CN107632087A - A kind of method that cyanide in white wine is determined using headspace gas chromatography - Google Patents
A kind of method that cyanide in white wine is determined using headspace gas chromatography Download PDFInfo
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- CN107632087A CN107632087A CN201710818339.6A CN201710818339A CN107632087A CN 107632087 A CN107632087 A CN 107632087A CN 201710818339 A CN201710818339 A CN 201710818339A CN 107632087 A CN107632087 A CN 107632087A
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Abstract
The invention discloses a kind of method that cyanide in white wine is determined using headspace gas chromatography, including the measure of (1) standard working curve, the pretreatment of (2) Wine Sample, the detection of (3) Wine Sample.The headspace gas chromatography of the present invention carries out quantitative analysis to the micro cyanide in wine sample indirectly by determining the hydrogen chloride in gas phase, sample is by 50 DEG C of hatchings, it is volatilizable less to the component in gas phase, separation in the case where sample introduction needle temperature is 60 DEG C, sample introduction speed is 500 μ L/s Jing Guo chromatographic column, object is disturbed less, compared to AAS, Headspace Gas Chromatography result is more accurate.
Description
Technical field
It is more particularly to a kind of to be determined using headspace gas chromatography the present invention relates to the detection technique field of cyanide in white wine
The method of cyanide in white wine.
Background technology
Cyanide is a kind of strong toxic condition pollutant containing cyano group, including simple cyanide, complex cyanide and is had
Machine cyanide (organic nitrile).It is widely present in nature, and in plant, cyanide is generally combined with glycan molecule, and with containing
Cyanogen glucosides (cyanogeniclycoside) form is present.Cyanide can enter human body by respiratory tract or alimentary canal, with line grain
Ferric iron in vivo oxidation type cytochrome oxidase combines, and the ferric iron back in oxidizing ferment is prevented, so as to hinder cell
Eupnea, make body hypoxia death.Because cyanide has serious toxic action, Spirit and its assembled alcoholic drinks food to human body
GB2757-2012 regulations cyanide limitation should be less than 8.0g/L (in terms of HCN, by 100% alcoholic strength folding in safe national standard
Calculate).Meanwhile cyanide is also urethanes generation precursor substance in white wine.Therefore, the assay method of micro cyanide is
The important technical of liquor industry quality safety monitoring.
At present, the method for determining cyanide content in food is more, such as isonicotinic acid-pyrazolone method, isonicotinic acid-barbital
The photometries such as acid system, Pyridine-barbituric acid, headspace gas chromatography, electrochemical process and volumetric method etc..Wherein isonicotinic acid-Ba Bi
Appropriate acid system is national standard GB/T5009.48 cyaniding object detecting methods, but detection is limited to 0.3g/L when this method is used for liquor determination, still
The measure requirement of more micro white wine hydrogen cyanide can not be met.Also, spectrophotometric principles are cyanides in wine weak
React generation hydrogen chloride under acid condition with toluene-sodium-sulfonchloramide, hydrogen chloride and isonicotinic acid react generates glutaconaldehyde through hydrolysis, then with a bar ratio
Appropriate acid reaction generates bluish violet complex compound.Microcomponent is more in white wine, it is understood that there may be the similar thing with glutaconaldehyde structure
Matter, generation bluish violet complex compound can be equally reacted with barbiturates, so as to cause measurement result higher.
The content of the invention
It is an object of the invention to：For being asked in national standard using spectrophotometry precision is low, measurement result is higher
Topic, the present invention provide a kind of precision the high method for determining cyanide in white wine using headspace gas chromatography.
The technical solution adopted by the present invention is as follows：
A kind of method that cyanide in white wine is determined using headspace gas chromatography, comprises the following steps：
(1) measure of standard working curve：
A), with distilled water constant volume, concentration is obtained in 50mL volumetric flasks using 50mg/L potassium cyanide standard liquid 0.5mL
For 500 μ g/L potassium cyanide standard liquid；
B) 12mL, 11.8mL, 10mL, 9.8mL, 9mL distilled water are drawn respectively in 5 20mL ml headspace bottle, are added successively
Enter 50 μ L, 100 μ L, 200 μ L, 400 μ L, 800 μ L 500 μ g/L potassium cyanide standard liquid；
C) the μ L phosphoric acid solutions of provisional configuration 200, the volume ratio of phosphoric acid and water is 1 in phosphoric acid solution:5；The μ L of provisional configuration 200
Liquor natrii hypochloritis, available chlorine content is more than 5% in liquor natrii hypochloritis；Phosphoric acid solution and liquor natrii hypochloritis divide equally when configuring
Not Cai Yong vortex mixer mixed, mixing number be 2~3 times, hybird environment is vacuum environment, phosphoric acid solution and hypochlorous acid
The water used in sodium solution is ultra-pure water；
D) 200 μ L phosphoric acid solutions and 200 μ L liquor natrii hypochloritises are added to 5 ml headspace bottles, tighten bottle cap sealing rapidly,
All ml headspace bottles are fixed on rotation blending instrument, and mixed with 20rmp/min rotating speed uniform rotation, rotation time 2
~3 minutes, ml headspace bottle constant temperature is warming up to 50~80 DEG C in rotation process；
E) mixed 5 ml headspace bottles are put into chromatographic sample injection disc simultaneously to be measured；
(2) pretreatment of Wine Sample：
1) it is another to take 20mL ml headspace bottles to add 50 μ L sulfur eliminations after cleaning, the mixing of 9.2mL distilled water jog is added, adds and treats
The μ L of wine sample 400 are surveyed, the 200 μ L phosphoric acid solutions with reference to step c) configurations and 200 μ L liquor natrii hypochloritises is separately added into, tightens rapidly
Bottle cap sealing, mix and heat up using method in step d)；
(3) detection of Wine Sample：
Wine Sample is extracted into headspace gas after head-space sampler and is measured using capillary chromatography, wherein,
The head space condition of the head-space sampler is：Incubation temperature：50℃；Brooding time：10min；Vibration frequency：250rmp/min；
Sample introduction needle temperature：60℃；Sample size：500uL, inhale sample speed：250 μ L/s, sample introduction speed：500μL/s；
The chromatographic condition of the capillary chromatography is：The injector temperature of capillary chromatographic column：150℃；It is not diverted into
Sample；Flow rate of carrier gas：30mL/min；Column oven：200 DEG C are risen to 20 DEG C/min after 40 DEG C of lasting 4min, continues 4min；Detector
Temperature：260℃.
In above method, the capillary chromatographic column is HP-5 capillary chromatographic columns, length 30m, internal diameter 3.0mm, thickness
0.25μm。
In above method, it according to mass ratio is 1 that the sulfur elimination, which is,:The phthalocyanine and phthalocyanine sulfonic acids cobalt of 1 mixing.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
1st, headspace gas chromatography of the invention is by determining the hydrogen chloride in gas phase come indirectly to the micro cyanogen in wine sample
Compound carries out quantitative analysis, and sample is hatched by 50 DEG C, volatilizable less to the component in gas phase, is 60 in sample introduction needle temperature
DEG C, sample introduction speed be separation Jing Guo chromatographic column under 500 μ L/s, object be disturbed it is less, compared to AAS, head space
Gas chromatography measurement result is more accurate.
2nd, phosphoric acid solution of the present invention and liquor natrii hypochloritis are configured using ultra-pure water, and purity is higher, reduce impurity to detection
Influence, and by the mixing of the vortex mixer in vacuum environment, mixing evenly, improves the measure of standard working curve
Precision；Sodium hypochlorite is measured instead of toluene-sodium-sulfonchloramide, can effectively solve toluene-sodium-sulfonchloramide easily lump, decomposition failure and difficulty not easy to maintain
Topic, can further solve the problems, such as to determine inaccurate.
3rd, degree of mixing can be improved using blending instrument progress solution mixing is rotated during standard working curve of the invention measure,
And 50~80 DEG C are warming up in advance in mixing, can make it that solute does not separate in solution, solution density is equal after can guarantee that mixing
It is even consistent, so as to further increase the accuracy of measure.
4th, the present invention can be removed part sulfide in white wine using sulfur elimination, and it is molten with phosphoric acid can effectively to solve sulfide
The problem of liquid and liquor natrii hypochloritis carry out neutralization reaction so that active ingredient is preserved, and can also eliminate sulfide pair
The influence of measure.
Brief description of the drawings
Fig. 1 is the standard working curve of HCN in the present invention；
Embodiment
The present invention is elaborated with reference to Fig. 1.
A kind of method that cyanide in white wine is determined using headspace gas chromatography, comprises the following steps：
(1) measure of standard working curve：
A), with distilled water constant volume, concentration is obtained in 50mL volumetric flasks using 50mg/L potassium cyanide standard liquid 0.5mL
For 500 μ g/L potassium cyanide standard liquid；
B) 12mL, 11.8mL, 10mL, 9.8mL, 9mL distilled water are drawn respectively in 5 20mL ml headspace bottle, are added successively
Enter 50 μ L, 100 μ L, 200 μ L, 400 μ L, 800 μ L 500 μ g/L potassium cyanide standard liquid；
C) the μ L phosphoric acid solutions of provisional configuration 200, the volume ratio of phosphoric acid and water is 1 in phosphoric acid solution:5；The μ L of provisional configuration 200
Liquor natrii hypochloritis, available chlorine content is more than 5% in liquor natrii hypochloritis；Phosphoric acid solution and liquor natrii hypochloritis divide equally when configuring
Not Cai Yong vortex mixer mixed, mixing number be 2~3 times, hybird environment is vacuum environment, phosphoric acid solution and hypochlorous acid
The water used in sodium solution is ultra-pure water；
D) 200 μ L phosphoric acid solutions and 200 μ L liquor natrii hypochloritises are added to 5 ml headspace bottles, tighten bottle cap sealing rapidly,
All ml headspace bottles are fixed on rotation blending instrument, and mixed with 20rmp/min rotating speed uniform rotation, rotation time 2
~3 minutes, ml headspace bottle constant temperature is warming up to 50~80 DEG C in rotation process；
E) mixed 5 ml headspace bottles are put into chromatographic sample injection disc simultaneously to be measured；
(2) pretreatment of Wine Sample：
1) it is another to take 20mL ml headspace bottles to add 50 μ L sulfur eliminations after cleaning, the mixing of 9.2mL distilled water jog is added, adds and treats
The μ L of wine sample 400 are surveyed, the 200 μ L phosphoric acid solutions with reference to step c) configurations and 200 μ L liquor natrii hypochloritises is separately added into, tightens rapidly
Bottle cap sealing, mix and heat up using method in step d)；
(3) detection of Wine Sample：
Wine Sample is extracted into headspace gas after head-space sampler and is measured using capillary chromatography, wherein,
The head space condition of the head-space sampler is：Incubation temperature：50℃；Brooding time：10min；Vibration frequency：250rmp/min；
Sample introduction needle temperature：60℃；Sample size：500uL, inhale sample speed：250 μ L/s, sample introduction speed：500μL/s；
The chromatographic condition of the capillary chromatography is：The injector temperature of capillary chromatographic column：150℃；It is not diverted into
Sample；Flow rate of carrier gas：30mL/min；Column oven：200 DEG C are risen to 20 DEG C/min after 40 DEG C of lasting 4min, continues 4min；Detector
Temperature：260℃.
In the present embodiment, it is determined that after incubation temperature and brooding time in head-space sampler, it is thus necessary to determine that sample introduction needle
Temperature and sample introduction speed.Because derivatization product CNCl boiling point is 13~14 DEG C, the boiling point of sample solvent water is 100 DEG C, is incubated
It is 50 DEG C to change temperature, therefore sample introduction needle temperature is less than the boiling point of water, therefore, the identical white wine sample of this experimental design higher than incubation temperature
The product sample introduction under the conditions of 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C respectively, the results are shown in Table 1.
Influence of the sample introduction needle temperature of table 1 to result
| Sample number into spectrum | Equilibrium temperature | Equilibration time | Peak area |
| 1 | 60 | 10 | 13825.2 |
| 2 | 70 | 10 | 15523.5 |
| 3 | 80 | 10 | 16135.6 |
| 4 | 90 | 10 | 16548.1 |
The result of table 1 shows that peak area response is raised and increased with temperature, improves sample introduction needle temperature and is advantageous to improve detection
Sensitivity, but to increase trend gradually gentle for response.Consider that high temperature can cause headspace gas hypertonia, during sampling syringe from
The pressure for opening the moment needle point of sample bottle is reduced to atmospheric pressure, and a part of sample can be caused to be escaped from needle point, made on the contrary under sensitivity
Drop, analytical error increase, and same sample is measured at 60 DEG C, relative standard deviation RSD is 7.7%, meets survey
Determine sensitivity and repeatability requires.Therefore, 60 DEG C of this experimental selection is sample introduction needle temperature.
Sample introduction speed is the flow that sample enters flow chamber, injects sample, sample gasifies in injection port, subsequently into chromatogram
Post, then form chromatographic peak to enter detector.If sample introduction speed is fast, the peak type of chromatographic peak is concentrated.If sample introduction at leisure, sample
Product will enter chromatographic column, detector in batches, and the peak type run out is disperseed, and has an effect on the measure of peak area.
Influence of the sample introduction speed of table 2 to result
| Sample introduction needle temperature (DEG C) | Sample introduction speed (μ L/s) | Peak area |
| 60 | 400 | 14174.2 |
| 60 | 500 | 14835.6 |
| 60 | 600 | 15238.4 |
| 60 | 700 | 15945.3 |
The result of table 2 shows that peak area response is accelerated two with sample introduction speed and increased, but increase tendency unobvious, can recognize
Vapor liquid equilibrium is reached in 60 DEG C of sample introduction needle, sample introduction speed 400 for system.To ensure that vapor-liquid two phases have time enough
Reach balance, avoid head space overlong time to cause ml headspace bottle air-tightness to be deteriorated and cause the reduction of dosing accuracy again, meanwhile, it is
Detection efficiency is improved, the sample introduction speed of this experimental selection is 500 μ L/s.Test result indicates that same sample is in 60 DEG C, sample introduction speed
For degree in 500 μ L/s, the relative standard deviation RSD for measuring CNCl contents is 4.9%, meets measure sensitivity and repeatability requires.
After sample introduction needle temperature and sample introduction speed is determined, the processing method as described in step 1 carries out derivation process configuration not
With the potassium cyanide standard liquid of concentration, with corresponding HCN concentration (μ g/L) for abscissa, peak area is that ordinate draws standard song
Line.As a result show, linear relationship is good in the range of 1 μ g/L to 100 μ g/L, can obtain regression equation y=187.8x+179.6, returns
Return coefficients R2=0.997, working curve is shown in Fig. 1.
In the case where head space condition and chromatographic condition are constant, 5 times are measured to certain Wine Sample different time, as a result
It is shown in Table 3.
The headspace gas chromatography tight ness rating result of the test of table 3
| Pendulous frequency | 1 | 2 | 3 | 4 | 5 | Relative standard deviation RSD (%) |
| Cyanide content | 42 | 41 | 39 | 38 | 38 | 4.6 |
From table 3 it can be seen that using middle cyanide content result in 5 measure Wine Samples of headspace gas chromatography
RSD is 4.564%, and precision is higher.
Standard liquid to being separately added into 30 μ g/L, 60 μ g/L, 80 μ g/L in Wine Sample, mark-on is calculated after sample introduction analysis
The rate of recovery, it the results are shown in Table 4.
The headspace gas chromatography recovery of standard addition of table 4
As can be seen from Table 4, the recovery of standard addition of Wine Sample is higher in 82%-89%, recovery of standard addition.
The headspace gas chromatography used in the present embodiment is by determining the cyanogen chloride in gas phase come indirectly in wine sample
Micro cyanide carries out quantitative analysis, and sample passes through 60 DEG C of incubation in low temperature, volatilizable less to the component in gas phase, and have passed through
The separation of chromatographic column, object are disturbed less.Method is in 1~100 μ g/L range of linearity internal regression coefficient 0.997, phase
It is 4.564% to standard deviation RSD, the rate of recovery is 82~89%, compared to AAS, Headspace Gas Chromatography result
It is more accurate.
For the precision of further optimization measurement result, the capillary chromatographic column selects HP-5 capillary chromatographic columns, length
30m, internal diameter 3.0mm, 0.25 μm of thickness, are advantageous in the accurate of measurement result.
For the precision of further optimization measurement result, it according to mass ratio is 1 that the sulfur elimination, which is,:The phthalocyanine and phthalein of 1 mixing
Cyanines sulfonic acid cobalt.Phthalocyanine and phthalocyanine sulfonic acids cobalt can react to form RSNH4, H2O, (NH4) 2CO2S and NH4 with most of sulfide
Deng more stable compound, the reaction effect of follow-up phosphoric acid and sodium hypochlorite and cyanide thereby may be ensured that.
It is embodiments of the invention as described above.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the enlightenment of the present invention, the technical schemes that are same or similar to the present invention, each fall within this
Within the protection domain of invention.
Claims (3)
- A kind of 1. method that cyanide in white wine is determined using headspace gas chromatography, it is characterised in that comprise the following steps：(1) measure of standard working curve：A) using 50mg/L potassium cyanide standard liquid 0.5mL in 50mL volumetric flasks, with distilled water constant volume, obtaining concentration is 500 μ g/L potassium cyanide standard liquid；B) 12mL, 11.8mL, 10mL, 9.8mL, 9mL distilled water are drawn respectively in 5 20mL ml headspace bottle, sequentially add 50 μ L, 100 μ L, 200 μ L, 400 μ L, 800 μ L 500 μ g/L potassium cyanide standard liquid；C) the μ L phosphoric acid solutions of provisional configuration 200, the volume ratio of phosphoric acid and water is 1 in phosphoric acid solution:5；Provisional configuration L chlorine of 200 μ Acid sodium solution, available chlorine content is more than 5% in liquor natrii hypochloritis；Phosphoric acid solution and liquor natrii hypochloritis respectively adopt when configuring Mixed with vortex mixer, mixing number is 2~3 times, and hybird environment is vacuum environment, and phosphoric acid solution and sodium hypochlorite are molten The water used in liquid is ultra-pure water；D) 200 μ L phosphoric acid solutions and 200 μ L liquor natrii hypochloritises are added to 5 ml headspace bottles, tightens bottle cap sealing rapidly, by institute There is ml headspace bottle to be fixed on rotation blending instrument, and mixed with 20rmp/min rotating speed uniform rotation, 2~3 points of rotation time Clock, ml headspace bottle constant temperature is warming up to 50~80 DEG C in rotation process；E) mixed 5 ml headspace bottles are put into chromatographic sample injection disc simultaneously to be measured；(2) pretreatment of Wine Sample：1) it is another to take 20mL ml headspace bottles to add 50 μ L sulfur eliminations after cleaning, the mixing of 9.2mL distilled water jog is added, adds wine to be measured The μ L of sample 400, the 200 μ L phosphoric acid solutions with reference to step c) configurations and 200 μ L liquor natrii hypochloritises are separately added into, tighten bottle cap rapidly Sealing, is mixed and is heated up using method in step d)；(3) detection of Wine Sample：Wine Sample is extracted into headspace gas after head-space sampler and is measured using capillary chromatography, wherein, it is described The head space condition of head-space sampler is：Incubation temperature：50℃；Brooding time：10min；Vibration frequency：250rmp/min；Sample introduction Pin temperature：60℃；Sample size：500uL, inhale sample speed：250 μ L/s, sample introduction speed：500μL/s；The chromatographic condition of the capillary chromatography is：The injector temperature of capillary chromatographic column：150℃；Splitless injecting samples；Carry Gas velocity：30mL/min；Column oven：200 DEG C are risen to 20 DEG C/min after 40 DEG C of lasting 4min, continues 4min；Detector temperature： 260℃。
- 2. a kind of method that cyanide in white wine is determined using headspace gas chromatography according to claim 1, its feature exist In, the capillary chromatographic column be HP-5 capillary chromatographic columns, length 30m, internal diameter 3.0mm, 0.25 μm of thickness.
- 3. a kind of method that cyanide in white wine is determined using headspace gas chromatography according to claim 1, its feature exist It according to mass ratio is 1 to be in, the sulfur elimination:The phthalocyanine and phthalocyanine sulfonic acids cobalt of 1 mixing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112881548A (en) * | 2021-01-12 | 2021-06-01 | 济南趵突泉酿酒有限责任公司 | Method for rapidly detecting cyanide in sorghum |
| CN115166106A (en) * | 2021-11-26 | 2022-10-11 | 国家食品安全风险评估中心 | Method for detecting cyanide content in white spirit or white spirit fermentation process sample |
-
2017
- 2017-09-12 CN CN201710818339.6A patent/CN107632087A/en active Pending
Non-Patent Citations (10)
| Title |
|---|
| 余远斌等: "酞菁类催化剂的研究进展", 《北京工业大学学报》 * |
| 向先国: "食品和水中微量氰化物的衍生化顶空气相色谱测定法", 《现代预防医学》 * |
| 周韩玲等: "白酒中微量氰化物检测方法的比对与探讨", 《酿酒科技》 * |
| 宁艳春等: "酞菁钴磺酸盐的制备及其催化脱硫的应用进展", 《石油化工》 * |
| 时振强等: "顶空气相色谱法测定酒中微量氰化物", 《中国卫生检验杂志》 * |
| 朱晓光等: "气相色谱法测定白酒中氰化物", 《安徽预防医学杂志》 * |
| 杜利君等: "顶空气相色谱法快速测定酒中氰化物含量", 《食品研究与开发》 * |
| 聂融等: "顶空-气相色谱法测定饮用水中微量氰化物", 《疾病预防控制通报》 * |
| 肖佳民等: "金属酞菁脱硫技术展望", 《化肥工业》 * |
| 阎冠洲等: "顶空气相色谱测定白酒中氰化物方法研究", 《酿酒科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112881548A (en) * | 2021-01-12 | 2021-06-01 | 济南趵突泉酿酒有限责任公司 | Method for rapidly detecting cyanide in sorghum |
| CN115166106A (en) * | 2021-11-26 | 2022-10-11 | 国家食品安全风险评估中心 | Method for detecting cyanide content in white spirit or white spirit fermentation process sample |
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Application publication date: 20180126 |