CN106501218A - A kind of assay method of Carbon bisulfide and device - Google Patents
A kind of assay method of Carbon bisulfide and device Download PDFInfo
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- CN106501218A CN106501218A CN201610970159.5A CN201610970159A CN106501218A CN 106501218 A CN106501218 A CN 106501218A CN 201610970159 A CN201610970159 A CN 201610970159A CN 106501218 A CN106501218 A CN 106501218A
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- solution
- carbon bisulfide
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- ethylenediamine
- assay method
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/47—Scattering, i.e. diffuse reflection
- G01N21/49—Scattering, i.e. diffuse reflection within a body or fluid
- G01N21/51—Scattering, i.e. diffuse reflection within a body or fluid inside a container, e.g. in an ampoule
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
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Abstract
Present invention is disclosed a kind of assay method of Carbon bisulfide and device, it is to absorb alkaline ethylenediamine solution excessive for Carbon bisulfide, make Carbon bisulfide and alkali and diethylamine react the deliquescent ethylenediamine dithio formate product of generation, the ethylenediamine dithio formate product in absorbing liquid again with acid solution（Or the element in acid solution）Mixing reacts generation with volatile volatile matter, by carrying out Quick gas-liquid separation to the solution containing volatile matter, makes the escaping gas that isolates pass through light scattering method（Or atomic spectroscopy）To determine the concentration of Carbon bisulfide.Also disclosing simultaneously carries out curing carbon measuring equipment, when mainly mixed solution is by flowing through above lamina membranacea, carries out bubbling by carrier gas is led to below lamina membranacea to solution above, so as to carry out gas-liquid separation.The volatile matter that isolates is used for the preparation of atomic spectrum gaseous state sample introduction or chemical vapor deposition precursor.
Description
Technical field
The invention belongs to environmental science, more particularly to a kind of assay method of Carbon bisulfide and device.
Background technology
Carbon bisulfide is colourless or the toxic liquid of yellow effumability, can manufacture viscose rayon, four atmosphere carbon, promotion
The products such as agent. it is also a kind of broad-spectrum organic solvent, its boiling point is relatively low (4 3 DEG C of .6), inflammable and explosive (quick-fried
The fried limit:1 .2 5% of lower bound, 44 % of high limit).Carbon disulfide gas through respiratory tract invade human body after, can make one headache,
Dizziness, general weakness, vision and sensory disturbance, digestive disorders. severe patient can cause refreshing essence system disorders.Therefore, Accurate Determining
Carbon bisulfide is significant
The method for being usually used in determining Carbon bisulfide at present has gas chromatography and absorption photometry.The former operates cumbersome, the latter
Sensitivity is low, and there is H2S etc. is disturbed, and can not meet the requirement of microanalysiss in environmental sample well.The latter's result is unstable
Fixed, and detection limit is poor.
At present, the present inventor under study for action, is acidified ethylenediamine dithiocarbonic acid sodium by online, and then sharp separation is generated
Volatile matter, it is found that volatile matter has very strong light scattering, therefore the present inventor is with regard to a kind of this curing Carbon analysis side of proposition
Method and device, so that complete the present invention.
Content of the invention
The present invention discloses a kind of assay method of Carbon bisulfide first, it is characterised in that by the excessive alkali of Carbon bisulfide
Property ethylenediamine solution absorb, make alkali and Carbon bisulfide and diethylamine react generation ethylenediamine dithio formate.Absorbing liquid
In ethylenediamine dithio formate again with acid solution or the acid solution containing element mixes to react and makes two sulfur of ethylenediamine
Acute pyogenic infection of nails hydrochlorate generates the ethylenediamine dithiocarbonic acid with volatile light scatter properties, or generates with volatile ethylenediamine
Dithiocarbonic acid element complex, by carrying out Quick gas-liquid separation to solution, makes the ethylenediamine dithiocarbonic acid gas that isolates
Body or ethylenediamine dithiocarbonic acid element complex determine the concentration of Carbon bisulfide by light scattering method or atomic spectroscopy.
In the present invention, absorbing liquid used refers to the ethylenediamine solution of alkalescence, refers to alkaline solutions of the pH more than 7.It is preferred that pH
Alkali metal potassium of the value more than 10, sodium, lithium（Or alkaline earth metals calcium, magnesium, strontium）Hydroxide solution and ethylenediamine mixed solution.
Wherein the content of hydroxide and the content of ethylenediamine are excessive for Carbon bisulfide to be determined.
In the present invention, reacted solution is reacted to online with acid solution through gas-liquid separation from absorbing liquid, when total
Between be less than 10 seconds, preferably smaller than 5 seconds.
In the present invention, the acidity of absorbing liquid solution after line is mixed with acid solution, is preferably inhaled between 0.1M for 0.01
The acidity of receipts liquid solution after line is mixed with acid solution is for 0.012 between 0.05M.
In the present invention, light scattering method excitation wavelength used during determination of volatile matter is the preferred excitation wavelengths of 190nm-800nm.
For 190nm-280nm.
As a particularly suitable instrument, coordinate the gas-liquid point in the present invention from an atomic fluorescence of zero dispersion photometer again
From device, it is easy to realize the measure of the present invention.
When the sample for determining is aqueous solution, then it is by adding excessive ethylenediamine and hydroxide to aqueous solution to be measured
To prepare testing sample solution.
In the present invention, when the concentration of Carbon bisulfide is determined using atomic spectroscopy, now also containing solid in acid solution
Quantitative metal ion.Its principle is that Carbon bisulfide can generate volatile gold with ethylenediamine and metal ion in acid condition
Category complex.When metal ion one timing of content in an acidic solution, two sulfur in the concentration of the metal volatile matter of generation and solution
Change concentration of carbon linear.Thus the atomic spectrum intensity of metal can be determined to determine the content of Carbon bisulfide.Using this
During method, described metal ion is preferred（But it is not limited to）Content is in the zinc of 5-100ppb, cadmium, nickel, cobalt, ferrum, manganese and chromium.
The present invention also proposes the device determined for Carbon bisulfide, is characterised by that the device includes acid solution or containing element
Acid solution ingress pipe（1）, the ingress pipe 2 of diethyldithio carbamate solution containing Carbon bisulfide, peristaltic pump 3,
3 ', 4 gas-liquid separator 5 of tee T, carrier gas inlet 6, carrier gas outlet 7 and discharging of waste liquid pipe 8；First peristaltic pump 3 passes through threeway 4
Be connected with gas-liquid separator 5, gas-liquid separator 5 have where bottom one a diameter of 25-50 centimetre, aperture 50-150 mesh many
The permeable watertight lamina membranacea 9 in hole, the permeable watertight lamina membranacea diameter of gas-liquid separator porous are preferably 30-40 centimetre, lamina membranacea hole
Footpath is preferably 70-90 mesh.Be connected with discharging of waste liquid pipe 8 on the lamina membranacea of permeable watertight, its discharging of waste liquid pipe and second wriggling
Pump（3’）It is connected.When mixed solution is by flowing through above lamina membranacea, bubbling is carried out to solution above by carrier gas is led to below lamina membranacea,
So as to carry out gas-liquid separation.
Acid solution（Or the acidity containing element）Sample solution ingress pipe 1, the diethyl-dithio amino containing Carbon bisulfide
Formates（M-DDTC）The flow velocity of the ingress pipe 2 of solution is 1.0-3.0 ml/mins.It is preferred that 1.5-2.5 ml/mins.
Diethyldithio carbamate on the device（M-DDTC）Solution and Element Solution on-line mixing to be measured
And the gas-liquid separation time amounts to and is less than 10 seconds.
Diethyldithio carbamate（M-DDTC）Solution and Element Solution on-line mixing to be measured and gas-liquid separation
Time amounts to and is less than 5 seconds.
Mixed solution acidity on the device is 0.0125-0.2 mol/Ls.
High spot reviews of the present invention Carbon bisulfide generates diethylamine dithio formate with diethylamine and alkali hydroxide reaction
Afterwards, the diethylamine dithiocarbonic acid that its product is generated in acid condition, or diethylamine dithiocarbonic acid-metal complex
Volatility.By this research, spy solves a curing Carbon analysis difficult problem, a kind of curing Carbon analysis side especially set out
Method.
The good effect that the assay method and device of Carbon bisulfide disclosed by the invention have compared with prior art exists
In：
（1）Finding speed is fast, as long as by the diethylamine dithiocarbonic acid containing Carbon bisulfide to be measured or its alkali that formed in element
Property aqueous solution and acid solution mixing and then carry out gas-liquid separation, instrument can determine the content of Carbon bisulfide.Unlike gas phase color
Spectrum and colorimetric spectrophotometer like that, need the pretreatment process that grows very much.
（2）Detection limit is good, between the detection limit 0.05ppm of the Carbon bisulfide determined by the present invention is arrived.It is better than existing point
Photolorimetry.
（3）Without any interference.Whether muddy solution or coloured solution, this method can be determined.And light splitting
Rule can not determine colored solutions.Especially disturbed by hydrogen sulfide.
Description of the drawings：
Fig. 1 is the installation drawing of the sample introduction suitable for the present invention；Wherein：
1st, acid solution or the acid solution ingress pipe containing element
2nd, the diethyldithio carbamate solution ingress pipe containing Carbon bisulfide
3rd, the first peristaltic pump, 3 ' second peristaltic pumps
4th, tee T 5, gas-liquid separator
6th, carrier gas inlet 7, carrier gas outlet
8th, discharging of waste liquid pipe 9, the permeable watertight lamina membranacea of aperture 50-150 mesh porous.
Specific embodiment
In order to more fully explain the enforcement of the present invention, there is provided following present invention prepare embodiment.These enforcements are real
Example is only to explain rather than limit the scope of the present invention.
Embodiment 1
（1）50 liters of certain working space gaseous sample is adopted with gas sampler, the Carbon bisulfide in gaseous sample is made by excessive hydrogen
Sodium oxide（pH=13）Absorb with diethylamine (40mM) mixed solution, then, adopt peristaltic pump to take out with the flow velocity of 1.2 ml/mins
Above-mentioned absorbent solution is taken, while with the hydrochloric acid solution that certain flow rate one acidity of extraction is 0.2 M, adjusting sour sample feeding pipe flow makes
The final acidity of two mixed solutions makes two strands of 1 sampling devices of solution by specification accompanying drawing converge in a tee T in 0.05M.
React after conjunction.
（2）By the volatile matter of generation and reacted solution, gas-liquid separator in 1 sampling device of Figure of description is carried out
Separate；
（3）The DDTC acid volatile matters that isolates are imported into an atomic fluorescence of zero dispersion photometer and carry out the scattered color measure of light（Use zinc
Hollow cathode lamp most excitation source）, Carbon bisulfide scattering strength and standard Carbon bisulfide are dissipated after intensity of colour contrast, are obtained big
In gas, content is 20ppm.This measured value is had with spectrophotometry value coincide well.
Embodiment 2
（1）To in 100 milliliters of certain aqueous sample to be measured excessive sodium hydroxide and diethylamine is added (to make mixed hydroxide
Na concn 0.15M, ethylenediamine 100mM), then, adopt peristaltic pump to extract above-mentioned absorbent solution with the flow velocity of 1.7 ml/mins,
While with the salpeter solution containing zinc 20ppb that same flow velocity one acidity of extraction is 0.2 M. make two strands of solution by specification accompanying drawings
1 sampling device reacts after converging in a tee T.
（2）By the volatile matter of generation and reacted solution, gas-liquid separator in 1 sampling device of Figure of description is carried out
Separate；
（3）The volatile matter of the DDTC zinc that isolates is imported into an atomic fluorescence of zero dispersion photometer and carries out atom fluorimetry
Determine, by testing the linear relationship of the fluorescence intensity for solving zinc and sulfuration concentration of carbon, obtaining content in waste water Carbon bisulfide is
5ppm.This measured value is had with spectrophotometry value coincide well.
Embodiment 3
A kind of device formed for element evaporation thing,
The device includes acidity（Or the acidity containing element）Solution ingress pipe 1, the diethyl-dithio amino first containing Carbon bisulfide
The ingress pipe 2 of acid salt solution, peristaltic pump 3,3 ', 4 gas-liquid separator 5 of tee T, carrier gas inlet 6, carrier gas outlet 7 and discharging of waste liquid
Pipe 8；First peristaltic pump 3 is connected with gas-liquid separator 5 by threeway 4, and gas-liquid separator 5 has a diameter where bottom
For 30 centimetres, the permeable watertight lamina membranacea 9 of 80 mesh porous of aperture, when mixed solution is by flowing through above lamina membranacea, by lamina membranacea under
The logical carrier gas in face carries out bubbling to solution above, so as to carry out gas-liquid separation.
Acid solution wherein on the device（Or the acid solution containing element）Ingress pipe（1）, containing Carbon bisulfide diethyl
Base dithiocar-bamate（（M-DDTC））The ingress pipe of solution（2）Flow velocity be 1.0-2.5 ml/mins, preferably 1.5-
2.0 ml/mins, the now ratio of two flow velocitys preferably 1:1.
Diethyldithio carbamate on the device（M-DDTC）Solution and acid solution on-line mixing to be measured
And the gas-liquid separation time amounts to and is less than 10 seconds.
Diethyldithio carbamate（M-DDTC）Solution with when the acid solution on-line mixing and gas-liquid separation
Between amount to be less than 5 seconds.
Mixed solution acidity on the device is 0.0125-0.2 mol/Ls.
Embodiment 4
Contrast test
Conclusion：
（1）Finding speed of the present invention is fast
（2）Do not disturbed by sample solution color.Especially do not disturbed by hydrogen sulfide.
（3）Detection limit is low, has method better than current.
After the preferred embodiment for describing in detail, it is familiar with the skilled worker and is clearly understood that, without departing from above-mentioned
Various change and modification can be carried out under claim and spirit, all technical spirits according to the present invention are to above example institute
Any simple modification, equivalent variations and the modification that makees, belongs to the scope of technical solution of the present invention.
Claims (10)
1. a kind of assay method of Carbon bisulfide, it is characterised in that by alkaline ethylenediamine solution absorption excessive for Carbon bisulfide,
Make Carbon bisulfide and alkali and diethylamine react and generate deliquescent ethylenediamine dithio formate product, the second in absorbing liquid
Diamidogen dithio formate product again with acid solution or the acid solution containing element mix react generation have volatility
Volatile matter, by carrying out Quick gas-liquid separation to the solution containing volatile matter, the escaping gas isolated is dissipated by light
Penetrate method or atomic spectroscopy to determine the concentration of Carbon bisulfide.
2. assay method according to claim 1, alkaline ethylenediamine solution are alkali metal of the pH value more than 7, alkaline-earth metal
Hydroxide solution and ethylenediamine mixed solution.
3. assay method according to claim 2, alkaline ethylenediamine solution are alkali metal of the pH value more than 10, alkaline-earth metal
Hydroxide solution and ethylenediamine mixed solution；Described alkali metal is potassium, sodium, lithium；Alkaline-earth metal refer to calcium, magnesium,
Strontium.
4. assay method according to claim 1, wherein absorbing liquid acidity of solution after line is mixed with acid solution is
0.01 between 0.1M.
5. method according to claim 4, the acidity of absorbing liquid solution after line is mixed with acid solution are arrived for 0.012
Between 0.05M.
6. assay method according to claim 1, light scattering method therein are referred to：Light scattering method excitation wavelength is
190nm -800nm.
7. assay method according to claim 1, wherein when the sample for determining is aqueous solution, is then by water to be measured
Solution adds excessive ethylenediamine and hydroxide to prepare testing sample solution.
8. assay method according to claim 1, when the concentration of Carbon bisulfide is determined using atomic spectroscopy, now
Also contain the deliquescent metal ion of fixed amount in acid solution.
9. assay method according to claim 1, described metal ion content the zinc of 5-100ppb, cadmium, nickel, cobalt,
Ferrum, manganese and chromium.
10. a kind of device determined for Carbon bisulfide, is characterised by that the device includes the acidity containing acid solution or containing element
Solution ingress pipe（1）, containing Carbon bisulfide diethyldithio carbamate solution ingress pipe（2）, peristaltic pump（3,3 '）、
Tee T（4）, gas-liquid separator（5）, carrier gas inlet（6）, carrier gas outlet（7）With discharging of waste liquid pipe（8）；First peristaltic pump
（3）By threeway（4）With gas-liquid separator（5）It is connected, gas-liquid separator（5）There is an a diameter of 25-50 where bottom
Centimetre, the permeable watertight lamina membranacea of aperture 50-150 mesh porous（9）, when mixed solution is by flowing through above lamina membranacea, by lamina membranacea
Below lead to carrier gas bubbling is carried out to solution above, so as to carry out gas-liquid separation, the volatile matter that isolates be used for light scattering method or
Atomic spectroscopy is determined, and is connected with discharging of waste liquid pipe on the lamina membranacea of permeable watertight（8）, its discharging of waste liquid pipe and second wriggling
Pump（3’）It is connected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610970159.5A CN106501218B (en) | 2016-11-07 | 2016-11-07 | A kind of measuring method and device of carbon disulfide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610970159.5A CN106501218B (en) | 2016-11-07 | 2016-11-07 | A kind of measuring method and device of carbon disulfide |
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| Publication Number | Publication Date |
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| CN106501218A true CN106501218A (en) | 2017-03-15 |
| CN106501218B CN106501218B (en) | 2019-10-15 |
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| CN201610970159.5A Expired - Fee Related CN106501218B (en) | 2016-11-07 | 2016-11-07 | A kind of measuring method and device of carbon disulfide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110806384A (en) * | 2019-12-06 | 2020-02-18 | 天津师范大学 | Sample introduction device of analytical instrument and use method |
| CN111551511A (en) * | 2020-06-04 | 2020-08-18 | 江苏康达检测技术股份有限公司 | Spectrophotometry for measuring content of carbon disulfide in air |
| CN114689715A (en) * | 2020-12-29 | 2022-07-01 | 北京海浈医药科技有限公司 | Method for detecting content of trimethylamine or trimethylamine salt |
-
2016
- 2016-11-07 CN CN201610970159.5A patent/CN106501218B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110806384A (en) * | 2019-12-06 | 2020-02-18 | 天津师范大学 | Sample introduction device of analytical instrument and use method |
| CN111551511A (en) * | 2020-06-04 | 2020-08-18 | 江苏康达检测技术股份有限公司 | Spectrophotometry for measuring content of carbon disulfide in air |
| CN114689715A (en) * | 2020-12-29 | 2022-07-01 | 北京海浈医药科技有限公司 | Method for detecting content of trimethylamine or trimethylamine salt |
| CN114689715B (en) * | 2020-12-29 | 2024-01-16 | 北京海浈医药科技有限公司 | Method for detecting trimethylamine or trimethylamine salt content |
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| CN106501218B (en) | 2019-10-15 |
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