CN103983592B - A kind of method that detects hydroxy free radical concentration in solution - Google Patents
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Abstract
Detect a method for hydroxy free radical concentration in solution, it relates to a kind of method that detects hydroxyl radical free radical. The object of the invention is to solve hydroxyl free concentration in existing method detection solution and have testing cost costliness, detection time is long, quantitatively poor effect, the repeatable poor and low problem of measuring accuracy. Step: one, the drafting of calibration curve; Two, the acquisition of regression equation; Three, obtain regression equation according to calibration curve: A=0.00476C (molL-1The concentration of hydroxyl radical free radical in solution is calculated in)+0.01271 (r=0.99951). First passage of the present invention adds FeSO4Successfully 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. The present invention can obtain a kind of method that detects hydroxy free radical concentration in solution.
Description
Technical field
The present invention relates to a kind of method that detects hydroxyl radical free radical.
Background technology
In known oxidant, the oxidability of OH is only second to F2, be a kind of nonselective oxidant, can hold very muchThe various organic matters of easy oxidation and inorganic matter, oxidation efficiency is high, and reaction speed is fast. Homogeneous phase and Heterogeneous oxidation at waste water fallIn solution process, all think that the principal element of oxidation is OH. In recent years, OH has been applied to deep Environmental ChemistryResearch, as in the research of Atmospheric Chemistry, natural water body chemistry and waste water advanced oxidation etc., relates to that many free radicals participate inChemical reaction, the conversion of free radical and pollutant and remove closely related. Because free radical is very active, concentration is low, existenceLife-span short, therefore in the research about relating to free radical, 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,XRF and AAS. Electron spin resonance instrument costliness, operating procedure complexity, detection time is long, quantitativelyPoor effect. Chemoluminescence method is simple to operate, but poor anti jamming capability, measuring accuracy is low. XRF detection speedHurry up, but accuracy of detection is poor equally. To have scope aspect OH wide quantitatively detecting for high performance liquid chromatography and AAS,The advantage that precision is high. But the high performance liquid chromatography operating time is long, instrument price is far above spectrophotometer. Research detects moltenIn liquid, the reliable AAS of the economy of OH concentration, for the Determination of Free Radicals that promotes extensively to adopt, promotes relevant neckTerritory research progress has realistic meaning.
Carrying out spectrophotometry OH concentration based on Russell reaction mechanism is an important research branch. First useDimethyl sulfoxide (DMSO) (DMSO), as the molecular probe of OH, generates methyl sulfinic acid MSIA, then carries out with various dyestuffsColoring reaction, product is carried out photometric detection after extractant extraction. The Babbs of Purdue University is to Russell reaction mechanismDetecting OH concentration probes into. Because methyl sulfinic acid MSIA can not be in occurring in nature existence steady in a long-term, research is usedBenzene sulfinic acid sodium salt or methyl sulfinic acid sodium replace the product MSIA drawing standard curve of DMSO and OH. UseDMSO makes OH capturing agent, adds fast blue BB salt reaction to generate diazonium sulfone product, with extractant extraction diazonium sulfone productCarry out photometric detection. But when extractant extraction diazonium sulfone product, can extract fast blue BB salt simultaneously, cause testPrecision is low, repeatable poor. Suppressing the extraction of extractant to fast blue BB salt, is that solvent selection ground only extracts diazoniumSulfone product is this detection method problem demanding prompt solution.
Summary of the invention
The object of the invention is to solve hydroxyl free concentration in existing method detection solution and have testing cost costliness, when detectionBetween long, quantitatively poor effect, the repeatable poor and low problem of measuring accuracy, and hydroxyl free in a kind of detection solution is providedThe method of base concentration.
A method that detects hydroxy free radical concentration in solution, specifically completes according to the following steps:
One, the drafting of calibration curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6.,Wherein 1. number adding molar concentration is 25 μ molL-1Methyl sulfinic acid sodium solution 1mL, 2. number add molar concentration to be50μmol·L-1Methyl sulfinic acid sodium solution 1mL, 3. number adding molar concentration is 75 μ molL-1Methyl sulfinic acid sodium moltenLiquid 1mL, 4. number adding molar concentration is 100 μ molL-1Methyl sulfinic acid sodium solution 1mL, 5. number add molar concentrationBe 150 μ molL-1Methyl sulfinic acid sodium solution 1mL; 6. number adding molar concentration is 250 μ molL-1Methyl sulfinic acidSodium solution 1mL; Then be placed in dark place by being numbered 1. to container 6., add in container 6. to being numbered 1. respectivelyMolar concentration is 2mmolL-1Fast blue BB salt, wherein 1. number add 1.25mL; 3. number 2. number add 2.50mL,Add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature reaction again1. 10min, obtain being numbered the mixed solution that contains diazonium sulfone product 6.; Again respectively to being numbered 1. containing 6.In the mixed solution of diazonium sulfone product, add FeSO4And 3mL toluene/butanols extractant, extraction 5min, removes subnatant,Obtain being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; Add in 3mL upper layer of extraction liquid 6. to being numbered 1. respectively again1mL pyridine, obtains being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, surveysDetermine 425nm place and be numbered the absorbance that 1. arrives extract to be measured 6.; Taking absorbance as ordinate, with methyl sulfinic acid sodiumConcentration is abscissa, drawing standard curve;
FeSO described in step 14Amount of substance be numbered 1. the mixed solution that contains diazonium sulfone product 6.Volume ratio is (200mmol～500mmol): 1L;
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:
Obtain regression equation: A=0.00476C (μ molL according to the calibration curve of step 1-1)+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 add in the solution that contains hydroxyl radical free radical to 1mL0.002g～0.02g dimethyl sulfoxide (DMSO), obtains the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL molar concentration is 2mmolL-1Heavily fortified pointThe blue BB salting liquid in jail, reacts 10min under room temperature, obtains the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO4, re-use 3mL toluene/butanols mixed extractant pairContain diazonium sulfone product mixed solution and extract, extraction time is 5min, removes subnatant, obtains upper strata liquid; UseButanol/water saturated solution cleans upper strata liquid 1 time～2 times, more centrifugal under the condition that is 500r/min～1000r/min at rotating speed2min～3min, then remove the subnatant after centrifugal, obtains the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyrrolePyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to step at 425nm placeHydroxy free radical concentration in regression equation calculation solution in two;
The FeSO of step 3 described in 3.4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be(200mmol～500mmol):1L；
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 capturing agent that the present invention uses is DMSO, and this capturing agent is the OH capturing agent that a kind of performance is extremely given prominence to,Be applicable to various liquid environments, and price is extremely low, capture effect is good; In one-time detection solution of the present invention, hydroxyl radical free radical is denseThe capturing agent of degree and the expense of other chemicals be less than 2 yuans, be only ten thousand of DMPO capturing agent expense/;
Two, the detecting instrument that this patent uses is only ultraviolet-uisible spectrophotometer, and technical device maturation is cheap;
Three, first passage of the present invention adds FeSO4Successfully suppress the extraction of extractant to fast blue BB salt, greatly weakenedThe impact of fast blue BB salt on testing result, improves accuracy of detection, detect error in 5%, and experiment is repeatableHigh;
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 equalBe suitable for;
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 is25μmol·L-1～250μmol·L-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 H2O2In system, organism,Bleach system, organic wastewater system etc. are all suitable for.
The present invention can obtain a kind of method that detects hydroxy free radical concentration in solution.
Brief description of the drawings
Fig. 1 is the methyl sulfinic acid na concn of test one drafting and the calibration curve of absorbance.
Detailed description of the invention
Detailed description of the invention one: present embodiment is a kind of method that detects hydroxy free radical concentration in solution, specifically by withLower step completes:
One, the drafting of calibration curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6.,Wherein 1. number adding molar concentration is 25 μ molL-1Methyl sulfinic acid sodium solution 1mL, 2. number add molar concentration to be50μmol·L-1Methyl sulfinic acid sodium solution 1mL, 3. number adding molar concentration is 75 μ molL-1Methyl sulfinic acid sodium moltenLiquid 1mL, 4. number adding molar concentration is 100 μ molL-1Methyl sulfinic acid sodium solution 1mL, 5. number add molar concentrationBe 150 μ molL-1Methyl sulfinic acid sodium solution 1mL; 6. number adding molar concentration is 250 μ molL-1Methyl sulfinic acidSodium solution 1mL; Then be placed in dark place by being numbered 1. to container 6., add in container 6. to being numbered 1. respectivelyMolar concentration is 2mmolL-1Fast blue BB salt, wherein 1. number add 1.25mL; 3. number 2. number add 2.50mL,Add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature reaction again1. 10min, obtain being numbered the mixed solution that contains diazonium sulfone product 6.; Again respectively to being numbered 1. containing 6.In the mixed solution of diazonium sulfone product, add FeSO4And 3mL toluene/butanols extractant, extraction 5min, removes subnatant,Obtain being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; Add in 3mL upper layer of extraction liquid 6. to being numbered 1. respectively again1mL pyridine, obtains being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, surveysDetermine 425nm place and be numbered the absorbance that 1. arrives extract to be measured 6.; Taking absorbance as ordinate, with methyl sulfinic acid sodiumConcentration is abscissa, drawing standard curve;
FeSO described in step 14Amount of substance be numbered 1. the mixed solution that contains diazonium sulfone product 6.Volume ratio is (200mmol～500mmol): 1L;
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:
Obtain regression equation: A=0.00476C (μ molL according to the calibration curve of step 1-1)+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 add in the solution that contains hydroxyl radical free radical to 1mL0.002g～0.02g dimethyl sulfoxide (DMSO), obtains the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL molar concentration is 2mmolL-1Heavily fortified pointThe blue BB salting liquid in jail, reacts 10min under room temperature, obtains the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO4, re-use 3mL toluene/butanols mixed extractant pairContain diazonium sulfone product mixed solution and extract, extraction time is 5min, removes subnatant, obtains upper strata liquid; UseButanol/water saturated solution cleans upper strata liquid 1 time～2 times, more centrifugal under the condition that is 500r/min～1000r/min at rotating speed2min～3min, then remove the subnatant after centrifugal, obtains the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyrrolePyridine, then use 1cm cuvette, butanols reagent blank is made reference, measures the absorbance of solution, according to step at 425nm placeHydroxy free radical concentration in regression equation calculation solution in two;
The FeSO of step 3 described in 3.4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be(200mmol～500mmol):1L；
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 capturing agent that present embodiment is used is DMSO, and this capturing agent is that the OH that a kind of performance is extremely given prominence to catchesAgent, is applicable to various liquid environments, and price is extremely low, and capture effect is good; Hydroxyl radical free radical in one-time detection solution of the present inventionThe capturing agent of concentration and the expense of other chemicals less than 2 yuans, be only DMPO capturing agent expense very muchOne of;
Two, the detecting instrument that present embodiment is used is only ultraviolet-uisible spectrophotometer, and technical device maturation is cheap;
Three, present embodiment first passage adds FeSO4Successfully suppress the extraction of extractant to fast blue BB salt, greatlyWeaken the impact of fast blue BB salt on testing result, improve accuracy of detection, detect error in 5%, and experiment can weighRenaturation is 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 alkaline system is moltenLiquid is all suitable for;
Five, the applicable OH concentration range of present embodiment relates to method of operating is large, and the best OH concentration of detection is25μmol·L-1～250μmol·L-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 H2O2System, organismIn, bleach system, organic wastewater system etc. are all suitable for.
Present embodiment can obtain a kind of method that detects hydroxy free radical concentration in solution.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: the FeSO described in step 14Amount of substance with being numbered 1. to the volume ratio of the mixed solution that contains diazonium sulfone product be 6.(250mmol～450mmol): 1L. Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two difference is: step 3 is got in 1. and containedThere is the solution 1mL of hydroxyl radical free radical, then add 0.002g～0.01g dimethyl in the solution that contains hydroxyl radical free radical to 1mLSulfoxide, obtains the solution containing methyl sulfinic acid. Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three difference is: step 3 is got in 1. and containedThere is the solution 1mL of hydroxyl radical free radical, then add 0.005g～0.02g dimethyl in the solution that contains hydroxyl radical free radical to 1mLSulfoxide, obtains the solution containing methyl sulfinic acid. Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four difference is: step 3 is got in 1. and containedThere is the solution 1mL of hydroxyl radical free radical, then add 0.01g～0.02g dimethyl in the solution that contains hydroxyl radical free radical to 1mLSulfoxide, obtains the solution containing methyl sulfinic acid. Other steps are identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five difference is: step 3 will contain in 2.The solution of methyl sulfinic acid is placed in dark place, and adding 1.25mL～2.5mL molar concentration is 2mmolL-1Fast blue BB saltSolution, reacts 10min under room temperature, obtains the mixed solution that contains diazonium sulfone product. Other steps and detailed description of the invention oneTo five identical.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six difference is: step 3 will contain in 2.The solution of methyl sulfinic acid is placed in dark place, and adding 5mL～10mL 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 and detailed description of the invention one to six phaseWith.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven difference is: step 3 will contain in 2.The solution of methyl sulfinic acid is placed in dark place, and adding 10mL～12.5mL molar concentration is 2mmolL-1Fast blue BB saltSolution, reacts 10min under room temperature, obtains the mixed solution that contains diazonium sulfone product. Other steps and detailed description of the invention oneTo seven identical.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight difference is: step 3 3. described inFeSO4Amount of substance be (300mmol～500mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine difference is: step 3 3. described inFeSO4Amount of substance be (200mmol～400mmol): 1L with the volume ratio of the mixed solution that contains diazonium sulfone product.Other steps are identical with detailed description of the invention one to nine.
Below in conjunction with embodiment, the present invention is further set forth:
Embodiment mono-:
One, the drafting of calibration curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6.,Wherein 1. number adding molar concentration is 25 μ molL-1Methyl sulfinic acid sodium solution 1mL, 2. number add molar concentration to be50μmol·L-1Methyl sulfinic acid sodium solution 1mL, 3. number adding molar concentration is 75 μ molL-1Methyl sulfinic acid sodium moltenLiquid 1mL, 4. number adding molar concentration is 100 μ molL-1Methyl sulfinic acid sodium solution 1mL, 5. number add molar concentrationBe 150 μ molL-1Methyl sulfinic acid sodium solution 1mL; 6. number adding molar concentration is 150 μ molL-1Methyl sulfinic acidSodium solution 1mL; Then be placed in dark place by being numbered 1. to container 6., add in container 6. to being numbered 1. respectivelyMolar concentration is 2mmolL-1Fast blue BB salt, wherein 1. number add 1.25mL; 3. number 2. number add 2.50mL,Add 3.75mL, 4. number add 5.00mL, 5. number add 7.50mL; 6. number add 12.5mL; At room temperature reaction again1. 10min, obtain being numbered the mixed solution that contains diazonium sulfone product 6.; Again respectively to being numbered 1. containing 6.In the mixed solution of diazonium sulfone product, add FeSO4And 3mL toluene/butanols extractant, extraction 5min, removes subnatant,Obtain being numbered the 3mL upper layer of extraction liquid 1. arriving 6.; Add in 3mL upper layer of extraction liquid 6. to being numbered 1. respectively again1mL pyridine, obtains being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, surveysDetermine 425nm place and be numbered the absorbance that 1. arrives extract to be measured 6.; Taking absorbance as ordinate, with methyl sulfinic acid sodiumConcentration is abscissa, drawing standard curve;
FeSO described in step 14Amount of substance be numbered 1. the mixed solution that contains diazonium sulfone product 6.Volume ratio is 300mmol:1L;
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:
Obtain regression equation: A=0.00476C (μ molL according to the calibration curve of step 1-1)+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 FeSO4Molar concentration be respectively 50mmolL-1And 1mmolL-1Solution 80mL; To80mLDMSO and FeSO4Molar concentration be respectively 50mmolL-1And 1mmolL-1Solution in add H2O2WithThe molar concentration of DMSO is respectively 250 μ molL-1And 50mmolL-1Solution 20mL, obtain hydroxy free radical concentrationBe 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, add 2.5mL molar concentration to be2mmol·L-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 FeSO4, re-use 3mL toluene/butanols mixed extractant pairContain diazonium sulfone product mixed solution and extract, extraction time is 5min, removes subnatant, obtains upper strata liquid; UseButanol/water saturated solution cleans upper strata liquid 2 times, more centrifugal 2min under the condition that is 800r/min at rotating speed, then remove fromSubnatant after the heart, obtains 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 regression equation calculation solution in step 2 at 425nm placeMiddle hydroxy free radical concentration;
The FeSO of step 3 described in 3.4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be300mmol:1L；
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.
Be 48.1 μ molL according to hydroxy free radical concentration in regression equation calculation embodiment mono-solution in step 2-1, with the hydroxyl of configurationBase number of free radical is 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 calibration curve of absorbance; According to Fig. 1 calibration curveObtain regression equation: A=0.00476C (μ molL-1)+0.01271 (r=0.99951); Wherein A is absorbance; C is methylSulfinic 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 in a kind of detection solution, hydroxyl radical free radical is denseThe method of degree specifically completes according to the following steps:
One, the drafting of calibration curve: methyl sulfinic acid sodium solution is joined respectively and is numbered 1. in six containers 6.,Wherein 1. number adding molar concentration is 25 μ molL-1Methyl sulfinic acid sodium solution 1mL, 2. number add molar concentration to be50μmol·L-1Methyl sulfinic acid sodium solution 1mL, 3. number adding molar concentration is 75 μ molL-1Methyl sulfinic acid sodium moltenLiquid 1mL, 4. number adding molar concentration is 100 μ molL-1Methyl sulfinic acid sodium solution 1mL, 5. number add molar concentration to be150μmol·L-1Methyl sulfinic acid sodium solution 1mL; 6. number adding molar concentration is 250 μ molL-1Methyl sulfinic acid sodiumSolution 1mL; Then be placed in dark place by being numbered 1. to container 6., in container 6., add mole to being numbered 1. respectivelyConcentration is 2mmolL-1Fast blue BB salt, wherein 1. number add 1.25mL; 2. number add 2.50mL, 3. number add3.75mL, 4. number adds 5.00mL, 5. number adds 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.; Produce to the diazonium sulfone that contains 6. to being numbered 1. respectively againIn the mixed solution of thing, add FeSO4And 3mL toluene/butanols mixed extractant, extraction 5min, removes subnatant, obtainsBe numbered the 3mL upper layer of extraction liquid 1. arriving 6.; In 3mL upper layer of extraction liquid 6., add 1mL to being numbered 1. respectively againPyridine, obtains being numbered the extract to be measured 1. arriving 6.; Use 1cm cuvette, butanols reagent blank is made reference, measures 425nmPlace is numbered the absorbance that 1. arrives extract to be measured 6.; Taking absorbance as ordinate, taking methyl sulfinic acid na concn as horizontal seatMark, drawing standard curve;
FeSO described in step 14Amount of substance be numbered the 1. body to the mixed solution that contains diazonium sulfone product 6.Long-pending than being (200mmol～500mmol): 1L;
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:
Obtain regression equation: A=0.00476C+0.01271, r=0.99951 according to the calibration curve of step 1; Wherein A is for inhalingLuminosity; C is methyl sulfinic acid na concn, and unit is μ molL-1；
Three, the mensuration of hydroxyl radical free radical in solution:
1. get the solution 1mL that contains hydroxyl radical free radical, then add in the solution that contains hydroxyl radical free radical to 1mL0.002g～0.02g dimethyl sulfoxide (DMSO), obtains the solution containing methyl sulfinic acid;
2. the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～12.5mL molar concentration is 2mmolL-1Heavily fortified pointThe blue BB salting liquid in jail, reacts 10min under room temperature, obtains the mixed solution that contains diazonium sulfone product;
3. in the mixed solution that contains diazonium sulfone product, add FeSO4, re-use 3mL toluene/butanols mixed extractant to containingHave the mixed solution of diazonium sulfone product to extract, extraction time is 5min, removes subnatant, obtains upper strata liquid; Use fourthAlcohol/water saturation solution cleans upper strata liquid 1 time～2 times, more centrifugal under the condition that is 500r/min～1000r/min at rotating speed2min～3min, then remove the subnatant after centrifugal, obtains the upper strata liquid after centrifugal; In the upper strata liquid after centrifugal, add pyridine,Use 1cm cuvette, butanols reagent blank is made reference again, measures the absorbance of solution at 425nm place, according to returning in step 2Return equation to calculate hydroxy free radical concentration in solution;
The FeSO of step 3 described in 3.4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be(200mmol～500mmol):1L；
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 step 1Described in FeSO4Amount of substance with being numbered 1. to the volume ratio of the mixed solution that contains diazonium sulfone product be 6.(250mmol～450mmol):1L。
3. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that step 31. in, get the solution 1mL that contains hydroxyl radical free radical, then add 0.002g～0.01g in the solution that contains hydroxyl radical free radical to 1mLDimethyl sulfoxide (DMSO), obtains the solution containing methyl sulfinic acid.
4. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that step 31. in, get the solution 1mL that contains hydroxyl radical free radical, then add 0.005g～0.02g in the solution that contains hydroxyl radical free radical to 1mLDimethyl sulfoxide (DMSO), obtains the solution containing methyl sulfinic acid.
5. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that step 31. in, get the solution 1mL that contains hydroxyl radical free radical, then add 0.01g～0.02g in the solution that contains hydroxyl radical free radical to 1mLDimethyl sulfoxide (DMSO), obtains 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 step 32. in, the solution containing methyl sulfinic acid is placed in to dark place, adding 1.25mL～2.5mL molar concentration is 2mmolL-1Fast blueBB salting liquid, reacts 10min under room temperature, obtains 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 step 32. in, the solution containing methyl sulfinic acid is placed in to dark place, adding 5mL～10mL molar concentration is 2mmolL-1Fast blue BBSalting liquid, reacts 10min under room temperature, obtains 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 step 32. in, the solution containing methyl sulfinic acid is placed in to dark place, adding 10mL～12.5mL molar concentration is 2mmolL-1Fast blueBB salting liquid, reacts 10min under room temperature, obtains 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 step 33. the FeSO described in4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be (300mmol～500mmol):1L。
10. a kind of method that detects hydroxy free radical concentration in solution according to claim 1, is characterized in that stepThree FeSO described in 3.4Amount of substance with the volume ratio of the mixed solution that contains diazonium sulfone product be(200mmol～400mmol):1L。
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| 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 |
| CN109060694B (en) * | 2018-10-15 | 2021-01-22 | 广州中医药大学(广州中医药研究院) | Colorimetric detection method for hydroxyl free radicals and application thereof |
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