTS.
ClO2+ABTS→ClO2 -+ABTS·+ (1)
ClO2 -+4ABTS+4H+→Cl-+4ABTS·++2H2O (2)
Around this principle, in pH 2, with nitrogen stripping chlorine dioxide, the chlorite in water can be carried out independent Determine.Chlorine dioxide and chlorite react the ABTS of generation with ABTS·+For green, surveyed by ultraviolet-uisible spectrophotometer Fixed its determines concentration in 405nm absorbance.
General operation is to take 21mL to contain chlorine dioxide and chloritic water sample, if chlorine dioxide in water sample to be measured It is more than this method detection range with chlorite, pure water can be added to be diluted to the concentration range.Take 0.1M phosphate buffer solution 3mL makes water sample pH to be measured be 6.5, then 1g/L ABTS solution 1mL is added water sample, determines its absorbance A1;Take 21mL same again Sample contains chlorine dioxide and chloritic water sample, is passed through chlorine dioxide in nitrogen stripping water sample, adds 0.3M hydrochloric acid 3mL and makes Water sample pH to be measured is 2, takes 1g/L ABTS solution 1mL, determines its absorbance A2
When also there is free chlorine simultaneously in water sample to be measured, 5g/L glycine solution 0.2mL need to be added before the assay, eventually Only all free chlorine, to eliminate the influence that free chlorine is determined to chlorine dioxide and chlorite.
The optimum range that this method can measure the concentration of chlorine dioxide is 0.15-2.65mg/L, chloritic concentration Optimum range is 0.07-0.7mg/L.If chlorine dioxide and chlorite are more than this concentration range in water sample to be measured, it can adopt The concentration range is diluted to pure water.
The chlorine dioxide and chloritic concentration in water sample are determined, is calculated by below equation:
Chlorine dioxide concentration (mg/L)=A1/(28500×b)×67.5×1000×V2/V1
=2.37A1/b×V2/V1 (3)
Chlorite concentration (mg/L)=A2/(31600×b)/4×67.5×1000×V2/V1
=0.53A2/b×V2/V1 (4)
Wherein, A1For the absorbance measured under the conditions of pH 6.5;A2For the absorbance measured under the conditions of pH 2.0;B is colorimetric Ware light path (cm);V1For the volume (mL) of institute's water sampling;V2To add the cumulative volume (mL) after various reagents.
Two groups of experiments have been carried out using this method:
Experiment one:
When containing chlorine dioxide and chlorite in water sample, to the measure of chlorine dioxide:
21mL is taken to contain chlorine dioxide and chloritic water sample, the 0.1mol/L phosphate buffer solutions 3mL of addition makes to treat It is 6.5 to survey water sample pH, and adds 1g/L ABTS solution 1mL, determines its absorbance A 1.Formula (3) is substituted into, is obtained two in water sample The concentration of chlorine monoxid.
When containing chlorine dioxide and chlorite in water sample, determined to chloritic:
Take 21mL to contain chlorine dioxide and chloritic water sample, be passed through dioxy in 20mL/min nitrogen 3min stripping water samples Change chlorine, add 0.3M hydrochloric acid 3mL up to water sample pH to be measured is 2, take 1g/L ABTS solution 1mL, determine its absorbance A2.Generation Enter formula (4), obtain chloritic concentration in water sample.
Experiment two:
When chlorine dioxide, chlorite and free chlorine coexist, to the measure of chlorine dioxide:
21mL is taken to contain after chlorine dioxide and chloritic water sample, addition 5g/L glycine 0.2mL terminations are all Free chlorine, the 0.1mol/L phosphate buffer solutions 3mL then added makes water sample pH to be measured be 6.5, and it is molten to add 1g/L ABTS Liquid 1mL, determines its absorbance A1.Formula (3) is substituted into, the concentration of chlorine dioxide in water sample is obtained.
When chlorine dioxide, chlorite and free chlorine coexist, determined to chloritic:
Take 21mL to contain chlorine dioxide and chloritic water sample, be passed through dioxy in 20mL/min nitrogen 3min stripping water samples Change chlorine, addition 5g/L glycine 0.2mL terminates all free chlorine, then adds 0.3M hydrochloric acid 3mL until water sample to be measured PH is 2, takes 1g/L ABTS solution 1mL, determines its absorbance A2.Formula (4) is substituted into, obtains chloritic dense in water sample Degree.
The same or analogous part of same or analogous label correspondence;
Position relationship is used for being given for example only property explanation described in accompanying drawing, it is impossible to be interpreted as the limitation to this patent;
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description To make other changes in different forms.There is no necessity and possibility to exhaust all the enbodiments.It is all this Any modifications, equivalent substitutions and improvements made within the spirit and principle of invention etc., should be included in the claims in the present invention Protection domain within.

Claims (6)

1. a kind of chlorine dioxide and chlorite rapid analysis method based on ABTS, it is characterised in that including chlorine dioxide Analysis method and chloritic analysis method;
The analysis method of the chlorine dioxide is:
Water sample to be measured is taken, regulation pH value is 6.5, adds ABTS solution, determine absorbance A of the solution under 405nm wavelength1, then Pass through formula:Chlorine dioxide concentration=2.37A1/b×V2/V1Calculate the concentration of chlorine dioxide;
The chloritic analysis method:
Water sample to be measured is taken, then the chlorine dioxide led in nitrogen stripping water sample adds acid for adjusting pH value to be 2, add ABTS solution, surveys Determine absorbance A of the solution under 405nm wavelength2, chlorite concentration=0.53A2/b×V2/V1, wherein, A1For the conditions of pH 6.5 Under the absorbance that measures;A2For the absorbance measured under the conditions of pH 2.0;B is cuvette light path;V1For the volume of institute's water sampling; V2To add the cumulative volume after various reagents.
2. chlorine dioxide and chlorite rapid analysis method according to claim 1 based on ABTS, it is characterised in that PH is adjusted to 6.5 using phosphate buffer solution, and makes phosphate concn be 12mM;Using in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid One or more adjust chloritic pH to 2 to be determined.
3. chlorine dioxide and chlorite rapid analysis method according to claim 2 based on ABTS, it is characterised in that Determine absorbance A1Process it is as follows:
Water sample 21mL to be measured is taken, the phosphate buffer solutions of pH 6.5 that 3mL concentration is 0.1M are added, 1mL concentration is added for 1g/L ABTS solution, then absorbance of the determination sample under 405nm wavelength.
4. chlorine dioxide and chlorite rapid analysis method according to claim 2 based on ABTS, it is characterised in that Determine absorbance A2Process it is as follows:
Water sample 21mL to be measured is taken, the nitrogen 3min that flow velocity is 20ml/min is passed through, adds 3mL equivalent concentration molten for 0.3M hydrochloric acid Liquid, adds the ABTS solution that 1mL concentration is 1g/L, then absorbance of the determination sample under 405nm wavelength.
5. the chlorine dioxide and chlorite rapid analysis method based on ABTS according to claim any one of 3-4, its Being characterised by, when there is free chlorine simultaneously in water sample to be measured, 5g/L glycine 0.2mL is added, to eliminate free chlorine to two The influence that chlorine monoxid and chlorite are determined.
6. chlorine dioxide and chlorite rapid analysis method according to claim 1 based on ABTS, it is characterised in that The concentration range that this method determines chlorine dioxide in water is 0.15-2.65mg/L, and chloritic concentration range is 0.07- 0.7mg/L;If chlorine dioxide and chlorite are more than this concentration range in water sample to be measured, the concentration model need to be diluted to using pure water Enclose.
CN201710179130.XA 2017-03-23 2017-03-23 A kind of chlorine dioxide and chlorite rapid analysis method based on ABTS Withdrawn CN107036991A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318728A (en) * 2008-07-16 2008-12-10 中山大学 Ultraviolet light catalysis disinfection method by chlorine dioxide for water
CN105527280A (en) * 2014-09-30 2016-04-27 深圳市水务(集团)有限公司 Method for detecting chlorine dioxide and chlorite concentration in water through LGB-HRP quantitative injection

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318728A (en) * 2008-07-16 2008-12-10 中山大学 Ultraviolet light catalysis disinfection method by chlorine dioxide for water
CN105527280A (en) * 2014-09-30 2016-04-27 深圳市水务(集团)有限公司 Method for detecting chlorine dioxide and chlorite concentration in water through LGB-HRP quantitative injection

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ULRICH PINKERNELL 等: "Methods For The Photometric Determination Of Reactive Bromine And Chlorine Species With ABTS", 《WATER RESEARCH》 *

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Application publication date: 20170811