CN103983592A - Method for detecting concentration of hydroxyl radicals in solution - Google Patents
Method for detecting concentration of hydroxyl radicals in solution Download PDFInfo
- Publication number
- CN103983592A CN103983592A CN201410249893.3A CN201410249893A CN103983592A CN 103983592 A CN103983592 A CN 103983592A CN 201410249893 A CN201410249893 A CN 201410249893A CN 103983592 A CN103983592 A CN 103983592A
- Authority
- CN
- China
- Prior art keywords
- solution
- free radical
- sulfinic acid
- concentration
- add
- 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
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting the concentration of hydroxyl radicals in a solution and relates to a method for detecting hydroxyl radicals. The method solves the problems that the existing method for detecting the concentration of hydroxyl radicals in the solution has high detection expenses, long detection time, poor quantifying effect, poor repeatability and low detection precision. The method comprises the following steps: I. drawing a standard curve; II. acquiring a regression equation; III. acquiring the regression equation according to the standard curve: A=0.00476C(mol.L<sup>-1</sup>) plus 0.01271(r=0.99951), and calculating the concentration of hydroxyl radicals in the solution. FeSO4 is firstly added to successfully inhibit extraction of extraction agents to Luxol fast blue BB salt, the effect of the Luxol fast blue BB salt on the detection result is greatly weakened, the detection precision is improved, the detection error is within 5%, and the experiment repeatability is high.
Description
Technical field
The present invention relates to a kind of method that detects hydroxyl radical free radical.
Background technology
In known oxygenant, the oxidability of OH is only second to F
2, be a kind of nonselective oxygenant, can be oxidized easily various organism and inorganics, oxidation efficiency is high, and reaction velocity is fast.In the homogeneous phase and Heterogeneous oxidation degradation process of waste water, all thought that the principal element of oxidation is OH.In recent years, OH has been applied to deep environmental chemistry study, in the research in Atmospheric Chemistry, natural water body chemistry and waste water advanced oxidation etc., relates to the chemical reaction that many free radicals participate in, the conversion of free radical and pollutant and remove closely related.Because free radical is very active, the life-span that concentration is low, exist is short, therefore in the relevant research that relates to free radical, and its assay method particular importance that just seems.
In solution, the detection method of hydroxyl radical free radical comprises: electron spin resonance, high performance liquid chromatography, chemoluminescence method, fluorometry and spectrophotometric method.Electron spin resonance instrument is expensive, and operation steps is complicated, and detection time is long, quantitatively poor effect.Chemoluminescence method is simple to operate, but poor anti jamming capability, measuring accuracy is low.Fluorometry detection speed is very fast, but accuracy of detection is poor equally.To have scope aspect OH wide quantitatively detecting for high performance liquid chromatography and spectrophotometric method, the advantage that precision is high.But the high performance liquid chromatography running time is long, instrument price is far above spectrophotometer.Research detects the reliable spectrophotometric method of economy of OH concentration in solution for the Determination of Free Radicals that promotes extensively to adopt, and promotes association area research progress and has realistic meaning.
Based on Russell reaction mechanism, carrying out spectrophotometry OH concentration is an important research branch.First use dimethyl sulfoxide (DMSO) (DMSO) as the molecular probe of OH, generate methyl sulfinic acid MSIA, then carry out coloring reaction with various dyestuffs, reaction product is carried out photometric detection after extractant extraction.The Babbs of Purdue University detects OH concentration to Russell reaction mechanism and probes into.Because methyl sulfinic acid MSIA can not be in occurring in nature existence steady in a long-term, for studying, benzene sulfinic acid sodium salt or methyl sulfinic acid sodium replace the reaction product MSIA drawing standard curve of DMSO and OH.Use DMSO to make OH trapping agent, add fast blue BB salt reaction to generate diazonium sulfone product, with extractant extraction diazonium sulfone product, carry out photometric detection.Yet in the time of extractant extraction diazonium sulfone product, can extract fast blue BB salt simultaneously, cause measuring accuracy low, repeatable poor.Suppressing the extraction of extractant to fast blue BB salt, is that only to extract diazonium sulfone product be this detection method problem demanding prompt solution on solvent selection ground.
Summary of the invention
The object of the invention is to solve hydroxyl free concentration in existing method detection solution exists testing cost expensive, detection time is long, quantitative poor effect, the repeatable poor and low problem of measuring accuracy, and a kind of method that detects hydroxy free radical concentration in solution is provided.
A method that detects hydroxy free radical concentration in solution, specifically completes according to the following steps:
One, the drafting of typical curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6., and wherein 1. number adding volumetric molar concentration is 25 μ molL
-1methyl sulfinic acid sodium solution 1mL, 2. number adding volumetric molar concentration is 50 μ molL
-1methyl sulfinic acid sodium solution 1mL, 3. number adding volumetric molar concentration is 75 μ molL
-1methyl sulfinic acid sodium solution 1mL, 4. number adding volumetric molar concentration is 100 μ molL
-1methyl sulfinic acid sodium solution 1mL, 5. number adding volumetric molar concentration is 150 μ molL
-1methyl sulfinic acid sodium solution 1mL; 6. number adding volumetric molar concentration is 250 μ molL
-1methyl sulfinic acid sodium solution 1mL; Then the container being numbered 1. is 6. placed in to dark place, to being numbered 1., in container 6., to add volumetric molar concentration be 2mmolL respectively
-1fast blue BB salt, wherein 1. number add 1.25mL; 2. number add 2.50mL, 3. number add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature react again 10min, obtain being numbered 1. the mixed solution that contains diazonium sulfone product 6.; To being numbered 1., in the mixed solution that contains diazonium sulfone product 6., add FeSO respectively again
4and 3mL toluene/butanols extractant, extraction 5min, removes subnatant, obtains being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; To being numbered 1., in 3mL upper layer of extraction liquid 6., add 1mL pyridine respectively again, obtain being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, measures 425nm place and is numbered the absorbance that 1. arrives extract to be measured 6.; Take absorbance as ordinate, and the methyl sulfinic acid na concn of take is horizontal ordinate, drawing standard curve;
FeSO described in step 1
4amount of substance be (200mmol～500mmol): 1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6.;
In toluene/butanols mixed extractant described in step 1, the mol ratio of toluene and butanols is 2:1;
Two, the acquisition of regression equation:
According to the typical curve of step 1, obtain regression equation: A=0.00476C (μ molL
-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methyl sulfinic acid na concn;
Three, the mensuration of hydroxyl radical free radical in solution:
1. get the solution 1mL that contains hydroxyl radical free radical, then in the solution that contains hydroxyl radical free radical to 1mL, add 0.002g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO
4, re-using 3mL toluene/butanols mixed extractant and extract containing diazonium sulfone product mixed solution, extraction time is 5min, removes subnatant, obtains upper strata liquid; Use butanol/water saturated solution that upper strata liquid is cleaned 1 time～2 times, more centrifugal 2min～3min under the condition that is 500r/min～1000r/min at rotating speed, then remove the subnatant after centrifugal, obtain the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to hydroxy free radical concentration in regression equation calculation solution in step 2 at 425nm place;
The FeSO of step 3 described in 3.
4amount of substance be (200mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product;
In toluene/butanols mixed extractant of step 3 described in 3., the mol ratio of toluene and butanols is 2:1;
The volume of the pyridine of step 3 described in 3. and centrifugal after the volume ratio of upper strata liquid be 1:3.
Beneficial effect of the present invention:
One, the trapping agent that the present invention uses is DMSO, and this trapping agent is the OH trapping agent that a kind of performance is extremely outstanding, is applicable to various liquid environments, and price is extremely low, and capture effect is good; In one-time detection solution of the present invention, the trapping agent of concentration of hydroxyl radical free radical and the expense of other chemicalss be less than 2 yuans, be only ten thousand of DMPO trapping agent expense/;
Two, the detecting instrument that this patent is used is only ultraviolet-visible pectrophotometer, and technical device is ripe, cheap;
Three, first passage of the present invention adds FeSO
4successfully suppressed the extraction of extractant to fast blue BB salt, greatly weakened the impact of fast blue BB salt on testing result, improved accuracy of detection, detected error in 5%, and experiment is repeatable high;
Four, it is little that the method for operating the present invention relates to is affected by pH value of solution, and no matter acid system or the solution of alkaline system are all applicable;
Five, the applicable OH concentration range of the method for operating that the present invention relates to is large, and the best OH concentration of detection is 25 μ molL
-1～250 μ molL
-1, for higher also can the detecting by dilution process of OH concentration;
Six, the method for operating the present invention relates to is applied widely, Fenton system, alkaline H
2o
2in system, biosome, bleach system, organic wastewater system etc. are all applicable.
The present invention can obtain a kind of method that detects hydroxy free radical concentration in solution.
Accompanying drawing explanation
Fig. 1 is the methyl sulfinic acid na concn of test one drafting and the typical curve of absorbance.
Embodiment
Embodiment one: present embodiment is a kind of method that detects hydroxy free radical concentration in solution, specifically completes according to the following steps:
One, the drafting of typical curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6., and wherein 1. number adding volumetric molar concentration is 25 μ molL
-1methyl sulfinic acid sodium solution 1mL, 2. number adding volumetric molar concentration is 50 μ molL
-1methyl sulfinic acid sodium solution 1mL, 3. number adding volumetric molar concentration is 75 μ molL
-1methyl sulfinic acid sodium solution 1mL, 4. number adding volumetric molar concentration is 100 μ molL
-1methyl sulfinic acid sodium solution 1mL, 5. number adding volumetric molar concentration is 150 μ molL
-1methyl sulfinic acid sodium solution 1mL; 6. number adding volumetric molar concentration is 250 μ molL
-1methyl sulfinic acid sodium solution 1mL; Then the container being numbered 1. is 6. placed in to dark place, to being numbered 1., in container 6., to add volumetric molar concentration be 2mmolL respectively
-1fast blue BB salt, wherein 1. number add 1.25mL; 2. number add 2.50mL, 3. number add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature react again 10min, obtain being numbered 1. the mixed solution that contains diazonium sulfone product 6.; To being numbered 1., in the mixed solution that contains diazonium sulfone product 6., add FeSO respectively again
4and 3mL toluene/butanols extractant, extraction 5min, removes subnatant, obtains being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; To being numbered 1., in 3mL upper layer of extraction liquid 6., add 1mL pyridine respectively again, obtain being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, measures 425nm place and is numbered the absorbance that 1. arrives extract to be measured 6.; Take absorbance as ordinate, and the methyl sulfinic acid na concn of take is horizontal ordinate, drawing standard curve;
FeSO described in step 1
4amount of substance be (200mmol～500mmol): 1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6.;
In toluene/butanols mixed extractant described in step 1, the mol ratio of toluene and butanols is 2:1;
Two, the acquisition of regression equation:
According to the typical curve of step 1, obtain regression equation: A=0.00476C (μ molL
-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methyl sulfinic acid na concn;
Three, the mensuration of hydroxyl radical free radical in solution:
1. get the solution 1mL that contains hydroxyl radical free radical, then in the solution that contains hydroxyl radical free radical to 1mL, add 0.002g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO
4, re-using 3mL toluene/butanols mixed extractant and extract containing diazonium sulfone product mixed solution, extraction time is 5min, removes subnatant, obtains upper strata liquid; Use butanol/water saturated solution that upper strata liquid is cleaned 1 time～2 times, more centrifugal 2min～3min under the condition that is 500r/min～1000r/min at rotating speed, then remove the subnatant after centrifugal, obtain the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to hydroxy free radical concentration in regression equation calculation solution in step 2 at 425nm place;
The FeSO of step 3 described in 3.
4amount of substance be (200mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product;
In toluene/butanols mixed extractant of step 3 described in 3., the mol ratio of toluene and butanols is 2:1;
The volume of the pyridine of step 3 described in 3. and centrifugal after the volume ratio of upper strata liquid be 1:3.
The beneficial effect of present embodiment:
One, the trapping agent that present embodiment is used is DMSO, and this trapping agent is the OH trapping agent that a kind of performance is extremely outstanding, is applicable to various liquid environments, and price is extremely low, and capture effect is good; In one-time detection solution of the present invention, the trapping agent of concentration of hydroxyl radical free radical and the expense of other chemicalss be less than 2 yuans, be only ten thousand of DMPO trapping agent expense/;
Two, the detecting instrument that present embodiment is used is only ultraviolet-visible pectrophotometer, and technical device is ripe, cheap;
Three, present embodiment first passage adds FeSO
4successfully suppressed the extraction of extractant to fast blue BB salt, greatly weakened the impact of fast blue BB salt on testing result, improved accuracy of detection, detected error in 5%, and experiment is repeatable high;
Four, it is little that the method for operating that present embodiment relates to is affected by pH value of solution, and no matter acid system or the solution of alkaline system are all applicable;
Five, the applicable OH concentration range of present embodiment relates to method of operating is large, and the best OH concentration of detection is 25 μ molL
-1～250 μ molL
-1, for higher also can the detecting by dilution process of OH concentration;
Six, the method for operating that present embodiment relates to is applied widely, Fenton system, alkaline H
2o
2in system, biosome, bleach system, organic wastewater system etc. are all applicable.
Present embodiment can obtain a kind of method that detects hydroxy free radical concentration in solution.
Embodiment two: present embodiment and embodiment one difference are: the FeSO described in step 1
4amount of substance be (250mmol～450mmol): 1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6..Other steps are identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two difference are: step 3 is got the solution 1mL that contains hydroxyl radical free radical in 1., in the solution that contains hydroxyl radical free radical to 1mL again, add 0.002g～0.01g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: step 3 is got the solution 1mL that contains hydroxyl radical free radical in 1., in the solution that contains hydroxyl radical free radical to 1mL again, add 0.005g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: step 3 is got the solution 1mL that contains hydroxyl radical free radical in 1., in the solution that contains hydroxyl radical free radical to 1mL again, add 0.01g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: step 3 will be placed in dark place containing the solution of methyl sulfinic acid in 2., and adding 1.25mL～2.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: step 3 will be placed in dark place containing the solution of methyl sulfinic acid in 2., and adding 5mL～10mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: step 3 will be placed in dark place containing the solution of methyl sulfinic acid in 2., and adding 10mL～12.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: the FeSO of step 3 described in 3.
4amount of substance be (300mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: the FeSO of step 3 described in 3.
4amount of substance be (200mmol～400mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.Other steps are identical with embodiment one to nine.
Below in conjunction with embodiment, the present invention is further set forth:
Embodiment mono-:
One, the drafting of typical curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6., and wherein 1. number adding volumetric molar concentration is 25 μ molL
-1methyl sulfinic acid sodium solution 1mL, 2. number adding volumetric molar concentration is 50 μ molL
-1methyl sulfinic acid sodium solution 1mL, 3. number adding volumetric molar concentration is 75 μ molL
-1methyl sulfinic acid sodium solution 1mL, 4. number adding volumetric molar concentration is 100 μ molL
-1methyl sulfinic acid sodium solution 1mL, 5. number adding volumetric molar concentration is 150 μ molL
-1methyl sulfinic acid sodium solution 1mL; 6. number adding volumetric molar concentration is 150 μ molL
-1methyl sulfinic acid sodium solution 1mL; Then the container being numbered 1. is 6. placed in to dark place, to being numbered 1., in container 6., to add volumetric molar concentration be 2mmolL respectively
-1fast blue BB salt, wherein 1. number add 1.25mL; 2. number add 2.50mL, 3. number add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature react again 10min, obtain being numbered 1. the mixed solution that contains diazonium sulfone product 6.; To being numbered 1., in the mixed solution that contains diazonium sulfone product 6., add FeSO respectively again
4and 3mL toluene/butanols extractant, extraction 5min, removes subnatant, obtains being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; To being numbered 1., in 3mL upper layer of extraction liquid 6., add 1mL pyridine respectively again, obtain being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, measures 425nm place and is numbered the absorbance that 1. arrives extract to be measured 6.; Take absorbance as ordinate, and the methyl sulfinic acid na concn of take is horizontal ordinate, drawing standard curve;
FeSO described in step 1
4amount of substance be 300mmol:1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6.;
In toluene/butanols mixed extractant described in step 1, the mol ratio of toluene and butanols is 2:1;
In toluene/butanols mixed extractant described in step 1, the mol ratio of toluene and butanols is 2:1;
Two, the acquisition of regression equation:
According to the typical curve of step 1, obtain regression equation: A=0.00476C (μ molL
-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methyl sulfinic acid na concn;
Three, preparing hydroxy free radical concentration is 50 μ molL
-1solution:
Get DMSO and FeSO
4volumetric molar concentration be respectively 50mmolL
-1and 1mmolL
-1solution 80mL; To 80mLDMSO and FeSO
4volumetric molar concentration be respectively 50mmolL
-1and 1mmolL
-1solution in add H
2o
2be respectively 250 μ molL with the volumetric molar concentration of DMSO
-1and 50mmolL
-1solution 20mL, obtaining hydroxy free radical concentration is 50 μ molL
-1solution;
Four, the mensuration of hydroxyl radical free radical in solution:
Getting hydroxy free radical concentration is 50 μ molL
-1solution 1mL be placed in dark place, adding 2.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO
4, re-using 3mL toluene/butanols mixed extractant and extract containing diazonium sulfone product mixed solution, extraction time is 5min, removes subnatant, obtains upper strata liquid; Use butanol/water saturated solution that upper strata liquid is cleaned 2 times, more centrifugal 2min under the condition that is 800r/min at rotating speed, then remove the subnatant after centrifugal, obtain the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to hydroxy free radical concentration in regression equation calculation solution in step 2 at 425nm place;
The FeSO of step 3 described in 3.
4amount of substance be 300mmol:1L with the volume ratio of the mixed solution that contains diazonium sulfone product;
In toluene/butanols mixed extractant of step 3 described in 3., the mol ratio of toluene and butanols is 2:1;
The volume of the pyridine of step 3 described in 3. and centrifugal after the volume ratio of upper strata liquid be 1:3.
According to hydroxy free radical concentration in regression equation calculation embodiment mono-solution in step 2, be 48.1 μ molL
-1, with configuration hydroxy free radical concentration be 50 μ molL
-1solution phase ratio, error is only 3.8%.
Fig. 1 is the methyl sulfinic acid na concn of test one drafting and the typical curve of absorbance; According to Fig. 1 typical curve obtain regression equation: A=0.00476C (μ molL
-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methyl sulfinic acid na concn, namely hydroxy free radical concentration.
Claims (10)
1. detect a method for hydroxy free radical concentration in solution, it is characterized in that a kind ofly detecting in solution that the method for hydroxy free radical concentration specifically completes according to the following steps:
One, the drafting of typical curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6., and wherein 1. number adding volumetric molar concentration is 25 μ molL
-1methyl sulfinic acid sodium solution 1mL, 2. number adding volumetric molar concentration is 50 μ molL
-1methyl sulfinic acid sodium solution 1mL, 3. number adding volumetric molar concentration is 75 μ molL
-1methyl sulfinic acid sodium solution 1mL, 4. number adding volumetric molar concentration is 100 μ molL
-1methyl sulfinic acid sodium solution 1mL, 5. number adding volumetric molar concentration is 150 μ molL
-1methyl sulfinic acid sodium solution 1mL; 6. number adding volumetric molar concentration is 250 μ molL
-1methyl sulfinic acid sodium solution 1mL; Then the container being numbered 1. is 6. placed in to dark place, to being numbered 1., in container 6., to add volumetric molar concentration be 2mmolL respectively
-1fast blue BB salt, wherein 1. number add 1.25mL; 2. number add 2.50mL, 3. number add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature react again 10min, obtain being numbered 1. the mixed solution that contains diazonium sulfone product 6.; To being numbered 1., in the mixed solution that contains diazonium sulfone product 6., add FeSO respectively again
4and 3mL toluene/butanols extractant, extraction 5min, removes subnatant, obtains being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; To being numbered 1., in 3mL upper layer of extraction liquid 6., add 1mL pyridine respectively again, obtain being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, measures 425nm place and is numbered the absorbance that 1. arrives extract to be measured 6.; Take absorbance as ordinate, and the methyl sulfinic acid na concn of take is horizontal ordinate, drawing standard curve;
FeSO described in step 1
4amount of substance be (200mmol～500mmol): 1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6.;
In toluene/butanols mixed extractant described in step 1, the mol ratio of toluene and butanols is 2:1;
Two, the acquisition of regression equation:
According to the typical curve of step 1, obtain regression equation: A=0.00476C (μ molL
-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methyl sulfinic acid na concn;
Three, the mensuration of hydroxyl radical free radical in solution:
1. get the solution 1mL that contains hydroxyl radical free radical, then in the solution that contains hydroxyl radical free radical to 1mL, add 0.002g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO
4, re-using 3mL toluene/butanols mixed extractant and extract containing diazonium sulfone product mixed solution, extraction time is 5min, removes subnatant, obtains upper strata liquid; Use butanol/water saturated solution that upper strata liquid is cleaned 1 time～2 times, more centrifugal 2min～3min under the condition that is 500r/min～1000r/min at rotating speed, then remove the subnatant after centrifugal, obtain the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to hydroxy free radical concentration in regression equation calculation solution in step 2 at 425nm place;
The FeSO of step 3 described in 3.
4amount of substance be (200mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product;
In toluene/butanols mixed extractant of step 3 described in 3., the mol ratio of toluene and butanols is 2:1;
The volume of the pyridine of step 3 described in 3. and centrifugal after the volume ratio of upper strata liquid be 1:3.
2. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that the FeSO described in step 1
4amount of substance be (250mmol～450mmol): 1L with the volume ratio that is numbered 1. the mixed solution that contains diazonium sulfone product 6..
3. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, it is characterized in that getting during step 3 1. the solution 1mL that contains hydroxyl radical free radical, in the solution that contains hydroxyl radical free radical to 1mL again, add 0.002g～0.01g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.
4. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, it is characterized in that getting during step 3 1. the solution 1mL that contains hydroxyl radical free radical, in the solution that contains hydroxyl radical free radical to 1mL again, add 0.005g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.
5. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, it is characterized in that getting during step 3 1. the solution 1mL that contains hydroxyl radical free radical, in the solution that contains hydroxyl radical free radical to 1mL again, add 0.01g～0.02g dimethyl sulfoxide (DMSO), obtain the solution containing methyl sulfinic acid.
6. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that, during step 3 2., the solution containing methyl sulfinic acid is placed in to dark place, and adding 1.25mL～2.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.
7. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that, during step 3 2., the solution containing methyl sulfinic acid is placed in to dark place, and adding 5mL～10mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.
8. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that, during step 3 2., the solution containing methyl sulfinic acid is placed in to dark place, and adding 10mL～12.5mL volumetric molar concentration is 2mmolL
-1fast blue BB salt solution, under room temperature, react 10min, obtain the mixed solution that contains diazonium sulfone product.
9. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that the FeSO described in step 3 3.
4amount of substance be (300mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.
10. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that the FeSO described in step 3 3.
4amount of substance be (200mmol～400mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410249893.3A CN103983592B (en) | 2014-06-06 | 2014-06-06 | A kind of method that detects hydroxy free radical concentration in solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410249893.3A CN103983592B (en) | 2014-06-06 | 2014-06-06 | A kind of method that detects hydroxy free radical concentration in solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103983592A true CN103983592A (en) | 2014-08-13 |
| CN103983592B CN103983592B (en) | 2016-05-11 |
Family
ID=51275651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410249893.3A Expired - Fee Related CN103983592B (en) | 2014-06-06 | 2014-06-06 | A kind of method that detects hydroxy free radical concentration in solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103983592B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105259126A (en) * | 2015-11-12 | 2016-01-20 | 东北石油大学 | Method for quantitatively detecting concentration of hydroxyl free radical in Fenton partition system |
| CN106596526A (en) * | 2015-10-20 | 2017-04-26 | 谱尼测试集团江苏有限公司 | Detection method for calcium peroxide content in flour |
| CN109060694A (en) * | 2018-10-15 | 2018-12-21 | 广州中医药大学(广州中医药研究院) | A kind of colorimetric detection method of hydroxyl radical free radical and its application |
| CN112285100A (en) * | 2020-10-16 | 2021-01-29 | 天津工业大学 | Method for detecting concentration of free radicals in sodium hypochlorite aqueous solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789219A (en) * | 2005-12-09 | 2006-06-21 | 华南理工大学 | Method for initiating, capturing and measuring hydroxy radical under high temperature |
| CN101413896A (en) * | 2008-12-02 | 2009-04-22 | 上海理工大学 | Method for measuring hydroxy free radical |
| CN101718705A (en) * | 2009-11-13 | 2010-06-02 | 上海理工大学 | Method for detecting hydroxyl radicals |
| CN102297875A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院生态环境研究中心 | Method for measuring hydroxyl free radical in plant body |
| CN102495015A (en) * | 2011-12-12 | 2012-06-13 | 江南大学 | Method for indirectly measuring hydroxyl radicals generated by Fenton reaction |
| CN103776808A (en) * | 2014-01-24 | 2014-05-07 | 鼎泰（湖北）生化科技设备制造有限公司 | Method for detecting hydroxyl radical concentration |
-
2014
- 2014-06-06 CN CN201410249893.3A patent/CN103983592B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789219A (en) * | 2005-12-09 | 2006-06-21 | 华南理工大学 | Method for initiating, capturing and measuring hydroxy radical under high temperature |
| CN101413896A (en) * | 2008-12-02 | 2009-04-22 | 上海理工大学 | Method for measuring hydroxy free radical |
| CN101718705A (en) * | 2009-11-13 | 2010-06-02 | 上海理工大学 | Method for detecting hydroxyl radicals |
| CN102297875A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院生态环境研究中心 | Method for measuring hydroxyl free radical in plant body |
| CN102495015A (en) * | 2011-12-12 | 2012-06-13 | 江南大学 | Method for indirectly measuring hydroxyl radicals generated by Fenton reaction |
| CN103776808A (en) * | 2014-01-24 | 2014-05-07 | 鼎泰（湖北）生化科技设备制造有限公司 | Method for detecting hydroxyl radical concentration |
Non-Patent Citations (2)
| Title |
|---|
| M.G. STEINER ET AL.: "Quantitation of the Hydroxyl Radical By Reaction with Dimethyl Sulfoxide", 《ARCHIVES OF BIOCHEMISTRY AND BIOPHYSICS》, vol. 278, no. 2, 1 May 1990 (1990-05-01), pages 478 - 481, XP024758510, DOI: doi:10.1016/0003-9861(90)90288-A * |
| 徐向荣等: "比色法测定Fenton反应产生的羟自由基及其应用", 《生物化学与生物物理进展》, vol. 26, no. 01, 28 February 1999 (1999-02-28), pages 67 - 69 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106596526A (en) * | 2015-10-20 | 2017-04-26 | 谱尼测试集团江苏有限公司 | Detection method for calcium peroxide content in flour |
| CN106596526B (en) * | 2015-10-20 | 2020-01-07 | 谱尼测试集团江苏有限公司 | Method for detecting content of calcium peroxide in flour |
| CN105259126A (en) * | 2015-11-12 | 2016-01-20 | 东北石油大学 | Method for quantitatively detecting concentration of hydroxyl free radical in Fenton partition system |
| CN105259126B (en) * | 2015-11-12 | 2017-11-10 | 东北石油大学 | A kind of method for quantitatively detecting hydroxy free radical concentration in Fenton decomposing solutions |
| CN109060694A (en) * | 2018-10-15 | 2018-12-21 | 广州中医药大学(广州中医药研究院) | A kind of colorimetric detection method of hydroxyl radical free radical and its application |
| CN112285100A (en) * | 2020-10-16 | 2021-01-29 | 天津工业大学 | Method for detecting concentration of free radicals in sodium hypochlorite aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103983592B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103983592A (en) | Method for detecting concentration of hydroxyl radicals in solution | |
| CN201974384U (en) | Test-paper card for detecting nitrite content | |
| CN103472051A (en) | SERS (Surface Enhanced Raman Spectroscopy) detection method for pesticide residues in fruits | |
| CN103785314B (en) | A kind of blender and flow type photometric detection automated analysis instrument | |
| CN101158638A (en) | Nano argentum spectrophotometry for detecting hydroxy free radical | |
| CN105241852A (en) | Preparation method and application of fluorescent probe | |
| Zilberman et al. | Microfluidic optoelectronic sensor based on a composite halochromic material for dissolved carbon dioxide detection | |
| CN102507482B (en) | Detection method and reagents for quantitatively detecting 6-methyl-2-thiopyridyl-N-acetyl-beta-D-glucosaminide (MPT-NAG) | |
| Páscoa et al. | Spectrophotometric determination of zinc and copper in a multi-syringe flow injection analysis system using a liquid waveguide capillary cell: Application to natural waters | |
| Jiang et al. | An environmentally-benign flow-batch system for headspace single-drop microextraction and on-drop conductometric detecting ammonium | |
| Hatta et al. | The performance of a new linear light path flow cell is compared with a liquid core waveguide and the linear cell is used for spectrophotometric determination of nitrite in sea water at nanomolar concentrations | |
| CN103134759A (en) | Detection method for quantitative detection of 6-methyl-2-thiopyridine-N-acetyl-beta-D-glucosaminide | |
| CN103048374A (en) | Electrochemical method for detecting anthracene of polycyclic aromatic hydrocarbon | |
| CN104155289A (en) | Solid electrochemical luminescence sensor for detecting mercury ions and preparation method and application of solid electrochemical luminescence sensor for detecting mercury ions | |
| CN104614421A (en) | Electrochemical method for detecting 2,4,6-trichlorophenol | |
| CN102288568B (en) | Method for rapidly measuring nanogold catalysis-silver nitrate reduction luminosity of UO2<2+> in water | |
| CN104502474B (en) | The liquid phase chromatography detection method of benzophenone anti-ultraviolet finishing agent in textile | |
| Powers et al. | MoDIE: Moderate dissolved inorganic carbon (DI13C) isotope enrichment for improved evaluation of DIC photochemical production in natural waters | |
| CN104251827A (en) | Method for determining concentration of mercury ions or silver ions in solution | |
| CN105259126A (en) | Method for quantitatively detecting concentration of hydroxyl free radical in Fenton partition system | |
| CN103115882B (en) | Method for detecting H2O2 | |
| CN101776611A (en) | Detection method for measuring sugar content in environmental water sample by spectrophotometer | |
| Somboot et al. | Environmentally friendly liquid medium for a cost-effective long-path absorption liquid core waveguide with a gas diffusion flow analysis system | |
| Christensen et al. | PARAFAC Modeling of Fluorescence Excitation− Emission Spectra of Fish Bile for Rapid En Route Screening of PAC Exposure | |
| CN101493419A (en) | Chemiluminescence method for detecting chlorophyll alpha |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160511 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |