CN102565262A - 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
- CN102565262A CN102565262A CN2011104374823A CN201110437482A CN102565262A CN 102565262 A CN102565262 A CN 102565262A CN 2011104374823 A CN2011104374823 A CN 2011104374823A CN 201110437482 A CN201110437482 A CN 201110437482A CN 102565262 A CN102565262 A CN 102565262A
- Authority
- CN
- China
- Prior art keywords
- cigarette
- methylene blue
- solution
- sulfuretted hydrogen
- 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.)
- Granted
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 the high-performance liquid chromatogram determination method of sulfuretted hydrogen in a kind of cigarette smoke specifically.
Background technology
Be rich in protein and amino acid in the tobacco, comprising sulfur-bearing protein 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 the intense stimulus effect.Acute toxicity (LC506): 18mg/m
3(rat suction); Subacute and chronic toxicity: rabbit sucks 0.01mg/L, and 2 hours/day, 3 months, cause that the function of central nervous system changes, tracheae, tunica mucosa bronchiorum irritation, pathological change appears in cerebral cortex.Mouse contacts low concentration hydrogen sulphide for a long time, and the infringement of stingy road is arranged.Therefore, a kind of reliably, the sulfuretted hydrogen assay method is significant for hydrogen sulfide content and corresponding harm reduction technological development in the monitoring cigarette smoke in the cigarette mainstream flue gas accurately.
In fields such as environmental water quality monitoring, mostly the method that detects sulfuretted hydrogen is methylene-blue colorimetric method, also has bibliographical information to cross fluorescence detection at present.The former is subject to disturb (referring to the high-efficient liquid phase chromatogram impurity peaks of accompanying drawing 3), and the required derivative reagent of the latter also is difficult to obtain at present.It is less that these methods are applied to the possibility that sulfuretted hydrogen in the flue gas detects, and its main difficult point is the capture of sulfuretted hydrogen in the flue gas, and effectively derives after capturing to can be used for the sample that high performance liquid chromatogram detects.How fully to capture, the sulfuretted hydrogen in the flue gas of deriving and accurately measuring, become problem demanding prompt solution in the present detection.
Summary of the invention
The present invention is directed to sulfuretted hydrogen in the present cigarette mainstream flue gas capture, derive and accurate problem such as mensuration, the assay method of sulfuretted hydrogen in a kind of cigarette mainstream flue gas is provided.Said assay method is to capture the sulfuretted hydrogen in the flue gas gas phase with the alkaline solution that contains zinc ion; And pass through N; N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate under acid condition to the absorbent solution that the contains sulfuretted hydrogen colour developing of deriving; Utilize the high performance liquid chromatograph be furnished with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector to detect afterwards, and the method qualitative, quantitative measurement that with the methylene blue is that standard items carry out.In order fully to capture the sulfuretted hydrogen in the flue gas, the molar equivalent ratio of sulfuretted hydrogen should be more than 100:1 in the zinc ion in the absorption liquid and the flue gas.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 with use N, N-dimethyl-p-phenylenediamine dihydrochloride equivalent generation methylene blue.For avoiding impurity to disturb, separate with RPLC.Detect under 665nm with ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector, compare, come whether to have sulfuretted hydrogen in the qualitative sample according to retention time through liquid chromatogram with the methylene blue standard items; Utilize external standard method, through typical curve, the concentration of methylene blue and conversion obtain the content of sulfuretted hydrogen in the cigarette mainstream flue gas in the quantitative liquid to be detected.In the capture process, can absorption liquid be put into trapping bottle disclosed by the invention, absorb capture.Certainly, the testing staff also can adopt drip catcher commonly used in the present flue gas mensuration, captures.
As practical implementation step of the present invention, the present invention discloses the qualitative checking method and the quantitative detecting method of sulfuretted hydrogen respectively.
The concrete steps of said qualitative determination method are:
(1) 4 ~ 10 cigarette of suction, the grain phase part with 44mm or 92mm spun glass filter disc interception main flume absorbs the sulfuretted hydrogen that captures in the flue gas gas phase part with the trapping bottle that 50mL milliliter zinc acetate-sodium acetate absorbent solution is housed; Regulate after the suction capacity, on smoking machine, press GB/T 19609 standard conditions cigarette smoking cigarette samples, suction is 2 mouthfuls after finishing;
(2) in absorption liquid, add derivative reagent N immediately successively; 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; Left standstill 5 minutes, and made that the sulphion complete reaction in the absorption liquid was generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
The testing conditions of said efficient liquid phase chromatographic analysis is: stationary phase is that C18 analyzes chromatographic column, and eluent is methyl alcohol aqueous formic acid (volume ratio is 45:1:55), and type of elution is an 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) retention time with methylene blue contrasts, and whether sulfuretted hydrogen exists in the qualitative sample.
The concrete steps of said method for quantitatively determining are:
(1) 4 ~ 10 cigarette of suction, the grain phase part with 44mm or 92mm spun glass filter disc interception main flume absorbs the sulfuretted hydrogen that captures in the flue gas gas phase part with the trapping bottle that 50mL milliliter zinc acetate-sodium acetate absorbent solution is housed; Regulate after the suction capacity, on smoking machine, press GB/T 19609 standard conditions cigarette smoking cigarette samples, suction is 2 mouthfuls after finishing;
(2) in absorption liquid, add derivative reagent N immediately successively; 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 left standstill 5 minutes, made that the sulphion reaction in the absorption liquid is generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
The testing conditions of said efficient liquid phase chromatographic analysis is: stationary phase is that C18 analyzes chromatographic column, and 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 the described chromatographic condition of step (3), the methylene blue series standard solution of preparation in the determination step (4) obtains the typical curve (R between peak area and the methylene blue concentration respectively
2Must not be less than 0.99).During working sample,, and substitute flue gas with the laboratory environment air and deduct sample, obtain the concentration of methylene blue, and convert according to following formula and to obtain the content of sulfuretted hydrogen as blank by the peak area of analyte derivative material methylene blue:
X=（34.076×
f×C×V）
/（319.85
×n）
In the formula:
XThe content of sulfuretted hydrogen in the-cigarette sample main flume, unit props up for μ g/;
f-extension rate is 10 here;
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 are mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight;
(6) result representes: as the final result that measures, the result is accurate to 0.01 μ g/ and props up with the mean value of twice mensuration.Relative deviation between the replicate determination result must be in 10%.
As improvement of the present invention, in above-mentioned qualitative and quantitative measurement, the concentration of said absorbent solution zinc acetate one sodium acetate is respectively (0.03mmol/mL ~ 0.09mmol/mL) (0.02mmol/mL ~ 0.06mmol/mL).Said derivative reagent N, the sulfuric acid solution of N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid concentration are 9.2 mmol/mL, N, N-dimethyl-p-phenylenediamine dihydrochloride concentration is 0.15mmol/m.The concentration of said ammonium ferric sulfate solution is 0.5mmol/mL.
In order to reduce the loss of sulfuretted hydrogen, guarantee the accuracy of detection, its dead volume of flue gas stream that the invention also discloses said serial connection trapping bottle is in 10ml.
Through disclosed technical scheme among the present invention; Can from the main flume of cigarette, directly capture hydrogen sulfide gas; And obtain methylene blue through deriving, thereby utilize ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector that it is carried out qualitative and quantitative detection.This law with methylene blue as standard substance, with traditional be that the method for examination criteria is compared with sodium sulphide, do not need complicated calibration process, can realize detecting fast.Simultaneously, do the method that reference material detects with sulfuretted hydrogen and compare with traditional, security improves.
Compare with the methylene-blue colorimetric method of in environment and water quality detection, using always at present, its antijamming capability is stronger; Compare with fluorescence detection, owing to saved the synthetic of standard fluorescence reagent, method simply is easy to popularize.
Description of drawings
Fig. 1 captures synoptic diagram for sulfuretted hydrogen;
Fig. 2 is a methylene blue HPLC chromatogram;
Fig. 3 is a sample HPLC chromatogram;
Fig. 4 is methylene blue typical curve and area-concentration regression equation.
Embodiment
Take by weighing the 92.00g concentrated sulphuric acid (98%), slowly add in an amount of ultrapure water, jog concussion, the 100mL that is settled to during to room temperature to be cooled, the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes by weighing 3.137g is greater than 99% N; N-dimethyl-p-phenylenediamine dihydrochloride; With the dissolving of the sulfuric acid solution of 9.2 mmol/mL and be settled in the brown volumetric flask of 100mL, concentration be the N of 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride sulfuric acid solution.
Take by weighing 24.109g 12 ferric sulfate hydrate ammoniums, be settled to 100 mL with ultrapure water, getting concentration is the ammonium ferric sulfate solution of 0.5mmol/mL.
Take by weighing in 0.330g Zinc diacetate dihydrate, the 0.082g anhydrous sodium acetate adding absorption bottle, measure the ultrapure water (being cooled to room temperature after boiling) that adds 50mL again, the jog dissolving makes the concentration of zinc acetate, sodium acetate be respectively 0.03mmol/mL, 0.02mmol/mL.
Take by weighing in 1.000 Zinc diacetate dihydrates, the 0.246 anhydrous sodium acetate adding absorption bottle, measure the ultrapure water (being cooled to room temperature after boiling) that adds 50mL again, the jog dissolving 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 the moving phase bottle, add formic acid 10mL, mixing, ultrasonic degas 5 minutes gets moving phase.
Accurately take by weighing 0.00500g methylene blue standard substance,, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, get the methylene blue standard reserving solution of 50 μ g/mL with an amount of ultrapure water dissolving.
With standard conditions (temperature 20
oC ± 2
OC, relative humidity 60% ± 5%) down 48 hours cigarette sample of balance (mean value ± 50mg), (mean value ± 50pa) screening is to obtain the testing sample of relative homogeneous for resistance to suction by quality;
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 spun glass filter disc, with the granule phase substance of interception 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, behind the adjusting suction capacity, begins by 4 ~ 10 of standard method smoking cigarettes, begins to capture the sulfuretted hydrogen in the main flume gas phase part; After capture finishes, 2 mouthfuls of suctions;
In absorption liquid, add derivative reagent N immediately successively; 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 left standstill 5 minutes, made that the sulphion reaction in the absorption liquid is generated as methylene blue;
Derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
To be furnished with the efficient liquid phase chromatographic analysis test samples of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: stationary phase is the conventional analysis chromatographic column of C18; Sample size is 10 μ L; Flow velocity is 1.0mL/min.; Column temperature 35
0C; Elution requirement is the WS (volume ratio the is 45:1:55) isocratic elution of methyl alcohol, formic acid; The detection wavelength is 665nm.
The HPLC chromatogram that obtains sample is as shown in Figure 3.
With 10 times of methylene blue standard reserving solution dilutions, according to above-mentioned HPLC assay method, sample introduction detects, and the HPLC chromatogram that obtains standard items is as shown in Figure 2, can see the retention time of the base peak of methylene blue.
Observe the sample peak retention time among Fig. 2, comparison is confirmed to contain methylene blue in the detected sample, thereby confirms to contain sulfuretted hydrogen in the flue gas.
The drafting of typical curve
Prepare sample and each reagent respectively according to the method among the embodiment 1.
With the methylene blue standard reserving solution of 50 μ g/mL is respectively 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 with the ultrapure water dilution; According to above-mentioned HPLC detection method, obtain a series of and the corresponding peak area of concentration.With the peak area is ordinate, and the methylene blue that with concentration is μ g/mL is a horizontal ordinate, and linear regression drawing standard curve gets 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.
Detection by quantitative
Draw analyte sample fluid, according to the method among the embodiment 1, obtain the HPLC peak area, and utilize above-mentioned typical curve to obtain the methylene blue concentration in the liquid to be measured, obtain the content of sulfuretted hydrogen in the cigarette sample main flume according to computes by peak area.
X=（34.076×
f×
C×
V）
/（319.85×
n）
In the formula:
XThe content of sulfuretted hydrogen in the-cigarette sample main flume, unit props up for μ g/;
f-extension rate is 10 here;
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 are mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
As the final result that measures, the result is accurate to 0.01 μ g/ and props up with the mean value of twice mensuration.Relative deviation between the replicate determination result must be in 10%.
The methodology checking of assay method when embodiment 3 aspirates 4
Specimen preparation, reagent preparation and analytical procedure are as implementing row 1 and 2.
Typical curve is drawn: 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 the standard inventory solution dilution with ultrapure water; Press above-mentioned condition analysis and drawing standard curve, R immediately
2Must not be less than 0.99;
The capture of sulfuretted hydrogen in cigarette smoking and the main flume: be connected in series the filter disc clamper of the spun glass filter disc that 44mm is housed, with the granule phase substance of interception 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 the concentration of zinc acetate, sodium acetate is respectively 0.03mmol/mL, 0.02mmol/mL in the absorption liquid; After regulating the suction capacity, beginning by 4 cigarette of standard method suction, begins to capture the sulfuretted hydrogen in the main flume gas phase part with preceding method simultaneously.
After capture finishes; In absorption liquid, add derivative reagent N immediately successively, aqueous sulfuric acid 1.0 mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL, airtight inversion jog 30 seconds; Left standstill 5 minutes, and made that the sulphion reaction in the absorption liquid was generated as methylene blue;
Precision is measured: with a certain cigarette sample is example, and parallel as stated above 6 mensuration obtain sample repeatability result such as following table 1:
Table 1: the high-performance liquid chromatogram determination of hydrogen sulfide content in the cigarette mainstream flue gas---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 an accuracy determination: in the 50mL trapping solution, add 50 μ L, 100 μ L, 200 μ L sodium sulfide solutions (using preceding demarcation) before the capture respectively, each handles repetition 6 times, measures result such as following table 2 with method:
Table 2: high-performance liquid chromatogram determination---the recovery of standard addition of sulfuretted hydrogen in the cigarette mainstream flue gas (sulphion) content
The methodology checking of assay method when embodiment 4 aspirates 10
Specimen preparation, reagent preparation and analytical procedure are as implementing row 1 and 2.
Typical curve is drawn: 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 the standard inventory solution dilution with standard solution with dilution; Press above-mentioned condition analysis and drawing standard curve, R immediately
2Must not be less than 0.99;
The capture of sulfuretted hydrogen in cigarette smoking and the main flume: be connected in series the filter disc clamper of the spun glass filter disc that 92mm is housed, with the granule phase substance of interception 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 the concentration of zinc acetate, sodium acetate is respectively 0.09mmol/mL, 0.06mmol/mL in the absorption liquid; After regulating the suction capacity, begin to begin to capture the sulfuretted hydrogen in the main flume gas phase part simultaneously by 10 cigarette of standard method suction; In absorption liquid, add derivative reagent N immediately successively; The aqueous sulfuric acid 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 2.0mL; Airtight inversion jog 30 seconds left standstill 5 minutes, made that the sulphion reaction in the absorption liquid is generated as methylene blue;
Precision is measured: with a certain cigarette sample is example, and parallel as stated above 6 mensuration obtain sample repeatability result such as following table 3:
Table 3: the high-performance liquid chromatogram determination of hydrogen sulfide content in the cigarette mainstream flue gas---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 an accuracy determination: in the 50mL trapping solution, add 100 μ L, 200 μ L, 400 μ L sodium sulfide solutions (using preceding demarcation) before the capture respectively, each handles repetition 6 times, measures result such as following table 4 with method:
Table 4: high-performance liquid chromatogram determination---the recovery of standard addition of sulfuretted hydrogen in the cigarette mainstream flue gas (sulphion) content
Specimen preparation, reagent preparation and analytical procedure are as implementing row 1 and implementing row 2.
The sulphion typical curve is drawn: with the sodium sulfide solution and the demarcation of deionized water (being cooled to room temperature after boiling) preparation debita spissitudo; Pipetting an amount of sodium sulfide solution immediately adds in the 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; Detect and the drawing standard curve R by said chromatographic condition with identical deriving method colour developing back
2Must not be less than 0.99;
The methylene blue typical curve is drawn: 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 and drawing standard curve, R
2Must not be less than 0.99;
The capture of sulfuretted hydrogen in cigarette smoking and the main flume: be connected in series the filter disc clamper of the spun glass filter disc that 44mm is housed, regulate the suction capacity after, begin to begin to capture the sulfuretted hydrogen in the main flume gas phase part simultaneously by 4 cigarette of standard method suction.
6 parallel comparative determinations of cigarette sample do not have marked difference during two kinds of standard substance drawing standard curves, result such as following table 5:
Table 5: methylene blue and sodium sulphide are done hydrogen sulfide content mensuration result's comparison (μ g/ props up) in the standard substance cigarette mainstream flue gas
| 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 by weighing the 92.00g concentrated sulphuric acid (98%), slowly add in an amount of ultrapure water, jog concussion, the 100mL that is settled to during to room temperature to be cooled, the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes by weighing 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, and getting concentration is the N of 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride aqueous sulfuric acid.
Take by weighing 24.109g 12 ferric sulfate hydrate ammoniums, be settled to 100 mL with ultrapure water, getting concentration is the ammonium ferric sulfate WS of 0.5mmol/mL.
Take by weighing in 0.330g Zinc diacetate dihydrate, the 0.082g anhydrous sodium acetate adding absorption bottle, measure the ultrapure water (being cooled to room temperature after boiling) that adds 50mL again, the jog dissolving makes the concentration of zinc acetate, sodium acetate be respectively 0.03mmol/mL, 0.02mmol/mL.
Pipette methyl alcohol 450mL, ultrapure water 550mL to the moving phase bottle, add formic acid 10mL, mixing, ultrasonic degas 5 minutes gets moving phase.
Take by weighing 0.00500g methylene blue standard substance,, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, get the methylene blue standard reserving solution of 50 μ g/mL with an amount of ultrapure water dissolving.
Accurately pipette an amount of methylene blue standard reserving solution respectively, 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 with ultrapure water.
2, analytical procedure
With standard conditions (temperature 20
oC ± 2
OC, relative humidity 60% ± 5%) down 48 hours cigarette sample of balance (mean value ± 50mg), (mean value ± 50pa) screening is to obtain the test sample of relative homogeneous for resistance to suction by quality;
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 spun glass filter disc, with the granule phase substance of interception 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, behind the adjusting suction capacity, begins to begin to capture the sulfuretted hydrogen in the main flume gas phase part simultaneously by 4 cigarette of standard method suction.Suction was 2 mouthfuls after suction finished;
In absorption liquid, add derivative reagent N immediately successively; Sulfuric acid solution 1.0 mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 1.0 mL; Airtight inversion jog 30 seconds left standstill 5 minutes, made that the sulphion reaction in the absorption liquid is generated as methylene blue;
Derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
Repeat to derive and the step of print pre-treatment, substitute flue gas with the laboratory environment air and deduct sample as blank.
To be furnished with the efficient liquid phase chromatographic analysis test samples of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: stationary phase is the conventional analysis chromatographic column of C18; Sample size is 10 μ L; Column temperature 35
0C; Elution requirement is the WS (volume ratio the is 45:1:55) isocratic elution of methyl alcohol formic acid; Flow velocity is 1.0mL/min.; The detection wavelength is 665nm.
Assay determination series standard working solution obtains the typical curve (R between peak area and the methylene blue concentration
2Must not be less than 0.99).During working sample,, and substitute flue gas with the laboratory environment air and deduct sample, obtain the concentration of methylene blue, and convert according to following formula and to obtain the content of sulfuretted hydrogen as blank by the peak area of analyte derivative material methylene blue:
X=（34.076×
f×
C×
V）
/（319.85×
n）…………………………………………?（1）
In the formula:
XThe content of sulfuretted hydrogen in the-cigarette sample main flume, unit props up for μ g/;
f-extension rate is 10 here;
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 are mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
3, the result calculates
As the final result's (with sulfuretted hydrogen) that measures, the result is accurate to 0.01 μ g/ and props up with the mean value of twice mensuration.Measure relative deviation between the result for twice in 10%.
According to embodiment 1 and said method, suction captures the sulfuretted hydrogen in 4 cigarette mainstream flue gas, measures result such as following table 1:
Table 6: the mensuration result of sulfuretted hydrogen in the part cigarette mainstream flue gas
| 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 by weighing the 92.00g concentrated sulphuric acid (98%), slowly add in an amount of ultrapure water, jog concussion, the 100mL that is settled to during to room temperature to be cooled, the sulfuric acid solution of 9.2 mmol/mL.
The purity that takes by weighing 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, and getting concentration is the N of 0.15mmol/mL, N-dimethyl-p-phenylenediamine dihydrochloride aqueous sulfuric acid.
Take by weighing 24.109g 12 ferric sulfate hydrate ammoniums, be settled to 100 mL with ultrapure water, getting concentration is the ammonium ferric sulfate WS of 0.5mmol/mL.
Take by weighing in 1.000 Zinc diacetate dihydrates, the 0.246 anhydrous sodium acetate adding absorption bottle, measure the ultrapure water (being cooled to room temperature after boiling) that adds 50mL again, the jog dissolving 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 the moving phase bottle, add formic acid 10mL, mixing, ultrasonic degas 5 minutes gets moving phase.
Take by weighing 0.00500g methylene blue standard substance,, add the sulfuric acid solution 1mL of 9.2mmol/mL, be settled to 100mL, get the methylene blue standard reserving solution of 50 μ g/mL with an amount of ultrapure water dissolving.
Accurately pipette an amount of methylene blue standard reserving solution respectively, 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 with ultrapure water.
2, analytical procedure
With standard conditions (temperature 20
oC ± 2
OC, relative humidity 60% ± 5%) down 48 hours cigarette sample of balance (mean value ± 50mg), (mean value ± 50pa) screening is to obtain the test sample of relative homogeneous for resistance to suction by quality;
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 spun glass filter disc, with the granule phase substance of interception 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, behind the adjusting suction capacity, begins to begin to capture the sulfuretted hydrogen in the main flume gas phase part simultaneously by 10 cigarette of standard method suction.Suction was 2 mouthfuls after suction finished;
In absorption liquid, add derivative reagent N immediately successively; The aqueous sulfuric acid 2.0mL of N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate solution 2.0mL; Airtight inversion jog 30 seconds left standstill 5 minutes, made that the sulphion reaction in the absorption liquid is generated as methylene blue;
Derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
Repeat to derive and the step of print pre-treatment, substitute flue gas with the laboratory environment air and deduct sample as blank.
To be furnished with the efficient liquid phase chromatographic analysis test samples of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector: stationary phase is the conventional analysis chromatographic column of C18; Sample size is 10 μ L; Column temperature 35
0C; Elution requirement is the WS (volume ratio the is 45:1:55) isocratic elution of methyl alcohol formic acid; Flow velocity is 1.0mL/min.; The detection wavelength is 665nm.
Assay determination series standard working solution obtains the typical curve (R between peak area and the methylene blue concentration
2Must not be less than 0.99).During working sample,, and substitute flue gas with the laboratory environment air and deduct sample, obtain the concentration of methylene blue, and convert according to following formula and to obtain the content of sulfuretted hydrogen as blank by the peak area of analyte derivative material methylene blue:
X=（34.076×
f×
C×
V）
/（319.85×
n）…………………………………………?（1）
In the formula:
XThe content of sulfuretted hydrogen in the-cigarette sample main flume, unit props up for μ g/;
f-extension rate is 10 here;
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 are mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight.
3, the result calculates
As the final result's (with sulfuretted hydrogen) that measures, the result is accurate to 0.01 μ g/ and props up with the mean value of twice mensuration.Measure relative deviation between the result for twice in 10%.
According to embodiment 1 and said method, suction captures the sulfuretted hydrogen in 10 cigarette mainstream flue gas, measures result such as following table 1:
Table 7: the mensuration result of sulfuretted hydrogen in the part cigarette mainstream flue gas
| 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 (7)
1. the assay method of sulfuretted hydrogen in the cigarette mainstream flue gas; It is characterized in that: said assay method is to capture the sulfuretted hydrogen in the flue gas gas phase with the alkaline solution that contains zinc ion; And pass through N; N-dimethyl-p-phenylenediamine dihydrochloride, ammonium ferric sulfate under acid condition to the sulfuretted hydrogen that is captured derive the colour developing after; Utilization is furnished with the high performance liquid chromatograph of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector, the method qualitative, quantitative measurement that with the methylene blue is that standard items carry out.
2. assay method as claimed in claim 1 is characterized in that the concrete steps of said qualitative determination method are:
(1) 4 ~ 10 cigarette of suction, the grain phase part with 44mm or 92mm spun glass filter disc interception main flume absorbs the sulfuretted hydrogen that captures in the gas phase part with the trapping bottle that 50mL milliliter zinc acetate-sodium acetate absorbent solution is housed; Regulate after the suction capacity, on smoking machine, press GB/T 19609 standard conditions smoking cigarette samples, suction is 2 mouthfuls after finishing;
(2) in absorption liquid, add derivative reagent N immediately successively; 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; Left standstill 5 minutes, and made that the sulphion complete reaction in the absorption liquid was generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
The testing conditions of said efficient liquid phase chromatographic analysis is: stationary phase is the analysis chromatographic column of C18, the methyl alcohol aqueous formic acid (volume ratio 45:1:55) that eluent is, and type of elution is an isocratic elution; Flow velocity is 1.0mL/min.; Sample size is 10 μ L; Column temperature 30
0C; The detection wavelength of ultraviolet-visible light multiwavelength detector or ultraviolet-visible photodiode array detector is 665nm;
(4) retention time with methylene blue contrasts, and whether sulfuretted hydrogen exists in the qualitative cigarette smoke.
3. assay method as claimed in claim 1 is characterized in that the concrete steps of said method for quantitatively determining are:
(1) 4 ~ 10 cigarette of suction, the grain phase part with 44mm or 92mm spun glass filter disc interception main flume absorbs the sulfuretted hydrogen that captures in the gas phase part with the trapping bottle that 50mL milliliter zinc acetate-sodium acetate absorbent solution is housed; Regulate after the suction capacity, on smoking machine, press GB/T 19609 standard conditions smoking cigarette samples, suction is 2 mouthfuls after finishing;
(2) in absorption liquid, add derivative reagent N immediately successively; 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; Left standstill 5 minutes, and made that the sulphion complete reaction in the absorption liquid was generated as methylene blue;
(3) derivative solution is shifted and be settled to 100mL fully, get wherein that 10mL is settled to 100mL with ultrapure water, get then and detect with efficient liquid phase chromatographic analysis after an amount of dilution is crossed 0.45 μ m filter membrane;
The testing conditions of said efficient liquid phase chromatographic analysis is: stationary phase is the analysis chromatographic column of C18, and eluent is methyl alcohol aqueous formic acid (volume ratio is 45:1:55), and type of elution is an 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) 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 the described chromatographic condition of step (3), respectively the methylene blue series standard solution of preparation in the determination step (4) obtains the typical curve (R between peak area and the methylene blue concentration
2Must not be less than 0.99).
4. substitute flue gas with the laboratory environment air and deduct sample, obtain the methylene blue concentration in the analytical sample, and convert according to following formula and to obtain the content of sulfuretted hydrogen with the typical curve regression equation as blank:
X=（34.076
×f×C×V）/（319.85
×n）
In the formula:
XThe content of sulfuretted hydrogen in the-cigarette sample main flume, unit props up for μ g/;
f-extension rate is 10 here;
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 are mL;
n-smoking cigarette quantity, unit is for propping up;
34.076-sulfuretted hydrogen molecular weight;
319.85-methylene blue molecular weight;
Like claim 2 or 3 described assay methods, it is characterized in that: the concentration of said absorbent solution zinc acetate one sodium acetate is respectively (0.03mmol/mL ~ 0.09mmol/mL) (0.02mmol/mL ~ 0.06mmol/mL).
5. like claim 2 or 3 described assay methods, it is characterized in that: the concentration of said ammonium ferric sulfate solution is 0.5mmol/mL.
6. like claim 2 or 3 described assay methods, it is characterized in that: said derivative reagent N, the sulfuric acid solution of N-dimethyl-p-phenylenediamine dihydrochloride, sulfuric acid concentration are 9.2 mmol/mL, N, N-dimethyl-p-phenylenediamine dihydrochloride concentration is 0.15mmol/m.
7. like claim 2 or 3 described assay methods, it is characterized in that: its dead volume of flue gas stream of said serial connection trapping bottle is in 10ml.
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 true CN102565262A (en) | 2012-07-11 |
| CN102565262B 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) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103226137A (en) * | 2013-01-07 | 2013-07-31 | 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 |
| CN105823741A (en) * | 2016-03-11 | 2016-08-03 | 山东省化工研究院 | Air for detecting content of butyraldehyde in 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335153A (en) * | 1991-05-13 | 1992-11-24 | Mitsubishi Heavy Ind Ltd | Hydrogen sulfide detection agent |
| CN101017158A (en) * | 2007-02-08 | 2007-08-15 | 江南大学 | Method for determining sulfide in spirit |
| JP2007292565A (en) * | 2006-04-24 | 2007-11-08 | Toyo Seikan Kaisha Ltd | New methylene blue analytical method |
| 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 |
-
2011
- 2011-12-23 CN CN201110437482.3A patent/CN102565262B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04335153A (en) * | 1991-05-13 | 1992-11-24 | Mitsubishi Heavy Ind Ltd | Hydrogen sulfide detection agent |
| JP2007292565A (en) * | 2006-04-24 | 2007-11-08 | Toyo Seikan Kaisha Ltd | New methylene blue analytical method |
| 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 (6)
| Title |
|---|
| 《Biochimica et Biophysica Acta》 20090731 Kenneth R. Olson et al Is hydrogen sulfide a circulating "gasotransmitter" in vertebrate blood? 第856-863页 1-7 第1787卷, 第7期 * |
| 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》 * |
| KENNETH R. OLSON ET AL: "Is hydrogen sulfide a circulating "gasotransmitter" in vertebrate blood?", 《BIOCHIMICA ET BIOPHYSICA ACTA》 * |
| 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》 * |
| 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》 * |
| 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》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103226137A (en) * | 2013-01-07 | 2013-07-31 | 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 |
| CN105823741A (en) * | 2016-03-11 | 2016-08-03 | 山东省化工研究院 | Air for detecting content of butyraldehyde in air |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102565262B (en) | 2014-01-22 |
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 | |
| CN108802256B (en) | Method for detecting content of monoethanolamine | |
| CN101762653B (en) | Method for determining main phenolic compounds in main stream smoke of cigarette | |
| 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 | |
| CN101109735A (en) | Fluorescence photometry for immune affinity column of aflatoxin in paddy | |
| CN104020246A (en) | Method for simultaneously detecting plurality of volatile trace carbonyl compounds in atmosphere | |
| CN102590386B (en) | Method for detecting nicotine and metabolites thereof in urine sample of smoker | |
| CN102749411A (en) | Determination method for acrylamide in main stream smoke of cigarette | |
| CN102980968A (en) | Liquid chromatogram tandem mass spectrum measuring method for creatinine in urine | |
| 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 | |
| CN104237408A (en) | Method for detecting compound chlorhexidine dihydrochloride and dyclonine hydrochloride cream | |
| CN102156103B (en) | Determination method for indirectly measuring sulfureted hydrogen in mainstream smoke gas phase of cigarette by copper color method | |
| CN101435770A (en) | Nicotinic fast analysis determination method in reconstituted tobacco production waste water | |
| CN104597163B (en) | Method of determining furan in cigarette mainstream smoke by virtue of gas chromatography-mass spectrometry | |
| CN102353668A (en) | Method for determining anionic surfactant in surface water | |
| CN102914513A (en) | Analysis detection method of iron element in vanadium carbide | |
| CN107688064B (en) | Method for simultaneously detecting carbonyl compound and phenolic compound in main stream smoke of cigarette | |
| CN107703222B (en) | Method for determining trace organic amine in atmospheric particulates | |
| 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 | |
| CN104698102B (en) | Measure the method for nicotine content in cigarette mainstream smoke total particulate matter | |
| CN102636582A (en) | Method for determining content of diminazene and antipyrine in diminazene particle |
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 |