CN101556246A - Mercury vapour generation method and device - Google Patents
Mercury vapour generation method and device Download PDFInfo
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- CN101556246A CN101556246A CNA2009100616633A CN200910061663A CN101556246A CN 101556246 A CN101556246 A CN 101556246A CN A2009100616633 A CNA2009100616633 A CN A2009100616633A CN 200910061663 A CN200910061663 A CN 200910061663A CN 101556246 A CN101556246 A CN 101556246A
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- G—PHYSICS
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/69—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/67—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using electric arcs or discharges
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Abstract
The invention discloses a mercury vapour generation method and a device; the method realizes the generation of mercury in liquid sample in vapour form by the discharge of liquid cathode, comprising the following steps: first putting an anode and a cathode connected with two electrodes of a direct current power supply in a sealed discharging device, leading electrolyte solution of the sample containing mercury in the discharging device by a capillary, generating the discharging between the anode and the liquid sample on the sharp end of the capillary so as to generate the mercury vapour. The invention also provides a mercury vapour generation device, comprising the anode and the cathode connected with the two electrodes of the direct current power supply, wherein the anode and the cathode are placed in the discharging device; the discharging device is provided with the capillary with inner diameter of 01-5mm; the sample containing mercury is led in the discharging device by the capillary; the distance between the opening of the capillary and the anode is 1-4mm. The invention realizes the vapour generation of mercury by discharging without any reducing agent so as to reduce the reagent wastage and pollution danger.
Description
Technical field
The present invention relates to a kind of mercury vapour generation method and device, specifically a kind of liquid cathode discharge is used for the method and the device of the steam generation of mercury, belongs to analytical chemistry steam generation method technical field.
Background technology
Mercury is the global pollution thing, and people very pay close attention to the monitoring and the mensuration of mercury.Cold steam generation technique (CVG) can improve sample introducing efficient significantly, the realization sample separates with matrix, and (CVG-AAS is to detect the modal method of Trace Hg at present CVG-AFS) to cold steam generation-atomic spectrum.Common cold steam generation method is to utilize reductive agent (NaBH for example
4Or SnCl
2) Hg in the liquid (II) is reduced to Hg
0This method of reducing efficient is very high, and is easy to realize intermittence or continued operation, thereby is widely adopted.Be exactly to use SnCl in the standard determination method of the Hg of U.S. EPA
2The Hg reduction is realized atomic absorption detecting.Yet this method has many problems.At first the reductive agent price is expensive, and unstable (essential matching while using), easily has the danger of polluting.Especially during borohydride reduction, transition metal is to the mensuration serious interference of Hg for this method in addition.This is because reductive agent also can reduce transition metal, even the associated metal surface that the mercury deposition that produces can reduced.Therefore, people are devoted to develop the cold steam method for generation of novel Hg, and it can not use any reductive agent just can realize the steam generation of Hg.
The galvanochemistry steam generation method is exactly the alternative method that the cold steam of a kind of electronation takes place.It can be regarded as uses electronics to serve as reduction and the mensuration that reductive agent is realized Hg.Its great advantage is not use any electronation reagent.Yet the galvanochemistry steam generation method also has significant disadvantages.At first, because cathode electrode material energy appreciable impact electrochemical process, people must select suitable electrode material to realize steam generation.In addition, cathode surface must often be handled, and all needs to carry out every day usually.Transition metal can be reduced and be deposited on cathode surface equally.In addition, thus the gas that electrochemical reaction produces also can be adsorbed on the efficient that electrode surface reduces steam generation.
Free radical also can cause reduction reaction, and has been applied to above the steam generation of the many elements that comprise mercury.(PI-CVG) takes place the cold steam of photochemical induction is a kind of emerging steam generation method, and the photochemical reaction that it utilizes UV-irradiation to cause waits and realizes that cold steam takes place.By the hydroperoxyl radical that photodestruciton inferior quality organic acid (formic acid, acetate, propionic acid etc.) produces, carboxyl free radical is reduced to Hg steam with mercury ion.This method is not used high-purity reductive agent equally, and not only inorganic mercury can be reduced, thereby the organic mercury reduction can also be applied to the morphological analysis of Hg.The interference of other ion is relative also lower in addition.But this method efficient is not very high, needs long reaction tube to realize the reduction of Hg.Recently, Gil etc. have reported the cold steam genetic method of ultrasonic auxiliary Hg (SI-CVG), and this method is utilized ultrasonic add to the reducing gas of the formic acid generation in the sample and the reduction that free radical is realized Hg (II).A shortcoming of this method is oxygenant (MnO
4 -, Cr
2O
7 2-) can hinder the generation of reduction reaction, even it is very low to contain the concentration of oxygenant in the sample, can both significantly suppress the reduction of Hg.In addition, this method only is applicable to batch operation, can not be used for Flow Injection Analysis, and this method can not realize organomercurial reduction.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, a kind of mercuryvapour method for generation and device thereof are provided, liquid cathode discharge is used for the steam generation of mercury, realizes that under the condition of not using reductive agent mercuryvapour takes place efficiently, thereby provide the basis for the mercury assay determination of sensitivity.
Realize the technical scheme that the object of the invention adopts: will be connected the anode at direct supply the two poles of the earth and the electric discharge device that negative electrode places sealing earlier, again electrolyte solution is imported in the electric discharge device by kapillary, until electrolyte solution apart from kapillary mouth of pipe 0-2mm place, electrolyte solution with mercurous sample is incorporated in the electric discharge device by kapillary then, produce discharge between the fluid sample of anode and capillary tip, thereby produce mercuryvapour.
The sparking voltage of used direct supply is 200V-2000V, and discharge current is 10mA-150mA.
Used electrolyte solution is one or more the potpourri in nitric acid, sulfuric acid or the formic acid, and the pH scope is 0.5-4.
When peristaltic pump or syringe pump imported electric discharge device by internal diameter for the 0.1mm-5mm kapillary with the electrolyte of mercurous sample, introducing port was apart from anode 1mm-4mm, and boot speed is 0.5-10mL/min.Mercurous sample is a kind of or potpourri in Hg (II), methyl mercury, ethyl mercury, phenyl mercury, the Sodium Mercurothiolate.
The present invention also provides a kind of mercury vapour generating means in addition, comprise that being connected sparking voltage is 200V-2000V, discharge current is the discharge anode and the negative electrode at direct supply the two poles of the earth of 10mA-150mA, wherein anode and negative electrode place the electric discharge device of sealing, it is the 0.1mm-5mm kapillary that electric discharge device is provided with internal diameter, mercurous sample imports in the anti-shock device by kapillary, and the mouth of pipe capillaceous and anode distance are 1mm-4mm.
Electric discharge device has carrier gas inlet and carrier gas outlet, and the carrier gas outlet is positioned at the top of carrier gas inlet.The bottom of electric discharge device has waste liquid outlet.
Above-mentioned anode is one or more the alloy in platinum, tungsten or the titanium, and the material of negative electrode is a kind of in graphite, platinum, copper or the stainless steel.
Earlier electrolyte solution is imported in the electric discharge device by kapillary when using this device to produce mercuryvapour, be higher than the surface level of liquid electrolyte until the place, tip of the kapillary mouth of pipe, distance is 0-2mm.Then with mercurous sample, electrolyte solution as one or more potpourris in Hg (II), methyl mercury, ethyl mercury, phenyl mercury or the Sodium Mercurothiolate, flow velocity with 0.5-10mL/min imports the electric discharge device from kapillary, and discharge produces between the tip of the metal anode and the kapillary mouth of pipe.With one or more the mixed gas the flow velocity bubbling air of 30-3000mL/min, oxygen, nitrogen, helium, the argon gas, the mercuryvapour of discharge generation is transferred to gas-liquid separator from the carrier gas outlet under carrier gas drives from carrier gas inlet.
The liquid cathode electric discharge device will have certain discharge height, chooses the solution of suitable pH value, takes suitable voltage just can reach good discharge, forms plasma relatively uniformly.The speed that sample is introduced electric discharge device also is the important parameter of discharge, also the discharge behavior is produced certain influence, thereby influences steam generation efficient.The difference in height of kapillary top and electric discharge device internal electrolyte solution liquid level also is an important parameters in addition, only could produce stable discharge under suitable distance.
The inventive method is to utilize liquid cathode discharge to realize the steam generation of mercury, without any need for reductive agent, reduced the danger of reagent loss and pollution; Organic mercury does not need pre-oxidationly just can directly produce mercuryvapour for inorganic mercury in the method, has saved analytical procedure and time.With the mercuryvapour efficient height that this method produces, matrix disturbs little.In addition, apparatus of the present invention are simple in structure, and are easy to operate, are suitable for extensive industry and use.
Description of drawings
Fig. 1 is the structural representation of apparatus of the present invention.
Among the figure, 1. metal anode, 2. negative electrode, 3. kapillary, 4. carrier gas inlet, 5. carrier gas outlet, 6. waste liquid outlet, 7. direct supply.
Fig. 2 measures the signal graph of 100ng/mL Hg (II) for mercuryvapour generation-atomic emissions.
Embodiment
The method that the present invention produces mercury vapour is: will be connected sparking voltage is 200V-2000V, discharge current is the anode at direct supply the two poles of the earth of 10mA-150mA and the electric discharge device that negative electrode places sealing, earlier electrolyte solution is imported in the electric discharge device by kapillary, until electrolyte solution apart from kapillary mouth of pipe 0-2mm place.The electrolyte that will contain the mercury sample then is that the kapillary of 0.1mm-5mm is that 0.5-10mL/min imports in the electric discharge device with the flow velocity by internal diameter, and introducing port discharges between anode and the sample apart from anode 1mm-4mm, promptly produces mercuryvapour.Used liquid electrolyte is one or more the potpourri in nitric acid, sulfuric acid or the formic acid, and the pH scope is 0.5-4.Used metal anode is one or more the alloy in platinum, tungsten or the titanium, and the material of negative electrode is in graphite, platinum, copper or the stainless steel.
The present invention also provides a kind of mercury vapour generating means, its structure as shown in Figure 1, comprise that being connected sparking voltage is 200V-2000V, discharge current is the discharge anode 1 and the negative electrode 2 at direct supply 7 the two poles of the earth of 10mA-150mA, wherein anode and negative electrode place the electric discharge device of sealing, internal diameter is that the kapillary 3 of 0.1mm-5mm passes liquid medium, and the mouth of pipe of kapillary 3 and anode 1 distance are 1mm-4mm.Electric discharge device has carrier gas inlet 4 and carrier gas outlet 5, and the carrier gas outlet is positioned at the top of carrier gas inlet.The bottom of electric discharge device has waste liquid outlet 6.
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Choose tungsten bar as metal anode, the discharge end diameter is 1mm.Cathode material is chosen platinum filament.Distance is 1mm between tungsten electrode and the kapillary, and capillary inner diameter is 0.1mm.Earlier electrolyte solution is imported in the electric discharge device by kapillary, concordant until electrolyte levels apart from capillary tip.The nitric acid that with the pH value is 1 mercurous sample then imports in the electric discharge device by kapillary with the flow velocity of 0.5ml/min.Power supply adopts 700V, discharge current 50mA.Argon gas is adopted in carrier gas, and flow velocity is that the 400mL/min. signal detects with atomic emissions, and signal is with the linear variation of sample concentration, and Fig. 2 has provided the flow injection-liquid cathode discharge mercuryvapour generation-atomic emissions of mercury and measured the signal graph of 100ng/mL Hg (II).
Choose the titanium rod as metal anode, the discharge end diameter is 3mm.Cathode material is chosen graphite.Distance is 4mm between titanium electrode and the kapillary, and capillary inner diameter is 5mm.Earlier electrolyte solution is imported in the electric discharge device by kapillary, until electrolyte levels apart from capillary tip 2mm place.The sulfuric acid that with the pH value is 3 mercurous sample then imports in the electric discharge device by kapillary with the flow velocity of 10ml/min, and power supply adopts 2000V, discharge current 150mA.Air is adopted in carrier gas, and flow velocity is 3000mL/min.Signal detects with atomic absorption, and signal is with the linear variation of methyl mercury sample concentration.
Choose platinum as metal anode, the discharge end diameter is 0.2mm.Cathode material is chosen stainless steel.Distance is 2mm between platinum electrode and the kapillary, and capillary inner diameter is 2mm.Earlier electrolyte solution is imported in the electric discharge device by kapillary, until electrolyte levels apart from capillary tip 1mm place, the formic acid that with the pH value is 2 mercurous sample then imports in the electric discharge device by kapillary with the flow velocity of 2ml/min, and power supply adopts 200V, discharge current 10mA.Helium is adopted in carrier gas, and flow velocity is 30mL/min.Signal detects with atomic fluorescence, and signal is with the linear variation of ethyl mercury sample concentration.
Choose tungsten as metal anode, the discharge end diameter is 0.5mm.Cathode material is chosen graphite.Distance is 1mm between tungsten electrode and the kapillary, capillary inner diameter is 0.4mm, earlier electrolyte solution is imported in the electric discharge device by kapillary, apart from capillary tip 0.5mm place, the pH value is that the formic acid of 1 mercurous sample is led by kapillary with the flow velocity of 3ml/min then until electrolyte levels.In the electric discharge device, power supply adopts 1000V, discharge current 100mA.Nitrogen is adopted in carrier gas, and flow velocity is 100mL/min.The signal Mass Spectrometer Method, signal is with the linear variation of phenyl mercury sample concentration.
Claims (10)
1. mercury vapour generation method, it is characterized in that: will be connected the anode at direct supply the two poles of the earth and the electric discharge device that negative electrode places sealing earlier, again electrolyte solution is imported in the electric discharge device by kapillary, until electrolyte solution apart from kapillary mouth of pipe 0-2mm place, electrolyte solution with mercurous sample is incorporated in the electric discharge device by kapillary then, produce discharge between the fluid sample of anode and capillary tip, thereby produce mercuryvapour.
2. mercury vapour generation method according to claim 1 is characterized in that: the sparking voltage of used direct supply is 200V-2000V, and discharge current is 10mA-150mA.
3. mercury vapour generation method according to claim 1 is characterized in that: anode is one or more the alloy in platinum, tungsten or the titanium, and the material of negative electrode is a kind of in graphite, platinum, copper or the stainless steel.
4. mercury vapour generation method according to claim 1 is characterized in that: when the electrolyte solution of mercurous sample imported electric discharge device by kapillary, the kapillary mouth of pipe was apart from anode 1mm-4mm, and the speed that imports is 0.5-10mL/min.
5. according to claim 1 or 4 described mercury vapour generation methods, it is characterized in that: used electrolyte solution is one or more the potpourri in nitric acid, sulfuric acid or the formic acid, and pH is 0.5-4.
6. according to claim 1 or 4 described mercury vapour generation methods, it is characterized in that: used internal diameter capillaceous is 0.1mm-5mm.
7. mercury vapour generating means, comprise the discharge anode and the negative electrode that are connected direct supply the two poles of the earth, it is characterized in that: anode and negative electrode place the electric discharge device of sealing, electric discharge device is provided with kapillary, mercurous sample imports in the electric discharge device by kapillary, and the mouth of pipe capillaceous and anode distance are 1mm-4mm.
8. mercury vapour generating means according to claim 7 is characterized in that: electric discharge device has carrier gas inlet and carrier gas outlet, and the carrier gas outlet is positioned at the top of carrier gas inlet.
9. require described mercury vapour generating means according to claim 7, it is characterized in that: the bottom of electric discharge device has waste liquid outlet.
10. mercury vapour generating means according to claim 7 is characterized in that: internal diameter capillaceous is 0.1mm-5mm.
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| CNA2009100616633A CN101556246A (en) | 2009-04-17 | 2009-04-17 | Mercury vapour generation method and device |
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|---|---|---|---|
| CNA2009100616633A CN101556246A (en) | 2009-04-17 | 2009-04-17 | Mercury vapour generation method and device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102033103A (en) * | 2010-10-26 | 2011-04-27 | 中国地质大学（武汉） | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
| CN104812155A (en) * | 2015-05-12 | 2015-07-29 | 重庆邮电大学 | Atmospheric pressure plasma generating device and method |
| CN106568833A (en) * | 2016-10-11 | 2017-04-19 | 中国科学院上海硅酸盐研究所 | Photochemical steam generator and liquid cathode glow discharge spectrometer coupled analysis apparatus and method for detecting heavy metal by using apparatus |
| CN109613181A (en) * | 2018-11-28 | 2019-04-12 | 中国计量科学研究院 | A kind of trace gaseous mercury standard generating system |
| CN112630208A (en) * | 2019-10-09 | 2021-04-09 | 中国科学院上海硅酸盐研究所 | Sample introduction system for atomic spectrum or mass spectrum |
| CN113504188A (en) * | 2021-06-02 | 2021-10-15 | 中国科学院上海硅酸盐研究所 | Semi-closed system magnetic confinement liquid cathode glow discharge device |
| CN114216808A (en) * | 2021-11-18 | 2022-03-22 | 中国人民解放军军事科学院国防工程研究院工程防护研究所 | Gas impurity detection device and detection method |
-
2009
- 2009-04-17 CN CNA2009100616633A patent/CN101556246A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102033103A (en) * | 2010-10-26 | 2011-04-27 | 中国地质大学（武汉） | Mercury morphological analysis method based on liquid cathode discharge and mercury vapor generating device |
| CN104812155A (en) * | 2015-05-12 | 2015-07-29 | 重庆邮电大学 | Atmospheric pressure plasma generating device and method |
| CN106568833A (en) * | 2016-10-11 | 2017-04-19 | 中国科学院上海硅酸盐研究所 | Photochemical steam generator and liquid cathode glow discharge spectrometer coupled analysis apparatus and method for detecting heavy metal by using apparatus |
| CN106568833B (en) * | 2016-10-11 | 2019-04-16 | 中国科学院上海硅酸盐研究所 | A kind of liquid cathode glow discharge optical emission spectrometry device and method for heavy metal analysis |
| CN109613181A (en) * | 2018-11-28 | 2019-04-12 | 中国计量科学研究院 | A kind of trace gaseous mercury standard generating system |
| CN109613181B (en) * | 2018-11-28 | 2022-03-22 | 中国计量科学研究院 | Trace gaseous mercury standard generation system |
| CN112630208A (en) * | 2019-10-09 | 2021-04-09 | 中国科学院上海硅酸盐研究所 | Sample introduction system for atomic spectrum or mass spectrum |
| CN113504188A (en) * | 2021-06-02 | 2021-10-15 | 中国科学院上海硅酸盐研究所 | Semi-closed system magnetic confinement liquid cathode glow discharge device |
| CN114216808A (en) * | 2021-11-18 | 2022-03-22 | 中国人民解放军军事科学院国防工程研究院工程防护研究所 | Gas impurity detection device and detection method |
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