CN101975756A - Method for quickly detecting hypermanganate index in water by molecular absorption spectrometry - Google Patents
Method for quickly detecting hypermanganate index in water by molecular absorption spectrometry Download PDFInfo
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- CN101975756A CN101975756A CN 201010510809 CN201010510809A CN101975756A CN 101975756 A CN101975756 A CN 101975756A CN 201010510809 CN201010510809 CN 201010510809 CN 201010510809 A CN201010510809 A CN 201010510809A CN 101975756 A CN101975756 A CN 101975756A
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- citric acid
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- 238000000034 method Methods 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004847 absorption spectroscopy Methods 0.000 title abstract description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000012159 carrier gas Substances 0.000 claims abstract description 9
- 230000031700 light absorption Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001228 spectrum Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 16
- 238000001514 detection method Methods 0.000 abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- QJWQYOHBMUQHGZ-UHFFFAOYSA-N ethanol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound CCO.OC(=O)CC(O)(C(O)=O)CC(O)=O QJWQYOHBMUQHGZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000004445 quantitative analysis Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000004401 flow injection analysis Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for quickly detecting hypermanganate index in water by molecular absorption spectrometry. The method comprises the following steps: selecting a color comparison tube to extract a water sample, adding proper sulfuric acid to ensure the water sample is of acidity; adding 0.01 to 0.2umol/L of hypermanganate solution, and heating for 30 minutes in a heat reactor at 100 DEG C; cooling, reducing the residual hypermanganate with nitrite, and adding excessive nitrite to react 3 to 5 minutes; putting 1ml of the reaction solution after constant volume in a 25ml color comparison tube; adding citric acid-ethanol solution, and converting the nitrite into nitrogen dioxide instantly; and carrying gas-phase molecules to an absorption tube by carrier gas, and detecting the light absorption value at the position of 213.9 nano-wavelength. The invention establishes a quick quantitative analysis method for the hypermanganate index in the water by an indirect nitrite detection mode, has the characteristics of quick detection, high accuracy, less turbidity influence, little reagent and safety and environmental protection, and can be widely applied to emergency, online detection, flowing injection, lab information management and the like.
Description
Technical field
The present invention relates to a kind of method to the water body quality testing, particularly a kind of indirect type is measured the method for water quality permanganate index, the method for permanganate index in specifically a kind of molecular spectrum absorption process fast measuring water.
Background technology
Permanganate index is that surface water body is subjected to organic contaminant or reducing inorganic pollutant, and the overall target of pollution level is meant in acid or alkaline medium the oxygen that is consumed when being the oxidizer treatment water sample with the permanganate, represents with the mg/l of oxygen.Reduce with sodium oxalate after generally adopting water sample by permanganate oxidation, measure with the method for the unnecessary sodium oxalate of permanganate titration again, method with the permanganate determination of residual amount behind reduction reaction and the heated oxide detects permanganate index in the water, adopt this method not only to need to prepare the sodium oxalate standard solution, and timing signal need two people eight parallel, time-consuming, during titration permanganate treating fluid parallel again twice, bother very much complex operation, reducing condition harshness.Therefore be difficult to adapt to heavy day by day water quality monitoring requirements of one's work.At present, along with the development of detection technique, existing multiple detection method and means, its operation is easier, and the efficient height, and speed helps testing process robotization and laboratory information management soon.But facts have proved adopt different reductive agents can influence the precision of detection, how its relative deviation difference could be effective fast, permanganate index is a technical matters to be solved by this invention in the high-quality mensuration water.
Summary of the invention
Technical matters to be solved by this invention is at above-mentioned prior art present situation, the method of permanganate index in a kind of molecular spectrum absorption process fast measuring water is provided, it can be by the mensuration to unnecessary reductive agent under the condition of normal temperature, realize rapidly and efficiently, the accurate detection, and it is few to have the turbidity influence, characteristics such as agents useful for same safety and environmental protection are particularly suitable for meeting an urgent need, the exploitation and the use of the instrument in on-line monitoring, flow injection field.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water, this method comprises that at first choosing color comparison tube extracts water sample, and add after an amount of sulfuric acid makes it be acidity, add the permanganate solution of 0.01umol/L to 0.2umol/L again and in the reactor heating of 100 degree, heat certain hour, taking-up is behind natural cooling, clear up remaining permanganate then with nitrite as reductive agent reduction and add excessive, reacted 3 to 5 minutes, behind the constant volume, the 1ml reactant liquor of taking-up behind constant volume is positioned in the 25ml color comparison tube, once more behind the constant volume, add citric acid-ethanolic solution again, in the medium of citric acid, be catalyzer with ethanol, nitrite moment is converted into nitrogen dioxide, and is written into gas molecule in space to absorbing in the light pipe, measure light absorption value at 213.9 nano wave length places with carrier gas.
The further technical measures of being taked also comprise:
Above-mentioned mensuration light absorption value adopts molecular absorption spectrometer to detect.
The above-mentioned color comparison tube of choosing is the 10ml color comparison tube, and extracts water sample 5ml, adds 3ml sulfuric acid 1+3 and 0.5ml potassium permanganate 1/5KMnO4=0.01mol/l, and heating is 30 minutes in 100 degree DG200 reactor heatings, and the cooling back adds 100mg/l nitrite 0.7ml.
Citric acid-the ethanolic solution of above-mentioned adding is C=0.5mol/L citric acid+10% ethanol.
It is pure that above-mentioned potassium permanganate, sulfuric acid, citric acid-ethanolic solution, nitrite are analysis.
Above-mentioned carrier gas nitrogen input pressure is 0.2MP, and the zinc hollow cathode lamp current of described molecular absorption spectrometer is 2.5Ma, and measuring peak height integral time is 2.0min.
Compared with prior art, the present invention as reductive agent, by the mode of indirect determination nitrite, has set up the quick quantitative analytic method of the permanganate index in the water with nitrite.After permanganate in the water sample adds sulfuric acid oxidation, reduce, measure nitrite, indirect determination permanganate index with molecular spectrum absorption process method again with nitrite.The result shows that the scope that detects of method is 0～9mg/l, detection limit 0.27mg/l, and average recovery rate 96.9～102.5%, relative standard deviation 3.1～5.2% is not higher than 10%.This method can be carried out unnecessary nitrite and be measured under the condition of normal temperature, have and measure fast, the accuracy height, the turbidity influence is few, advantages such as the few and safety and environmental protection of agents useful for same amount are particularly suitable for meeting an urgent need, the exploitation and the use of the instrument in on-line monitoring, flow injection field.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
The method of permanganate index in a kind of molecular spectrum absorption process fast measuring water of the present invention, this method comprises that at first choosing color comparison tube extracts water sample, and add after an amount of sulfuric acid makes it be acidity, add the permanganate solution of 0.01umol/L to 0.2umol/L again and in the reactor heating of 100 degree, heat certain hour, taking-up is behind natural cooling, clear up remaining permanganate then with nitrite as reductive agent reduction and add excessive, reacted 3 to 5 minutes, behind the constant volume, the 1ml reactant liquor of taking-up behind constant volume is positioned in the 25ml color comparison tube, once more behind the constant volume, adding citric acid-ethanolic solution again, is catalyzer with ethanol in the medium of citric acid, and nitrite moment is converted into nitrogen dioxide, and be written into gas molecule in space to absorbing in the light pipe with carrier gas, measure light absorption value at 213.9 nano wave length places.
For obtaining better technique effect, improve accuracy of detection, the present invention also comprises:
Above-mentioned mensuration light absorption value adopts molecular absorption spectrometer to detect.
The above-mentioned color comparison tube of choosing is the 10ml color comparison tube, and extraction water sample 5ml, add 3ml sulfuric acid 1+3 and 0.5ml potassium permanganate 1/5KMnO4=0.01mol/l, heating is 30 minutes in 100 degree DG200 reactor heatings, and the cooling back adds 100mg/l nitrite 0.7ml.
Above-mentioned adding citric acid-ethanolic solution is C=0.5mol/L citric acid+10% ethanol.
It is pure that above-mentioned potassium permanganate, sulfuric acid, citric acid-ethanolic solution, nitrite are analysis.
Above-mentioned carrier gas nitrogen input pressure is 0.2MP, and the zinc hollow cathode lamp current of described molecular absorption spectrometer is 2.5Ma, and measuring peak height integral time is 2.0min.
The present invention adopts molecular absorption spectrometer to detect and the heating of DG200 reactor heating, and be reductive agent with the sodium nitrite, can detect at normal temperatures, result of study shows, it is good that this method has fast and convenient, highly sensitive precision, advantages such as the reagent sample size is few, and cost is low, and the turbidity influence is few, and environmental protection, non-secondary pollution helps realizing testing process robotization and laboratory information management, is particularly suitable for meeting an urgent need, the exploitation and the use of the instrument in on-line monitoring, flow injection field.This method can obtain promising result through test of many times.Its principle, parameter and result are as follows:
1, detects principle
After water sample adding sulfuric acid is acidity, add the permanganate solution of 0.01umol/L to 0.2umol/L and heat certain hours at 100 degree boiling water baths, remaining permanganate with sodium nitrite reduction and add excessive, add citric acid-ethanolic solution again, in the medium of citric acid, adding ethanol is catalyzer, and nitrite moment is converted into NO2, be written into gas molecule in space with carrier gas and absorb in the light pipe, measure light absorption value at 213.9 nano wave length places.
2, experimental section
2.1 instrument and reagent:
Molecular absorption spectrometer adopts the abundant company in north, Shanghai product, and the DG200 reactor heating is a Hash company product.Reagent is potassium permanganate 1/5KMnO4=0.01mol/l, 1+3 sulfuric acid, citric acid-ethanolic solution, and it is pure that C=0.5mol/L citric acid+10% ethanol, 100mg/l nitrite, above reagent are analysis.
2.2 test method:
Get the 10ml color comparison tube, draw samples 5ml, add 0.5ml potassium permanganate, 3ml sulfuric acid 1+3 was in 100 degree DG200 reactor heating heating 30 minutes, the cooling back adds 100mg/l sodium nitrite 0.7ml, reacted 3-5 minute, getting the 1ml reactant liquor is settled in the 25ml color comparison tube, add citric acid-ethanolic solution again, C=0.5mol/L citric acid+10% ethanol is a catalyzer with ethanol in the medium of citric acid, and nitrite moment is converted into nitrogen dioxide, and be written into gas molecule in space to absorbing in the light pipe with carrier gas, measure light absorption value at 213.9 nano wave length places.
2.3 the influence of type of heating:
Is that the standard solution of 4.2mg/L heats with water-bath and DG200 reactor heating to concentration, and replication shows that two kinds of type of heating do not have obvious influence to test result for 3 times, can the phase trans-substitution.
2.4 condition of work:
Zinc hollow cathode lamp current: 2.5Ma; Operation wavelength 213.9nm; Nitrogen input pressure is 0.2MP; Measuring method: peak height; Integral time 2.0min
3, result and discussion
3.1 the selection of reductive agent:
Nitrite is few for the inorganic reaction intermediate product with the permanganate reaction.Molecular absorption spectrometry is applicable to the mensuration of all kinds of water such as seawater surface water industrial sewage, and the scope that detects is big by 1.
3.2 the selection of acidity:
Clear up finish after, press the chemical equation EQUILIBRIUM CALCULATION FOR PROCESS, add to wait mole nitrite NO2-N100mg/l reduction.Through test, can directly advance molecular absorption spectrometer after clearing up and detect, peracidity does not have obviously influence to measuring.
3.3 the elimination of disturbing:
Because it is oxidized that water sample is cleared up in the water sample of back reducing substances such as original sulphite, do not influence mensuration; Permanganates etc. are by reduction such as nitrite, and concentration is hanged down and also do not influenced mensuration.
3.4 the making of working curve:
Get and newly join 9.60mg/l permanganate standard solution 0.0,0.5,1.0,1.5 ... 5.0, respectively by the experimental procedure operation, measure absorbance and production standard curve, typical curve is Y=0.0364x+5E-5, the range of linearity of permanganate index is 0.0～9mg/L, related coefficient is 0.999, detects to be limited to 0.27mg/L.
3.5 the detection of sample and the recovery and precision:
Get each 2 in variable concentrations standard solution and sample, detect, try to achieve permanganate index, the results are shown in following table with calibration curve method by experimental technique:
The mensuration of permanganate index
| Sample | Average mg/L * | Add scalar | Measured value | Recovery of standard addition % | Repetition rate % |
| Standard 1 (203138) | 7.44 | 3.72 | 11.12 | 98.9 | 3.1 |
| Standard 2 (203137) | 2.38 | 2.38 | 4.82 | 102.5 | 4.7 |
| Sample 1 | 8.21 | 5.21 | 13.26 | 96.9 | 5.2 |
| Sample 2 | 2.15 | 4.22 | 6.38 | 100.2 | 3.4 |
More than all replicate determinations 5 times.
3.6 the comparison of different analytical approachs:
Through check, this law and GB monitoring result do not have obvious difference.
4, conclusion:
Adopt the DG200 reactor heating to clear up, after the nitrite reduction, directly carry out method for measuring with the molecule absorption atomic absorption spectrography (AAS).The result shows that the scope that detects of method is 0～9mg/l, detection limit 0.27mg/l, and average recovery rate 96.9～102.5%, relative standard deviation 3.1～5.2% is not higher than 10%.This method has to be measured fast, the accuracy height, and the turbidity influence is few, and the characteristics of agents useful for same safety and environmental protection are particularly suitable for meeting an urgent need, the exploitation and the use of the instrument in on-line monitoring, flow injection field.
Most preferred embodiment of the present invention is illustrated, and various variations or the remodeling made by those of ordinary skills can not depart from the scope of the present invention.
Claims (6)
1. the method for permanganate index in the molecular spectrum absorption process fast measuring water, it is characterized in that: this method comprises that at first choosing color comparison tube extracts water sample, and add after an amount of sulfuric acid makes it be acidity, add the permanganate solution of 0.01umol/L to 0.2umol/L again and in the reactor heating of 100 degree, heat certain hour, taking-up is behind natural cooling, clear up remaining permanganate then with nitrite as reductive agent reduction and add excessive, reacted 3 to 5 minutes, behind the constant volume, the 1ml reactant liquor of taking-up behind constant volume is positioned in the 25ml color comparison tube, once more behind the constant volume, adding citric acid-ethanolic solution again, is catalyzer with ethanol in the medium of citric acid, and nitrite moment is converted into nitrogen dioxide, and be written into gas molecule in space to absorbing in the light pipe with carrier gas, measure light absorption value at 213.9 nano wave length places.
2. the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water according to claim 1 is characterized in that: described mensuration light absorption value adopts molecular absorption spectrometer to detect.
3. the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water according to claim 2, it is characterized in that: the described color comparison tube of choosing is the 10ml color comparison tube, and extraction water sample 5ml, add 3ml sulfuric acid 1+3 and 0.5ml potassium permanganate 1/5KMnO4=0.01mol/l, heating is 30 minutes in 100 degree DG200 reactor heatings, and the cooling back adds 100mg/l nitrite 0.7ml.
4. the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water according to claim 3, it is characterized in that: described adding citric acid-ethanolic solution is C=0.5mol/L citric acid+10% ethanol.
5. the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water according to claim 4 is characterized in that: it is pure that described potassium permanganate, sulfuric acid, citric acid-ethanolic solution, nitrite are analysis.
6. the method for permanganate index in a kind of molecular spectrum absorption process fast measuring water according to claim 5, it is characterized in that: described carrier gas nitrogen input pressure is 0.2MP, the zinc hollow cathode lamp current of described molecular absorption spectrometer is 2.5Ma, and measuring peak height integral time is 2.0min.
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Cited By (9)
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| CN102313707A (en) * | 2011-08-03 | 2012-01-11 | 中粮生物化学（安徽）股份有限公司 | Method for determining silicon dioxide content in substances containing citric acid |
| CN102692412A (en) * | 2012-06-11 | 2012-09-26 | 宁波市环境监测中心 | Fast detection reagent kit of anionic surfactants and detection method by using fast detection reagent kit |
| CN103528975A (en) * | 2013-09-30 | 2014-01-22 | 中粮生物化学（安徽）股份有限公司 | Determination method for readily carbonizable substances in calcium salt of citric acid and applications |
| CN104792780A (en) * | 2015-04-27 | 2015-07-22 | 北京连华永兴科技发展有限公司 | Method for measuring permanganate index with phenanthroline-ferrous ion color development method and application |
| CN104792714A (en) * | 2015-04-27 | 2015-07-22 | 北京连华永兴科技发展有限公司 | Measurement method for permanganate index and application |
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| CN107132226A (en) * | 2017-06-29 | 2017-09-05 | 沈忠伟 | A kind of citric acid Quality identification method |
| CN107727586A (en) * | 2017-09-11 | 2018-02-23 | 华侨大学 | A kind of method that permanganate indices in water is determined with DPD |
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Cited By (13)
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| CN102313707A (en) * | 2011-08-03 | 2012-01-11 | 中粮生物化学（安徽）股份有限公司 | Method for determining silicon dioxide content in substances containing citric acid |
| CN102692412B (en) * | 2012-06-11 | 2014-04-16 | 宁波市环境监测中心 | Fast detection reagent kit of anionic surfactants and detection method by using fast detection reagent kit |
| CN102692412A (en) * | 2012-06-11 | 2012-09-26 | 宁波市环境监测中心 | Fast detection reagent kit of anionic surfactants and detection method by using fast detection reagent kit |
| CN103528975B (en) * | 2013-09-30 | 2016-01-13 | 中粮生物化学（安徽）股份有限公司 | The assay method of readily carbonizable substance and application thereof in a kind of calcium citrate salts |
| CN103528975A (en) * | 2013-09-30 | 2014-01-22 | 中粮生物化学（安徽）股份有限公司 | Determination method for readily carbonizable substances in calcium salt of citric acid and applications |
| CN104614370B (en) * | 2015-01-20 | 2017-08-04 | 河南工程学院 | A kind of method of the quick detection nitrite anions based on nanogold |
| CN104792780A (en) * | 2015-04-27 | 2015-07-22 | 北京连华永兴科技发展有限公司 | Method for measuring permanganate index with phenanthroline-ferrous ion color development method and application |
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| CN104792714B (en) * | 2015-04-27 | 2017-10-13 | 北京连华永兴科技发展有限公司 | The assay method of permanganate index and application |
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| CN107202860A (en) * | 2017-06-29 | 2017-09-26 | 沈忠伟 | A kind of citric acid Quality identification method |
| CN107727586A (en) * | 2017-09-11 | 2018-02-23 | 华侨大学 | A kind of method that permanganate indices in water is determined with DPD |
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