CN1437014A - Sample entering method for atomic spectrometer - Google Patents

Sample entering method for atomic spectrometer Download PDF

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Publication number
CN1437014A
CN1437014A CN 03103223 CN03103223A CN1437014A CN 1437014 A CN1437014 A CN 1437014A CN 03103223 CN03103223 CN 03103223 CN 03103223 A CN03103223 A CN 03103223A CN 1437014 A CN1437014 A CN 1437014A
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CN
China
Prior art keywords
hydride
sample
solution
reaction
heating
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CN 03103223
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Chinese (zh)
Inventor
段旭川
李鸿敏
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李学璧
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Priority to CN02103663 priority
Application filed by 李学璧 filed Critical 李学璧
Priority to CN 03103223 priority patent/CN1437014A/en
Publication of CN1437014A publication Critical patent/CN1437014A/en

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Abstract

The present invention relates to analyzing instrument. The present invention includes the following steps: heating the reaction system of sample solution and hydrogen for reaction at temperature higher than room temperature; separating the produced hydride from the sample solution; eliminating the solution fog accompanying the hydride; and introducing the produced hydride with carrying gas into atomizing unit of spectrometer for spectral or mass spectrum test. The said method may be used in various atomic spectrometers and may be used for the sample of nine elements easy to form hydride as well as for the sample of other decades of elements.

Description

Sample entering method for atomic spectrometer
The invention relates to a kind of (or increasing) element that in atomic spectrograph hydrogenation sampling system, improves and form the percentile method of hydride, especially about the sample solution that contains element by heating and the reaction system of going back protohydrogen, thereby the low-down element of productive rate (under the normal temperature nine of easy hydrogenation the plumbous selen-tellurjum mercury of element arsenic antimony bismuth germanium tin except) that improves the hydride that at normal temperatures hydrogenation can take place but generate forms the method for high yield hydride.
No matter employed hydride generation sampling system in the current atom spectrometer is discontinuous sample introduction or continous way sample introduction, all is the normal temperature hydrogenation system that reacts.These normal temperature hydrogenation generating meanss can have been bought from many companies.Their purposes is to be used for making nine elements (arsenic, antimony, bismuth, germanium, tin, lead, selenium, tellurium, mercury) that easily form hydride traditionally to be imported into atomic spectrograph by hydrogenation generation sampling system to measure.These nine elements just have the ability of very strong formation hydride at normal temperatures, and the percent that forms volatile hydride has relation with hydrogenation apparatus shape and structure, but concern not quite.
In recent years, because the not section development of instrument, the research that hydrogenation formation hydride can take place relevant other element also deepens continuously.Guo Xiaowei equals nineteen ninety-five and has found that zinc and cadmium in the acidic aqueous solution at normal temperatures can be reduced into volatile hydride by sodium borohydride solution, and uses this discovery to measure zinc and the cadmium in the actual sample on atomic fluorescence spectrometer.
Aderval.S Luna and P.Pohl be respectively at 2000 and calendar year 2001 reported for work some elements such as gold, silver, and copper, manganese, titanium etc. can form more weak hydride at normal temperatures.But these results of study also have following problem to need to solve: (1) sensitivity and detection limit are not to be better than conventional pneumatic nebulization sample introduction.This is that the hydride productive rate is very low because the ability of the hydride of these elements formation volatiles is very weak under the normal temperature, and the element part in the sample solution is hydrogenated volatilization, and another part also remains in the solution.(2) serious residual effect.This is because most elements is arranged very also in solution in the previous sample, after solution is discharged from, also have trace element to be bonded at hydrogenation generator inwall, when moving as blank with acid blank solution that does not contain element and sodium borohydride, produce very strong blank signal, and make method almost can't be applied to real work.
The present invention has following advantage: (1) has improved the hydrogenation generation productive rate of element significantly.Many hydride at normal temperatures form very low element (Au, Ag, Ni, the Pd of percent, Pt, Rh, Ru, Zn, Cu, Co, Sc, Y, Ti, V, Cr, Mn, Fe, Zr, Deng) after improving the hydrogenation temperature, its hydrogenation productive rate significantly improves, and makes the element that can measure on atomic spectrograph by the hydrogenation genetic method expand present tens kinds to from original nine kinds.(2) improve the sensitivity of ultimate analysis significantly, reduced detection limit.(3) eliminate residual effect, improved the accuracy and the sample analysis speed of sample analysis.
The present invention is made up of following four steps: (one) heating contains the reduction reaction system of sample solution and hydrogen of element, and this reaction (generation hydride) is carried out being higher than under the temperature of room temperature.(2) the element hydride of generation is separated from sample solution (or residue).(3) remove the solvent aerosol of following with the hydride of separating.(4) making the hydride that removes behind the aerosol that desolvates be imported atom (ion) in the atomic spectrograph by carrier gas changes in the device and is carried out spectrum or mass spectroscopy.
Below four steps of the present invention are described:
(1) heating contains the reduction reaction system of sample solution and hydrogen of element, and this reaction (generation hydride) is carried out being higher than under the temperature of room temperature
To a certain concrete sample solution that contains element, the heated actual temp of reduction reaction system of itself and hydrogen depends on following factors: the character that forms the element of hydride, the stability of formed hydride, character (the viscosity of the solvent of dissolving element, volatility etc.), character (the sample state that contains the sample of element, constituent content, matrix properties etc.), to the requirement of detection limit, the concrete structure of hydrogenation sampling system contains the sample solution of element and go back the mode that protohydrogen is entered before reaction, type of heating that is adopted and method, a series of actual conditionses such as type of the spectral instrument of mensuration element.
When the sample solution that contains element is aqueous solution, and the remaining main body behind the hydrogenation is when being still aqueous solution, and the heated temperature range of reaction system should be to be less than or equal to 100 degrees centigrade greater than room temperature, preferably 70-100 degree centigrade.
When the sample solution that contains element is an aqueous solution, and all water all is vaporized when becoming water vapour in the hydrogenation afterreaction system, and the heated temperature of reaction system should be greater than 100 degrees centigrade, so preferably big 100 degrees centigrade and less than 140 degrees centigrade.
The heated mode of hydrogenation system is: promptly can heat earlier the sample solution that contains element and (or) go back protohydrogen to uniform temperature, mixed then they react together; Also can be in reactor, to mix sample solution earlier and go back protohydrogen (normal-temperature reaction to take place) this moment, and then the heating reaction system make the two further complete reaction to uniform temperature together.Or with preceding two kinds of diverse type of heating.
Being used to heat the thermal source of hydrogenation, can be all thermals source that can produce thermal effect, and these thermals source comprise microwave heating, Infrared Heating, electromagnetism heating, resistance heated, light heating etc.
The sample solution that contains element comprises that promptly solute is dissolved in the true solution in the solvent fully, also comprises some milky solution and aaerosol solution.Some sample can be evenly dispersed in the solution with emulsus or suspended state, but some element in the sample really still can carry out the hydrogenation genetic method with going back protohydrogen generation hydrogenation to be measured, in this case can be directly by the element in this inventive method working sample.
The input mode of sample can be a continuous sample introduction before the reaction, is interrupted sample introduction, or flow injection.
When the sample solution that contains element is nine element (arsenic of traditional easy formation hydride, antimony, bismuth, germanium, tin, plumbous, selenium, tellurium, mercury) in one or several element when being dissolved in the water formed aqueous solution, react this this moment is that heated temperature should be greater than 50 degrees centigrade less than 100 degrees centigrade, preferably 80-100 degree centigrade; And input mode is continuous sample introduction or flow injection sample introduction.
(2) the element hydride of generation is separated from sample solution (or residue).
Although the element hydride that generates is that gaseous state is volatilizable, it has certain solubleness in solution, when reacted remaining main body is still solution, contain a certain amount of hydride in this solution.In order to make the hydride that generates in the reaction atomic spectrum instrument that is imported into as much as possible, preferably use carrier gas atomizing heating reacted solution, or advertise method such as bubble with carrier gas from the solution the inside and effectively extract the residual hydride of dissolving the solution.Certainly, also can use other effective ways to come the hydride that makes as much as possible from solution, to separate.
(3) remove the solvent aerosol of following with the hydride of separating.
In step () and (two) process, to produce the steam and fog (if the aqueous solution of some solvents, what then produce is steam and water smoke), they are with the hydride that generates in the adjoint process, and the atom (ion) that is written into the atomic spectrum instrument by carrier gas is together changed the mensuration process that participates in element in the device.If the solvent aerosol that produces in the process (as steam or water smoke) is not influence when atomic spectrograph is carried out element determination, then should invention form by step () and (two) and (four).(as make flame instability if the solvent aerosol that produces in the process (as steam or water smoke) is influential when atomic spectrograph is carried out element determination, the background of measuring adds ambassador's measurement result instability etc.), then must use suitable method (to condense as cold water, refrigerant condenses, chemical water absorbing agent absorption etc.) remove all or part of solvent aerosol.
(4) making the hydride that removes behind the aerosol that desolvates be imported atom (ion) in the atomic spectrograph by carrier gas changes in the device and is carried out spectrum or mass spectroscopy.
Should be noted that: four steps that this invention is included are not being perfectly clear separately in concrete experiment or work, adjacent two in these four steps sometimes, and three, even four steps are overlapped or are all overlaped.These four steps are to divide from the microcosmic order of entire method, and its macro manifestations is obviously not obvious sometimes sometimes, and this depends on the concrete implementing process and the equipment of this method.
Embodiment:
Example 1.Contain the experiment of the reduction reaction generation hydride of element sample solution and hydrogen by following described experimental technique.Used atomic spectrograph is an inductance lotus root and the plasma emission spectrometer oneself assembled.Select for use 1% sodium borohydride aqueous solution as the hydrogen source of going back protohydrogen.Peristaltic pump 1 and 2 is continuous drawing sodium borohydride and sample solution (acidity is 2% nitric acid, and constituent content is Pd, Cu, Ni, each 1ppm of Zn) respectively, and the extraction amount respectively is 3 ml/min.Two solution are passed through two polyfluortetraethylene pipes (35 centimetres of length, internal diameters 1 respectively.5 millimeters) enter electric furnace.Heated two solution spray into 20 centimetres of length after the hybrid reaction in a little T type glass tube, in the glass separation vessel that internal diameter is 3 centimetres, this moment, temperature of reaction was about 93 degrees centigrade.The flow that hydride that produces and steam are blasted by bottom the glass separation vessel (being covered with thin glass bead) is that 0.5 liter/minute argon gas enters 25 centimetres of length from carrying, the water condenser that internal diameter is 1 centimetre, here, steam is condensed, and the hydride of element is measured in the plasma flare of carrier gas (argon gas) lead-in light spectrometer.Each detection limits of using this method to obtain is as follows:
Pd:0.51ng/ml; Cu:0.45ng/ml;
Ni:0.46ng/ml; Zn:0.59ng/ml;

Claims (9)

1. one kind is used for improving (or increasing) element and forms the percentile method of hydride, this method be applied to atomic spectrograph (AFS, AAS, AES, ICP-AES, ICP-MS, etc.) in sample enter system.It is characterized in that this method is made up of following four steps: (1) heating contains the reduction reaction system of the sample solution and the hydrogen of element, and this reaction (generation hydride) is carried out being higher than under the temperature of room temperature.(2) the element hydride of generation is separated from sample solution (or residue).(3) remove the solvent aerosol of following with the hydride of separating.(4) making the hydride that removes behind the aerosol that desolvates be imported atom (ion) in the atomic spectrograph by carrier gas changes in the device and is carried out spectrum or mass spectroscopy.
2. method according to claim 1, the solvent aerosol (as steam or water smoke) that produces in step (1) and (2) process not influence when atomic spectrograph is carried out element determination it is characterized in that: if then should be made up of step (1) and (2) and (4) in invention.
3. method according to claim 1, it is characterized in that: to a certain concrete sample solution that contains element, the heated actual temp of reduction reaction system of itself and hydrogen depends on following factors: the character that forms the element of hydride, the stability of formed hydride, character (the viscosity of the solvent of dissolving element, volatility etc.), character (the sample state that contains the sample of element, constituent content, matrix properties etc.), requirement to detection limit, the concrete structure of hydrogenation sampling system, contain the sample solution of element and go back the mode that protohydrogen is entered before reaction, type of heating that is adopted and method, a series of actual conditionses such as type of the spectral instrument of mensuration element.
4. method according to claim 1 is characterized in that: when the sample solution that contains element is an aqueous solution, and the remaining main body behind the hydrogenation is when being still aqueous solution, and the heated temperature range of reaction system should be to be less than or equal to 100 degrees centigrade greater than room temperature; Preferably 70-100 degree centigrade.
5. method according to claim 1, it is characterized in that: when the sample solution that contains element is an aqueous solution, and all water all is vaporized when becoming water vapour in the hydrogenation afterreaction system, and the heated temperature of reaction system should be less than the decomposition temperature of the hydride that is generated greater than 100 degrees centigrade; So it is preferably big 100 degrees centigrade and less than 140 degrees centigrade.
6. method according to claim 1 is characterized in that: the heated mode of hydrogenation system is: promptly can heat earlier the sample solution that contains element and (or) go back protohydrogen to uniform temperature, mixed then they react together; Also can be in reactor, to mix sample solution earlier and go back protohydrogen (normal-temperature reaction to take place) this moment, and then the heating reaction system make the two further complete reaction to uniform temperature together; Or with all different other type of heating of preceding two kinds of type of heating.
7. method according to claim 1 is characterized in that: being used to heat the thermal source of hydrogenation, can be all thermals source that can produce thermal effect, and these thermals source comprise microwave heating, Infrared Heating, electromagnetism heating, resistance heated, light heating etc.
8. method according to claim 1 is characterized in that: contain the sample solution of element, comprise that promptly solute is dissolved in the true solution in the solvent fully, also comprises some milky solution and aaerosol solution.Input mode can be a continuous sample introduction, is interrupted sample introduction, or flow injection.Preferably use the continuous sample introduction mode.
9. according to claim 1, it is characterized in that: be nine elements, that is: arsenic of traditional easy formation hydride when the sample solution that contains element, antimony, bismuth, germanium, tin, plumbous, when selenium, tellurium, one or several element in the mercury are dissolved in the water formed aqueous solution, the heated temperature of reaction system this moment should be greater than 50 degrees centigrade less than 100 degrees centigrade, preferably 70-100 degree centigrade; And input mode is continuous sample introduction or flow injection sample introduction.
CN 03103223 2002-02-04 2003-01-25 Sample entering method for atomic spectrometer CN1437014A (en)

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CN02103663 2002-02-04
CN 03103223 CN1437014A (en) 2002-02-04 2003-01-25 Sample entering method for atomic spectrometer

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100356161C (en) * 2004-12-27 2007-12-19 郴州钻石钨制品有限责任公司 Rapid analysis and detection method for tin element in tungsten smelting
CN101113969B (en) * 2006-07-27 2010-05-12 中国科学院大连化学物理研究所 Sample feeder device of solid body and liquid example
CN101551357B (en) * 2009-02-26 2013-02-06 中国兵器工业集团第五三研究所 ICP-MS measuring method of trace metal impurities in high purity lead
CN103196894A (en) * 2013-03-13 2013-07-10 天津师范大学 Plasma atomic emission spectroscopy analysis method and plasma atomic emission spectroscopy analysis apparatus using gaseous sample injection
CN103411892A (en) * 2013-07-17 2013-11-27 天津师范大学 Analysis sample injection apparatus and method for making element form volatile by using organic matter cracking
CN103792131A (en) * 2014-01-23 2014-05-14 天津师范大学 Curie-point pyrolyser of volatile matter generated by element in element determination
CN107462569A (en) * 2016-08-30 2017-12-12 天津师范大学 A kind of method and device that element is determined by Element generation volatile matter

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100356161C (en) * 2004-12-27 2007-12-19 郴州钻石钨制品有限责任公司 Rapid analysis and detection method for tin element in tungsten smelting
CN101113969B (en) * 2006-07-27 2010-05-12 中国科学院大连化学物理研究所 Sample feeder device of solid body and liquid example
CN101551357B (en) * 2009-02-26 2013-02-06 中国兵器工业集团第五三研究所 ICP-MS measuring method of trace metal impurities in high purity lead
CN103196894A (en) * 2013-03-13 2013-07-10 天津师范大学 Plasma atomic emission spectroscopy analysis method and plasma atomic emission spectroscopy analysis apparatus using gaseous sample injection
CN103411892A (en) * 2013-07-17 2013-11-27 天津师范大学 Analysis sample injection apparatus and method for making element form volatile by using organic matter cracking
WO2015007217A1 (en) * 2013-07-17 2015-01-22 Duan Xuchuan Element analysis method and injection device making use of organic cracking to cause an element to form a volatile
CN103792131A (en) * 2014-01-23 2014-05-14 天津师范大学 Curie-point pyrolyser of volatile matter generated by element in element determination
CN107462569A (en) * 2016-08-30 2017-12-12 天津师范大学 A kind of method and device that element is determined by Element generation volatile matter

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