CN102565262B - Determination method for hydrogen sulfide in mainstream smoke of cigarette - Google Patents
Determination method for hydrogen sulfide in mainstream smoke of cigarette Download PDFInfo
- Publication number
- CN102565262B CN102565262B CN201110437482.3A CN201110437482A CN102565262B CN 102565262 B CN102565262 B CN 102565262B CN 201110437482 A CN201110437482 A CN 201110437482A CN 102565262 B CN102565262 B CN 102565262B
- Authority
- CN
- China
- Prior art keywords
- cigarette
- methylene blue
- solution
- ultraviolet
- concentration
- 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.)
- Active
Links
Images
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to a determination method for hydrogen sulfide in mainstream smoke of a cigarette, in particular to a high efficiency liquid chromatogram determination method for the hydrogen sulfide in the smoke of the cigarette aiming at solving the problems of complete capture and impurity interference of the hydrogen sulfide in the mainstream smoke of the cigarette at present. The determination method comprises utilizing alkaline solution containing zinc irons to adsorb the hydrogen sulfide in gas phase of the captured smoke, after the hydrogen sulfide is developed through N, N-dimethyl-p-phenylenediamine dihydrochloride and ferric ammonium sulfate, a high efficiency liquid chromatograph provided with an ultraviolet-visible light multi-wavelength detector or an ultraviolet-visible light diode array detector is utilized to perform nature and quantifying determination on methylene blue serving as a standard substance. Compared with a traditional method, the determination method for the hydrogen sulfide in the mainstream smoke of the cigarette has the advantages of being simple to operate, strong in safety and interference resistance, high in accuracy and the like.
Description
Technical field
The present invention relates to the assay method of sulfuretted hydrogen in a kind of cigarette smoke, relate to specifically the high-performance liquid chromatogram determination method of sulfuretted hydrogen in a kind of cigarette smoke.
Background technology
In tobacco, be rich in protein and amino acids, comprising containing prot th and sulfur-containing amino acid.Under the condition of suction burning, these sulfurous organic compounds can cracking generate multiple sulfide, and wherein sulfuretted hydrogen is of paramount importance a kind of.
Sulfuretted hydrogen is the most a kind of in sulphur-II oxidized compound, is strong neurotoxin, and mucous membrane is had to intense stimulus effect.Acute toxicity (LC506): 18mg/m
3(rat suction); Subacute and chronic toxicity: rabbit sucks 0.01mg/L, 2 hours/day, 3 months, cause that the function of central nervous system changes, tracheae, tunica mucosa bronchiorum irritation, there is pathological change in cerebral cortex.Mouse Long Term Contact low concentration hydrogen sulphide, has small airway infringement.Therefore, a kind of reliably, hydrogen sulfide in mainstream smoke of cigarette assay method is significant for hydrogen sulfide content and corresponding harm reduction technological development in monitoring cigarette smoke accurately.
In the fields such as environmental water quality monitoring, the method that detects sulfuretted hydrogen mostly is methylene-blue colorimetric method, also has bibliographical information to cross fluorescence detection at present.The former is easily disturbed (referring to the high-efficient liquid phase chromatogram impurity peaks of accompanying drawing 3), and the required derivative reagent of the latter is also difficult to obtain at present.The possibility that these methods are applied to the detection of sulfureous in flue gas hydrogen is less, and its Major Difficulties is the trapping of sulfureous in flue gas hydrogen, and effectively derives the sample detecting for can be used for high efficiency liquid phase after trapping.How fully to trap, derive the sulfuretted hydrogen in flue gas and give Accurate Determining, become problem demanding prompt solution in current detection.
Summary of the invention
The present invention is directed to the problems such as the trapping of current hydrogen sulfide in mainstream smoke of cigarette, derivative and Accurate Determining, a kind of assay method of hydrogen sulfide in mainstream smoke of cigarette is provided.Described assay method is the sulfuretted hydrogen in the alkaline solution trapping flue gas gas phase that contains zinc ion, and pass through N, N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate develop the color to the absorbent solution that contains sulfuretted hydrogen is derivative under acid condition, utilize afterwards the high performance liquid chromatograph be furnished with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector to detect, and take methylene blue and carry out method qualitative, quantitative measurement as standard items.In order fully to trap the sulfuretted hydrogen in flue gas, the zinc ion in absorption liquid should be more than 100:1 with the molar equivalent ratio of sulfureous in flue gas hydrogen.Utilize N, N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate develop the color to it under acid condition, and reaction principle is under the redox of ferric ion, sulfuretted hydrogen and use N, and N-dimethyl-p-phenylenediamine dihydrochloride equivalent generates methylene blue.For avoiding impurity to disturb, separated with reversed-phase high-performance liquid chromatography.With ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector, under 665nm, detect, by contrasting with the liquid chromatogram of methylene blue standard items, according to retention time, come whether to have sulfuretted hydrogen in qualitative sample; Utilize external standard method, by typical curve, the concentration of quantitative liquid Methylene Blue to be detected conversion obtain the content of hydrogen sulfide in mainstream smoke of cigarette.In trapping process, absorption liquid can be put into trapping bottle disclosed by the invention, absorb trapping.Certainly, testing staff also can adopt conventional drip catcher in current flue gas mensuration, traps.
As specific embodiment of the invention step, the present invention discloses respectively qualitative checking method and the quantitative detecting method of sulfuretted hydrogen.
The concrete steps of described qualitative determination method are:
(1) aspirate 4 ~ 10 cigarette, with the grain phase part of 44mm or 92mm glass fiber filter interception main flume, so that the trapping bottle of 50mL milliliter zinc acetate-sodium acetate absorbent solution to be housed, absorb the sulfuretted hydrogen in trapping flue gas gas phase part; After regulating suction capacity, on smoking machine, press GB/T 19609 standard conditions cigarette smoking cigarette samples, 2 mouthfuls of complete suctions afterwards;
(2) in absorption liquid, add successively derivative reagent N immediately, the sulfuric acid solution 1.0 mL ~ 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL ~ 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, make the sulphion complete reaction in absorption liquid be generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis;
The testing conditions of described efficient liquid phase chromatographic analysis is: fixing mutually for C18 analyzes chromatographic column, eluent is methyl alcohol aqueous formic acid (volume ratio is 45:1:55), and type of elution is isocratic elution; Flow velocity is 1.0mL/min.; Sample size is 10 μ L; Column temperature 35
0c; The detection wavelength of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector is 665nm;
(4) contrast with the retention time of methylene blue, in qualitative sample, whether sulfuretted hydrogen exists.
The concrete steps of described method for quantitatively determining are:
(1) aspirate 4 ~ 10 cigarette, with the grain phase part of 44mm or 92mm glass fiber filter interception main flume, so that the trapping bottle of 50mL milliliter zinc acetate-sodium acetate absorbent solution to be housed, absorb the sulfuretted hydrogen in trapping flue gas gas phase part; After regulating suction capacity, on smoking machine, press GB/T 19609 standard conditions cigarette smoking cigarette samples, 2 mouthfuls of complete suctions afterwards;
(2) in absorption liquid, add successively derivative reagent N immediately, the sulfuric acid solution 1.0 mL ~ 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL ~ 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion reaction in absorption liquid be generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis;
The testing conditions of described efficient liquid phase chromatographic analysis is: fixing mutually for C18 analyzes chromatographic column, eluent is methyl alcohol aqueous formic acid (volume ratio is 45:1:55); Sample size is 10 μ L; Flow velocity is 1.0mL/min.; Column temperature 35
0c; The detection wavelength of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector is 665nm;
(4) accurately prepare 0.2 μ g/mL ~ 5.0 μ g/mL, be no less than the methylene blue series standard solution of 5 concentration gradients;
(5), according to chromatographic condition step (3) Suo Shu, the methylene blue series standard solution of preparation in determination step (4), obtains the typical curve (R between peak area and methylene blue concentration respectively
2must not be less than 0.99).During working sample, by the peak area of analyte derivative material methylene blue, and using laboratory environment air and substitute flue gas and deduct sample as blank, obtain the concentration of methylene blue, and convert and obtain the content of sulfuretted hydrogen according to following formula:
X=（34.076×
f×C×V）
/（319.85
×n）
In formula:
xthe content of sulfuretted hydrogen in-cigarette sample main flume, unit is that μ g/ props up;
f-extension rate is 10 herein;
c-methylene blue concentration that detect through high performance liquid chromatography, that calculate on by typical curve, unit is μ g/mL;
v-constant volume, unit is mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight;
(6) result represents: using the mean value of twice mensuration as final measurement result, result is accurate to 0.01 μ g/ and props up.Relative deviation between replicate determination result must be in 10%.
As improvement of the present invention, in above-mentioned quantitative and qualitative analysis is measured, the concentration of described absorbent solution zinc acetate one sodium acetate is respectively (0.03mmol/mL ~ 0.09mmol/mL) (0.02mmol/mL ~ 0.06mmol/mL).Described derivative reagent N, the sulfuric acid solution of N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid concentration is 9.2 mmol/mL, N, N-dimethyl-p-phenylenediamine dihydrochloride concentration is 0.15mmol/m.The concentration of described ammonium ferric sulfate solution is 0.5mmol/mL.
In order to reduce the loss of sulfuretted hydrogen, guarantee the accuracy of detection, the invention also discloses its dead volume of flue gas stream of described serial connection trapping bottle in 10ml.
By disclosed technical scheme in the present invention, can from the main flume of cigarette, directly trap hydrogen sulfide gas, and by derivative, obtain methylene blue, thereby utilize ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector to carry out the detection of quantitative and qualitative analysis to it.This law is usingd methylene blue as standard substance, take the method that sodium sulphide is examination criteria and compares with traditional, does not need complicated calibration process, can realize fast and detecting.Meanwhile, do the method that reference material detects and compare with traditional with sulfuretted hydrogen, security improves.
Compare with current methylene-blue colorimetric method conventional in environment and water quality detection, its antijamming capability is stronger; Compare with fluorescence detection, owing to having saved the synthetic of standard fluorescence reagent, method is simply easy to popularize.
Accompanying drawing explanation
Fig. 1 is sulfuretted hydrogen trapping schematic diagram;
Fig. 2 is methylene blue HPLC chromatogram;
Fig. 3 is sample HPLC chromatogram;
Fig. 4 is methylene blue typical curve and area-concentration regression equation.
Embodiment
Take the 92.00g concentrated sulphuric acid (98%), slowly add in appropriate ultrapure water, jog concussion, is to be cooledly settled to 100mL during to room temperature, obtains the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes 3.137g is greater than 99% N, N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid solution with 9.2 mmol/mL dissolves and is settled in the brown volumetric flask of 100mL, obtains the N that concentration is 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride sulfuric acid solution.
Take 24.109g 12 ferric sulfate hydrate ammoniums, with ultrapure water, be settled to 100 mL, obtain the ammonium ferric sulfate solution that concentration is 0.5mmol/mL.
Take 0.330g Zinc diacetate dihydrate, 0.082g anhydrous sodium acetate adds in absorption bottle, measure again the ultrapure water (being cooled to room temperature after boiling) that adds 50mL, jog dissolves, and makes the concentration of zinc acetate, sodium acetate be respectively 0.03mmol/mL, 0.02mmol/mL.
Take 1.000 Zinc diacetate dihydrates, 0.246 anhydrous sodium acetate adds in absorption bottle, measure again the ultrapure water (being cooled to room temperature after boiling) that adds 50mL, jog dissolves, and makes the concentration of zinc acetate, sodium acetate be respectively 0.09 mmol/mL, 0.06mmol/mL.
Pipette methyl alcohol 450mL, ultrapure water 550mL to mobile phase bottle, add formic acid 10mL, mix, ultrasonic degas 5 minutes, obtains mobile phase.
Accurately take 0.00500g methylene blue standard substance, with appropriate ultrapure water, dissolve, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, obtain the methylene blue standard reserving solution of 50 μ g/mL.
By standard conditions (temperature 20
oc ± 2
oC, relative humidity 60% ± 5%) and the lower balance cigarette sample of 48 hours is pressed quality (mean value ± 50mg), resistance to suction (mean value ± 50pa) is screened, to obtain the testing sample of relative homogeneous;
By equipment operation and GB/T 19609 standard conditions requirements, preheating, debugging smoking machine are to stand-by state;
Serial connection is equipped with the filter disc clamper of 44mm or 92mm glass fiber filter, to tackle the granule phase substance of main flume; Serial connection is equipped with the trapping bottle (its dead volume of serial connection flue gas stream is in 10mL) of 50mL absorption liquid, regulates after suction capacity, starts, by 4 ~ 10 of standard method smoking cigarettes, to start to trap the sulfuretted hydrogen in main flume gas phase part; After trapping, 2 mouthfuls of suctions;
In absorption liquid, add successively derivative reagent N immediately, the sulfuric acid solution 1.0 mL ~ 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL ~ 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion reaction in absorption liquid be generated as methylene blue;
Derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis;
Take the efficient liquid phase chromatographic analysis test samples of being furnished with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: fixing is the conventional analysis chromatographic column of C18 mutually; Sample size is 10 μ L; Flow velocity is 1.0mL/min.; Column temperature 35
0c; Elution requirement is methyl alcohol, first aqueous acid (volume ratio is 45:1:55) isocratic elution; Detection wavelength is 665nm.
Obtain the HPLC chromatogram of sample as shown in Figure 3.
By 10 times of methylene blue standard reserving solution dilutions, according to above-mentioned HPLC assay method, sample introduction, detects, and obtains the HPLC chromatogram of standard items as shown in Figure 2, can see the retention time of the base peak of methylene blue.
Observe the sample peak retention time in Fig. 2, in the definite detected sample of comparison, contain methylene blue, thereby contain sulfuretted hydrogen in definite flue gas.
The drafting of typical curve
According to the method in embodiment 1, prepare respectively sample and each reagent.
The methylene blue standard reserving solution of 50 μ g/mL be take respectively to the methylene blue series standard working solution of ultrapure water dilution as 0.2 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 3.0 μ g/mL, 5.0 μ g/mL, according to above-mentioned HPLC detection method, obtain a series of peak areas of answering with relative concentration.Take peak area as ordinate, and the methylene blue that the concentration of take is μ g/mL is horizontal ordinate, linear regression drawing standard curve, obtaining peak area-concentration regression equation A=130.786836C+1.8552838(related coefficient is 0.99991).Typical curve and regression equation are as shown in Figure 4.
Quantitatively detect
Draw analyte sample fluid, according to the method in embodiment 1, obtain HPLC peak area, and utilize above-mentioned typical curve to obtain the methylene blue concentration in liquid to be measured by peak area, calculate according to the following formula the content of sulfuretted hydrogen in cigarette sample main flume.
X=（34.076×
f×
C×
V）
/（319.85×
n）
In formula:
xthe content of sulfuretted hydrogen in-cigarette sample main flume, unit is that μ g/ props up;
f-extension rate is 10 herein;
c-methylene blue concentration that detect through high performance liquid chromatography, that calculate on by typical curve, unit is μ g/mL;
v-constant volume, unit is mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
Using the mean value of twice mensuration as final measurement result, and result is accurate to 0.01 μ g/ and props up.Relative deviation between replicate determination result must be in 10%.
The methodology checking of assay method when embodiment 3 aspirates 4
Sample preparation, reagent preparation and analytical procedure are as implementation column 1 and 2.
Specification Curve of Increasing: become concentration to be about the methylene blue series standard working solution of 0.2 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 3.0 μ g/mL, 5.0 μ g/mL standard inventory solution dilution with ultrapure water, press immediately above-mentioned condition analysis drawing standard curve, R
2must not be less than 0.99;
The trapping of cigarette smoking and sulfuretted hydrogen in main flume: be connected in series the filter disc clamper of the glass fiber filter that 44mm is housed, to tackle the granule phase substance of main flume; Serial connection is equipped with the trapping bottle (its dead volume of serial connection flue gas stream is in 10mL) of 50mL absorption liquid, and in absorption liquid, the concentration of zinc acetate, sodium acetate is respectively 0.03mmol/mL, 0.02mmol/mL; Regulate after suction capacity, start by standard method, to aspirate 4 cigarette with preceding method, start to trap the sulfuretted hydrogen in main flume gas phase part simultaneously.
Trap complete after, in absorption liquid, add successively derivative reagent N immediately, aqueous sulfuric acid 1.0 mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL, airtight inversion jog 30 seconds, standing 5 minutes, make the sulphion reaction in absorption liquid be generated as methylene blue;
Precision is measured: take a certain cigarette sample as example, measure for parallel 6 times as stated above, obtain sample repeatability result as following table 1:
Table 1: the high-performance liquid chromatogram determination of hydrogen sulfide in mainstream smoke of cigarette content---sample repeatability
| Parallel | 1# | 2# | 3# | 4# | 5# | 6# | Mean value | RSD(%) |
| Content ((μ g/ props up)) | 31.025 | 33.075 | 30.950 | 34.885 | 32.425 | 32.350 | 32.45 | 4.49 |
The recovery is accuracy determination: before trapping, add respectively in 50mL trapping solution 50 μ L, 100 μ L, 200 μ L sodium sulfide solutions (using front demarcation), each process to repeat 6 times, is measured in the same method, and result is as following table 2:
Table 2: high-performance liquid chromatogram determination---the recovery of standard addition of hydrogen sulfide in mainstream smoke of cigarette (sulphion) content
The methodology checking of assay method when embodiment 4 aspirates 10
Sample preparation, reagent preparation and analytical procedure are as implementation column 1 and 2.
Specification Curve of Increasing: become concentration to be about the methylene blue series standard working solution of 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 4.0 μ g/mL, 6.0 μ g/mL, 10.0 μ g/mL standard inventory solution dilution with dilution with standard solution, press immediately above-mentioned condition analysis drawing standard curve, R
2must not be less than 0.99;
The trapping of cigarette smoking and sulfuretted hydrogen in main flume: be connected in series the filter disc clamper of the glass fiber filter that 92mm is housed, to tackle the granule phase substance of main flume; Serial connection is equipped with the trapping bottle (its dead volume of serial connection flue gas stream is in 10mL) of 50mL absorption liquid, and in absorption liquid, the concentration of zinc acetate, sodium acetate is respectively 0.09mmol/mL, 0.06mmol/mL; Regulate after suction capacity, start, by 10 cigarette of standard method suction, to start to trap the sulfuretted hydrogen in main flume gas phase part simultaneously; In absorption liquid, add successively derivative reagent N immediately, the aqueous sulfuric acid 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion reaction in absorption liquid be generated as methylene blue;
Precision is measured: take a certain cigarette sample as example, measure for parallel 6 times as stated above, obtain sample repeatability result as following table 3:
Table 3: the high-performance liquid chromatogram determination of hydrogen sulfide in mainstream smoke of cigarette content---sample repeatability
| Parallel | 1# | 2# | 3# | 4# | 5# | 6# | Mean value | RSD(%) |
| Content ((μ g/ props up)) | 32.033 | 32.840 | 29.539 | 34.107 | 31.741 | 31.208 | 31.91 | 4.82 |
The recovery is accuracy determination: before trapping, add respectively in 50mL trapping solution 100 μ L, 200 μ L, 400 μ L sodium sulfide solutions (using front demarcation), each process to repeat 6 times, is measured in the same method, and result is as following table 4:
Table 4: high-performance liquid chromatogram determination---the recovery of standard addition of hydrogen sulfide in mainstream smoke of cigarette (sulphion) content
Embodiment 5 and sodium sulphide are done the comparison of standard substance measurement result
Sample preparation, reagent preparation and analytical procedure are as implementation column 1 and implementation column 2.
Sulphion Specification Curve of Increasing: with sodium sulfide solution the demarcation of deionized water (being cooled to room temperature after boiling) preparation debita spissitudo, pipetting immediately appropriate sodium sulfide solution adds in 50mL absorption liquid, formulation content is about the sulphion series standard working solution of 0.02 μ g/mL, 0.05 μ g/mL, 0.10 μ g/mL, 0.20 μ g/mL, 0.50 μ g/mL, to detect and drawing standard curve by described chromatographic condition after identical deriving method colour developing, R
2must not be less than 0.99;
Methylene blue Specification Curve of Increasing: accurately compound concentration is about the methylene blue series standard working solution of 0.2 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 3.0 μ g/mL, 5.0 μ g/mL, by same procedure analysis drawing standard curve, R
2must not be less than 0.99;
The trapping of cigarette smoking and sulfuretted hydrogen in main flume: be connected in series the filter disc clamper of the glass fiber filter that 44mm is housed, regulate after suction capacity, start, by 4 cigarette of standard method suction, to start to trap the sulfuretted hydrogen in main flume gas phase part simultaneously.
During two kinds of standard substance drawing standard curves, 6 parallel comparative determinations of cigarette sample are without marked difference, and result is as following table 5:
Table 5: methylene blue and sodium sulphide are done standard substance hydrogen sulfide in mainstream smoke of cigarette assay result comparison (μ g/ props up)
| Parallel | 1# | 2# | 3# | 4# | 5# | 6# | Mean value | RSD(%) |
| Methylene blue | 31.024 | 33.076 | 30.950 | 34.889 | 32.421 | 32.350 | 32.45 | 4.49 |
| Sodium sulphide | 31.943 | 31.093 | 31.123 | 31.120 | 32.923 | 34.527 | 32.12 | 4.29 |
The analysis of sulfuretted hydrogen in cigarette sample main flume during 4 cigarette of embodiment 6 suctions
1, reagent and solution preparation
Take the 92.00g concentrated sulphuric acid (98%), slowly add in appropriate ultrapure water, jog concussion, is to be cooledly settled to 100mL during to room temperature, obtains the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes 3.137g is greater than 99% N, N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid solution with 9.2 mmol/mL is settled in the brown volumetric flask of 100mL, obtains the N that concentration is 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride aqueous sulfuric acid.
Take 24.109g 12 ferric sulfate hydrate ammoniums, with ultrapure water, be settled to 100 mL, obtaining concentration is the ammonium ferric sulfate aqueous solution of 0.5mmol/mL.
Take 0.330g Zinc diacetate dihydrate, 0.082g anhydrous sodium acetate adds in absorption bottle, measure again the ultrapure water (being cooled to room temperature after boiling) that adds 50mL, jog dissolves, and makes the concentration of zinc acetate, sodium acetate be respectively 0.03mmol/mL, 0.02mmol/mL.
Pipette methyl alcohol 450mL, ultrapure water 550mL to mobile phase bottle, add formic acid 10mL, mix, ultrasonic degas 5 minutes, obtains mobile phase.
Take 0.00500g methylene blue standard substance, with appropriate ultrapure water, dissolve, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, obtain the methylene blue standard reserving solution of 50 μ g/mL.
Accurately pipette respectively appropriate methylene blue standard reserving solution, with ultrapure water, prepare 0.2 μ g/mL ~ 5.0 μ g/mL, be no less than the methylene blue series standard working solution of 5 concentration gradients.
2, analytical procedure
By standard conditions (temperature 20
oc ± 2
oC, relative humidity 60% ± 5%) and the lower balance cigarette sample of 48 hours is pressed quality (mean value ± 50mg), resistance to suction (mean value ± 50pa) is screened, to obtain the detection sample of relative homogeneous;
By equipment operation and GB/T 19609 standard conditions requirements, preheating, debugging smoking machine are to stand-by state;
Serial connection is equipped with the filter disc clamper of 44mm glass fiber filter, to tackle the granule phase substance of main flume; Serial connection is equipped with the trapping bottle (its dead volume of serial connection flue gas stream is in 10mL) of 50mL absorption liquid, regulates after suction capacity, starts, by 4 cigarette of standard method suction, to start to trap the sulfuretted hydrogen in main flume gas phase part simultaneously.Aspirate 2 mouthfuls of complete suctions afterwards;
In absorption liquid, add successively derivative reagent N immediately, sulfuric acid solution 1.0 mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion reaction in absorption liquid be generated as methylene blue;
Derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis;
Repeat the step of derivative and print pre-treatment, the laboratory environment air of usining substitutes flue gas and deducts sample as blank.
Take the efficient liquid phase chromatographic analysis test samples of being furnished with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: fixing is the conventional analysis chromatographic column of C18 mutually; Sample size is 10 μ L; Column temperature 35
0c; Elution requirement is methyl alcohol first aqueous acid (volume ratio is 45:1:55) isocratic elution; Flow velocity is 1.0mL/min.; Detection wavelength is 665nm.
Analyze and measure series standard working solution, obtain the typical curve (R between peak area and methylene blue concentration
2must not be less than 0.99).During working sample, by the peak area of analyte derivative material methylene blue, and using laboratory environment air and substitute flue gas and deduct sample as blank, obtain the concentration of methylene blue, and convert and obtain the content of sulfuretted hydrogen according to following formula:
X=（34.076×
f×
C×
V）
/（319.85×
n）…………………………………………?（1）
In formula:
xthe content of sulfuretted hydrogen in-cigarette sample main flume, unit is that μ g/ props up;
f-extension rate is 10 herein;
c-methylene blue concentration that detect through high performance liquid chromatography, that calculate on by typical curve, unit is μ g/mL;
v-constant volume, unit is mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
3, result is calculated
Using the mean value of twice mensuration as final measurement result (with sulfuretted hydrogen), and result is accurate to 0.01 μ g/ and props up.Relative deviation between twice measurement result is in 10%.
According to embodiment 1 and said method, the sulfuretted hydrogen in 4 cigarette mainstream flue gas of suction trapping, measurement result is as following table 1:
Table 6: the measurement result of part hydrogen sulfide in mainstream smoke of cigarette
| Sample number into spectrum | A | B | C | D | E | F | G | H | I |
| Content (μ g/ props up) | 33.84 | 30.79 | 35.18 | 24.05 | 24.24 | 30.10 | 14.12 | 34.97 | 30.21 |
The analysis result of sulfuretted hydrogen in part cigarette sample main flume during 10 cigarette of embodiment 7 suctions
1, reagent and solution preparation
Take the 92.00g concentrated sulphuric acid (98%), slowly add in appropriate ultrapure water, jog concussion, is to be cooledly settled to 100mL during to room temperature, obtains the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes 3.137g is greater than 99% N, N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid solution with 9.2 mmol/mL is settled in the brown volumetric flask of 100mL, obtains the N that concentration is 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride aqueous sulfuric acid.
Take 24.109g 12 ferric sulfate hydrate ammoniums, with ultrapure water, be settled to 100 mL, obtaining concentration is the ammonium ferric sulfate aqueous solution of 0.5mmol/mL.
Take 1.000 Zinc diacetate dihydrates, 0.246 anhydrous sodium acetate adds in absorption bottle, measure again the ultrapure water (being cooled to room temperature after boiling) that adds 50mL, jog dissolves, and makes the concentration of zinc acetate, sodium acetate be respectively 0.09 mmol/mL, 0.06mmol/mL.
Pipette methyl alcohol 450mL, ultrapure water 550mL to mobile phase bottle, add formic acid 10mL, mix, ultrasonic degas 5 minutes, obtains mobile phase.
Take 0.00500g methylene blue standard substance, with appropriate ultrapure water, dissolve, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, obtain the methylene blue standard reserving solution of 50 μ g/mL.
Accurately pipette respectively appropriate methylene blue standard reserving solution, with ultrapure water, prepare 0.2 μ g/mL ~ 5.0 μ g/mL, be no less than the methylene blue series standard working solution of 5 concentration gradients.
2, analytical procedure
By standard conditions (temperature 20
oc ± 2
oC, relative humidity 60% ± 5%) and the lower balance cigarette sample of 48 hours is pressed quality (mean value ± 50mg), resistance to suction (mean value ± 50pa) is screened, to obtain the detection sample of relative homogeneous;
By equipment operation and GB/T 19609 standard conditions requirements, preheating, debugging smoking machine are to stand-by state;
Serial connection is equipped with the filter disc clamper of 92mm glass fiber filter, to tackle the granule phase substance of main flume; Serial connection is equipped with the absorption bottle (its dead volume of serial connection flue gas stream is in 10mL) of 50mL absorption liquid, regulates after suction capacity, starts, by 10 cigarette of standard method suction, to start to trap the sulfuretted hydrogen in main flume gas phase part simultaneously.Aspirate 2 mouthfuls of complete suctions afterwards;
In absorption liquid, add successively derivative reagent N immediately, the aqueous sulfuric acid 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion reaction in absorption liquid be generated as methylene blue;
Derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis;
Repeat the step of derivative and print pre-treatment, the laboratory environment air of usining substitutes flue gas and deducts sample as blank.
Take the efficient liquid phase chromatographic analysis test samples of being furnished with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: fixing is the conventional analysis chromatographic column of C18 mutually; Sample size is 10 μ L; Column temperature 35
0c; Elution requirement is methyl alcohol first aqueous acid (volume ratio is 45:1:55) isocratic elution; Flow velocity is 1.0mL/min.; Detection wavelength is 665nm.
Analyze and measure series standard working solution, obtain the typical curve (R between peak area and methylene blue concentration
2must not be less than 0.99).During working sample, by the peak area of analyte derivative material methylene blue, and using laboratory environment air and substitute flue gas and deduct sample as blank, obtain the concentration of methylene blue, and convert and obtain the content of sulfuretted hydrogen according to following formula:
X=（34.076×
f×
C×
V）
/（319.85×
n）…………………………………………?（1）
In formula:
xthe content of sulfuretted hydrogen in-cigarette sample main flume, unit is that μ g/ props up;
f-extension rate is 10 herein;
c-methylene blue concentration that detect through high performance liquid chromatography, that calculate on by typical curve, unit is μ g/mL;
v-constant volume, unit is mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
3, result is calculated
Using the mean value of twice mensuration as final measurement result (with sulfuretted hydrogen), and result is accurate to 0.01 μ g/ and props up.Relative deviation between twice measurement result is in 10%.
According to embodiment 1 and said method, the sulfuretted hydrogen in 10 cigarette mainstream flue gas of suction trapping, measurement result is as following table 1:
Table 7: the measurement result of part hydrogen sulfide in mainstream smoke of cigarette
| Sample number into spectrum | A | B | C | D | E | F | G | H | I |
| Content (μ g/ props up) | 34.15 | 28.50 | 35.72 | 23.07 | 22.58 | 32.83 | 13.18 | 36.45 | 30.94 |
Claims (5)
1. the assay method of a hydrogen sulfide in mainstream smoke of cigarette, it is characterized in that: described assay method is the sulfuretted hydrogen in the alkaline solution trapping flue gas gas phase that contains zinc ion, and pass through N, N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate derive after colour developing trapped sulfuretted hydrogen under acid condition, utilization is furnished with the high performance liquid chromatograph of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector, with methylene blue standard items, carry out the method for qualitative determination, the concrete steps of described qualitative determination method are:
(1) aspirate 4 ~ 10 cigarette, with the grain phase part of 44mm or 92mm glass fiber filter interception main flume, so that the trapping bottle of 50mL zinc acetate-sodium acetate absorbent solution to be housed, absorb the sulfuretted hydrogen in trapping gas phase part; After regulating suction capacity, on smoking machine, press GB/T 19609 standard conditions smoking cigarette samples, 2 mouthfuls of complete suctions afterwards;
(2) in absorption liquid, add successively derivative reagent N immediately, sulfuric acid solution 1.0mL ~ the 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0mL ~ 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion complete reaction in absorption liquid be generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis; The testing conditions of described efficient liquid phase chromatographic analysis is: fixing is the analysis chromatographic column of C18 mutually, and eluent is methyl alcohol aqueous formic acid, and wherein the volume ratio of methyl alcohol, formic acid, water is 45:1:55, and type of elution is isocratic elution; Flow velocity is 1.0mL/min; Sample size is 10 μ L; 35 ℃ of column temperatures; The detection wavelength of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector is 665nm;
(4) contrast with the retention time of methylene blue standard items, in qualitative cigarette smoke, whether sulfuretted hydrogen exists.
2. the assay method of a hydrogen sulfide in mainstream smoke of cigarette, it is characterized in that: described assay method is the sulfuretted hydrogen in the alkaline solution trapping flue gas gas phase that contains zinc ion, and pass through N, N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate derive after colour developing trapped sulfuretted hydrogen under acid condition, utilization is furnished with the high performance liquid chromatograph of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector, with methylene blue standard items, carry out the method for quantitative measurement, the concrete steps of described method for quantitatively determining are:
(1) aspirate 4 ~ 10 cigarette, with the grain phase part of 44mm or 92mm glass fiber filter interception main flume, so that the trapping bottle of 50mL zinc acetate-sodium acetate absorbent solution to be housed, absorb the sulfuretted hydrogen in trapping gas phase part; After regulating suction capacity, on smoking machine, press GB/T 19609 standard conditions smoking cigarette samples, 2 mouthfuls of complete suctions afterwards;
(2) in absorption liquid, add successively derivative reagent N immediately, sulfuric acid solution 1.0mL ~ the 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0mL ~ 2.0mL, airtight inversion jog 30 seconds, standing 5 minutes, makes the sulphion complete reaction in absorption liquid be generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL completely, get wherein 10mL and be settled to 100mL with ultrapure water, then get after appropriate dilution is crossed 0.45 μ m filter membrane and detect with efficient liquid phase chromatographic analysis; The testing conditions of described efficient liquid phase chromatographic analysis is: fixing is the analysis chromatographic column of C18 mutually, and eluent is methyl alcohol aqueous formic acid, and wherein the volume ratio of methyl alcohol, formic acid, water is 45:1:55, and type of elution is isocratic elution; Flow velocity is 1.0mL/min; Sample size is 10 μ L; 35 ℃ of column temperatures; The detection wavelength of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector is 665nm;
(4) accurately prepare 0.2 μ g/mL ~ 5.0 μ g/mL, be no less than the methylene blue series standard solution of 5 concentration gradients;
(5), according to chromatographic condition step (3) Suo Shu, the methylene blue series standard solution of preparation in determination step (4), obtains the typical curve between peak area and methylene blue concentration, R respectively
2must not be less than 0.99;
The laboratory environment air of usining substitutes flue gas and deducts sample as blank, with typical curve regression equation, obtains the methylene blue concentration in analytical sample, and converts and obtain the content of sulfuretted hydrogen according to following formula:
X=（34.076×f×C×V）/（319.85×n）
In formula:
The content of sulfuretted hydrogen in X-cigarette sample main flume, unit is that μ g/ props up;
F-extension rate is 10 herein;
Methylene blue concentration C-detect through high performance liquid chromatography, that calculate on by typical curve, unit is μ g/mL;
V-constant volume, unit is mL;
N-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
3. assay method as claimed in claim 1 or 2, is characterized in that: the concentration of described absorbent solution zinc acetate-sodium acetate is respectively (0.03mmol/mL ~ 0.09mmol/mL)-(0.02mmol/mL ~ 0.06mmol/mL).
4. assay method as claimed in claim 1 or 2, is characterized in that: the concentration of described ammonium ferric sulfate solution is 0.5mmol/mL.
5. assay method as claimed in claim 1 or 2, is characterized in that: described derivative reagent N, and the sulfuric acid solution of N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid concentration is 9.2mmol/mL, N, N-dimethyl-p-phenylenediamine dihydrochloride concentration is 0.15mmol/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110437482.3A CN102565262B (en) | 2011-12-23 | 2011-12-23 | Determination method for hydrogen sulfide in mainstream smoke of cigarette |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110437482.3A CN102565262B (en) | 2011-12-23 | 2011-12-23 | Determination method for hydrogen sulfide in mainstream smoke of cigarette |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102565262A CN102565262A (en) | 2012-07-11 |
| CN102565262B true CN102565262B (en) | 2014-01-22 |
Family
ID=46411223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110437482.3A Active CN102565262B (en) | 2011-12-23 | 2011-12-23 | Determination method for hydrogen sulfide in mainstream smoke of cigarette |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102565262B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103226137B (en) * | 2013-01-07 | 2014-08-13 | 中国建材检验认证集团股份有限公司 | Method for determination of low-concentration H2S in air |
| CN103884794A (en) * | 2014-03-31 | 2014-06-25 | 李新华 | Method for measuring trace hydrogen sulfide gas in atmosphere |
| CN105823741B (en) * | 2016-03-11 | 2018-05-15 | 青岛科技大学 | The detection method of butyraldehyde content in a kind of air |
| CN105954275A (en) * | 2016-05-25 | 2016-09-21 | 河北中烟工业有限责任公司 | Method for determination of sulfides in cigarette smoke |
| CN110987844A (en) * | 2019-11-19 | 2020-04-10 | 佛山中纺联检验技术服务有限公司 | Method for detecting sulfide content in textile clothes |
| CN111122542A (en) * | 2019-12-26 | 2020-05-08 | 厦门大学 | Method for measuring sulfide in water by using surface enhanced Raman spectroscopy |
| CN113125366A (en) * | 2021-04-20 | 2021-07-16 | 苏州朗易生物医药研究有限公司 | Method for detecting content of hydrogen sulfide in acetylcysteine solution for inhalation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101017158A (en) * | 2007-02-08 | 2007-08-15 | 江南大学 | Method for determining sulfide in spirit |
| CN101598674A (en) * | 2009-05-19 | 2009-12-09 | 谱尼测试科技（北京）有限公司 | The assay method of sulfide content in a kind of soil |
| CN102156103A (en) * | 2011-03-08 | 2011-08-17 | 重庆烟草工业有限责任公司 | Determination method for indirectly measuring sulfureted hydrogen in mainstream smoke gas phase of cigarette by copper color method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335153A (en) * | 1991-05-13 | 1992-11-24 | Mitsubishi Heavy Ind Ltd | Hydrogen sulfide detection agent |
| JP4840692B2 (en) * | 2006-04-24 | 2011-12-21 | 東洋製罐株式会社 | New methylene blue analysis method |
-
2011
- 2011-12-23 CN CN201110437482.3A patent/CN102565262B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101017158A (en) * | 2007-02-08 | 2007-08-15 | 江南大学 | Method for determining sulfide in spirit |
| CN101598674A (en) * | 2009-05-19 | 2009-12-09 | 谱尼测试科技（北京）有限公司 | The assay method of sulfide content in a kind of soil |
| CN102156103A (en) * | 2011-03-08 | 2011-08-17 | 重庆烟草工业有限责任公司 | Determination method for indirectly measuring sulfureted hydrogen in mainstream smoke gas phase of cigarette by copper color method |
Non-Patent Citations (12)
| Title |
|---|
| Degui Tang et al.Sensitive determination of dissolved sulfide in estuarine water by solid-phase extraction and high-performance liquid chromatography.《Journal of Chromatography A》.2000,第883卷(第1-2期), |
| Is hydrogen sulfide a circulating "gasotransmitter" in vertebrate blood?;Kenneth R. Olson et al;《Biochimica et Biophysica Acta》;20090731;第1787卷(第7期);第856-863页 * |
| JP特开2007-292565A 2007.11.08 |
| JP特开平4-335153A 1992.11.24 |
| Kenneth R. Olson et al.Is hydrogen sulfide a circulating "gasotransmitter" in vertebrate blood?.《Biochimica et Biophysica Acta》.2009,第1787卷(第7期),第856-863页. |
| Sensitive determination of dissolved sulfide in estuarine water by solid-phase extraction and high-performance liquid chromatography;Degui Tang et al;《Journal of Chromatography A》;20000623;第883卷(第1-2期);第305-309页 * |
| 亚甲基蓝分光光度法测定水中硫化物影响因素的探讨;林李秋;《化学工程师》;20061031(第10期);第32-33、35页 * |
| 李莉 等.高效液相色谱法测定亚甲基蓝原料药的有关物质.《药物分析杂志》.2008,第28卷(第10期),第1698-1701页. |
| 杨方 等.液相色谱法检测水产品中亚甲蓝及其代谢物残留.《分析化学》.2009,第37卷(第4期),第517-521页. |
| 林李秋.亚甲基蓝分光光度法测定水中硫化物影响因素的探讨.《化学工程师》.2006,(第10期), |
| 液相色谱法检测水产品中亚甲蓝及其代谢物残留;杨方 等;《分析化学》;20090430;第37卷(第4期);第517-521页 * |
| 高效液相色谱法测定亚甲基蓝原料药的有关物质;李莉 等;《药物分析杂志》;20081031;第28卷(第10期);第1698-1701页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102565262A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102565262B (en) | Determination method for hydrogen sulfide in mainstream smoke of cigarette | |
| CN102128885B (en) | Method for quickly and simultaneously detecting 16 inorganic anions and organic acids in tobacco | |
| CN102539558B (en) | Method for measuring hydrogen sulfide in mainstream cigarette smoke | |
| CN102012409B (en) | Analysis method for trace tobacco specific N-nitrosamine (TSNAs) in animal blood sample | |
| CN107271584B (en) | Method for trapping carbonyl compounds and tobacco-specific nitrosamines in cigarette mainstream smoke, extraction method and determination method | |
| CN101762653B (en) | Method for determining main phenolic compounds in main stream smoke of cigarette | |
| CN108802256B (en) | Method for detecting content of monoethanolamine | |
| CN104020246A (en) | Method for simultaneously detecting plurality of volatile trace carbonyl compounds in atmosphere | |
| CN101109735A (en) | Fluorescence photometry for immune affinity column of aflatoxin in paddy | |
| CN102590386B (en) | Method for detecting nicotine and metabolites thereof in urine sample of smoker | |
| CN104535694A (en) | Method for detecting four tobacco-specific nitrosamines (TSNAs) in lateral exhaust gas of cigarettes by virtue of gas chromatography-tandem mass spectrometry | |
| CN102980968A (en) | Liquid chromatogram tandem mass spectrum measuring method for creatinine in urine | |
| CN102156103B (en) | Determination method for indirectly measuring sulfureted hydrogen in mainstream smoke gas phase of cigarette by copper color method | |
| US9110048B2 (en) | Devices and methods for measuring the acidity of airborne matter using UV-visible spectrometry | |
| Chen et al. | Development of a high-performance liquid chromatography method for the simultaneous quantification of four organoarsenic compounds in the feeds of swine and chicken | |
| CN102353668A (en) | Method for determining anionic surfactant in surface water | |
| CN104007202A (en) | HPLC (high performance liquid chromatography) analyzing method for 3-aminopiperidine | |
| CN109917062B (en) | Method for analyzing imidacloprid synthetic intermediate content by liquid chromatography-mass spectrometry | |
| CN105784886A (en) | Gas chromatography-tandem mass spectrum detection method for hydrazine in cigarette mainstream smoke | |
| CN105004819A (en) | Method for measuring content of HCN (hydrogen cyanide) in main stream smoke of cigarettes | |
| CN105911200B (en) | The assay method of (N methyl Ns nitrosamine) 1 (3 pyridine radicals) butanone 4 in a kind of cigarette mainstream flue gas | |
| CN102393436A (en) | Measuring method of phenol content in toy material | |
| Ouyang et al. | Determination of sulfonylurea herbicides in water using solid-phase extraction followed by liquid chromatography with electrospray ion trap mass spectrometry | |
| Rodríguez‐Gonzalo et al. | Automated sample treatment with the injection of large sample volumes for the determination of contaminants and metabolites in urine | |
| Wu et al. | Determination of N-nitrososarcosine in tobacco and smokeless tobacco products using isotope dilution liquid chromatography tandem mass spectrometry |
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 |