CN104655598A - Hydride generation and sample introduction method of germanium - Google Patents
Hydride generation and sample introduction method of germanium Download PDFInfo
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- CN104655598A CN104655598A CN201310606980.5A CN201310606980A CN104655598A CN 104655598 A CN104655598 A CN 104655598A CN 201310606980 A CN201310606980 A CN 201310606980A CN 104655598 A CN104655598 A CN 104655598A
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Abstract
The invention discloses a hydride generation and sample introduction method of germanium. The method comprises the following steps: inorganically digesting a to-be-detected sample to obtain a digested solution; adding solid acid and soluble salt containing phosphate anions into the digested solution, and fixing the volume with pure water to obtain a to-be-detected sample solution; respectively extracting the to-be-detected sample solution and an alkaline potassium borohydride solution by virtue of a sampling pump, and mixing; reacting germanium in the to-be-detected sample solution with potassium borohydride under an acidic condition to generate hydrogen germanide and hydrogen after the to-be-detected sample solution and the alkaline potassium borohydride solution are mixed; separating liquid-state components of the generated hydrogen germanide and hydrogen in a gas-liquid separator, and feeding into an atomizer of atomic fluorescence so as to complete the hydride generation and sample introduction processes. Compared with the method only using sulfamic acid, the method has the advantages that 90 percent of reagent consumption is reduced, and the problem that detection is influenced by easily crystallized high-concentration sulfamic acid is solved. The method has excellent popularization and application values.
Description
Technical field
The present invention relates to atomic spectroscopic analysis field, in particular to a kind of hydride generation sample injection method of Ge element.
Background technology
In atomic spectroscopic analysis field, hydride generation/steam generation sampling technique is because have higher sample introduction efficiency relative to the nebulization sampling of routine, one of sample introduction means being always used as atomic spectrum instrument, to obtain higher sensitivity for analysis, make Matrix effects greatly reduce simultaneously.
The hydride generation sampling technique of Ge element is widely used in atomic spectrum alanysis instrument at present, as atomic absorption spectrophotometer (AAS), atomic fluorescence spectrometer, inductively coupled plasma-emission spectrometer and sense coupled plasma-mass spectrum etc.
Application number is 201210238016.7, name is called that a kind of sulfaminic acid that uses that patent discloses of the solid acid compressing tablet of portable atomic fluorescence field quick detection and its preparation method and application substitutes concentrated acid as solid acid, when solving atomic fluorescence field quick detection, concentrated acid is difficult to carry, potential danger is large and field environment is changeable, quantitatively pipettes the problem of comparatively difficulty.But above-mentioned patent is when being applied to the hydride generation sampling technique of Ge element, and with optimal conditions, when the mass concentration of sulfaminic acid is 20%, its sensitivity is only 1/5 of traditional 20% phosphonate method.Therefore, when tackling the extreme trace analysis of Ge element, there is very large difficulty.In addition, the consumption of sulfaminic acid is very big, and analysis cost is higher, and the sulfaminic acid of higher concentration very easily crystallization, affect the mensuration of Ge element.
Patent also not relevant at present or document propose the method solved to the problems referred to above.
Summary of the invention
The invention provides a kind of hydride generation sample injection method of Ge element, the hydrogen ion needed for hydride generation is provided by solid acid, soluble-salt containing phosphate anion provides the anionic atmosphere required for Ge element generation germanium hydrogen, relative to the reagent consumption only using the method for sulfaminic acid to save 90%, and there is not the problem of high concentration sulfaminic acid easy crystallization impact mensuration, there are preferably promotion and application and be worth.
For achieving the above object, the invention provides a kind of hydride generation sample injection method of Ge element, comprising the following steps:
At testing sample after inorganization clearing up, obtain digestion solution;
In digestion solution, add solid acid and the soluble-salt containing phosphate anion, obtain testing sample solution with after pure water constant volume;
Extract testing sample solution respectively by sampling pump and alkaline solution of potassium borohydride mixes, the Ge element after the two mixing in testing sample solution reacts with potassium borohydride in acid condition and generates germanium hydrogen and hydrogen;
The germanium hydrogen generated and hydrogen enter the atomizer of atomic fluorescence in gas-liquid separator after separation of liquid component, namely complete hydride generation sample introduction process.
Optionally, extract testing sample solution and alkaline solution of potassium borohydride respectively by sampling pump to carry out blend step and comprise:
Be kept in accessing ring by the first peristaltic pump pumps testing sample solution;
The alkaline solution of potassium borohydride synchronously extracted by the testing sample solution in the first peristaltic pump promotion accessing ring and the second peristaltic pump is mixed in threeway mixing module.
Optionally, the atomizer step that the germanium hydrogen generated and hydrogen enter atomic fluorescence in gas-liquid separator after separation of liquid component comprises:
The germanium hydrogen generated and hydrogen and reacted mixed liquor are sent into gas-liquid separator by threeway mixing module and are carried out gas-liquid separation, germanium hydrogen after separation and hydrogen enter the atomizer of atomic fluorescence, wherein the top of gas-liquid separator is communicated with the atomizer of atomic fluorescence, the bottom of gas-liquid separator is communicated with waste liquid cup, and the upper portion side wall of gas-liquid separator is communicated with argon gas source.
Optionally, solid acid is at least one in trichloroacetic acid, sulfaminic acid, oxalic acid and tartrate.
Optionally, the soluble-salt containing phosphate anion is at least one in dihydric phosphate, hydrophosphate and phosphate.
Optionally, the mass concentration of solid acid in testing sample solution is 0% ~ 10%.
Optionally, the mass concentration of soluble-salt in testing sample solution is 0.5% ~ 30%.
Optionally, dihydric phosphate is KH
2pO
4, NaH
2pO
4, NH
4h
2pO
4in at least one.
Optionally, hydrophosphate is K
2hPO
4, Na
2hPO
4, (NH
4)
2hPO
4in at least one.
Optionally, when the mass concentration of solid acid is 0%, soluble-salt is only dihydric phosphate.
The present invention utilizes solid acid to provide hydrogen ion needed for hydride generation, soluble-salt containing phosphate anion provides the anionic atmosphere required for Ge element generation germanium hydrogen, because reagent used in the present invention is solid, environmental pollution is little, little to human injury, and it is simple to operate, with traditional 20% phosphonate method, there is identical sensitivity, and the consumption solving sulfaminic acid greatly, the higher and sulfaminic acid of higher concentration of analysis cost is very easily because temperature variation crystallization affects the problem of the mensuration of Ge element; Relative to the reagent consumption only using the method for sulfaminic acid can save 90%, and there is not the problem of high concentration sulfaminic acid easy crystallization impact mensuration, there are preferably promotion and application and be worth.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the hydride generation sampling device structural representation of the Ge element of one embodiment of the invention;
Fig. 2 is the hydride generation sample injection method process flow diagram of the Ge element of one embodiment of the invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not paying the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Fig. 1 is the hydride generation sampling device structural representation of the Ge element of one embodiment of the invention; As shown in the figure, this device comprises: 1-testing sample solution; 2-first peristaltic pump; 3-accessing ring; 4-threeway mixing module; 5-gas-liquid separator; 6-argon gas source of the gas; 7-waste liquid cup; 8-second peristaltic pump; 9-solution of potassium borohydride.
Fig. 2 is the hydride generation sample injection method process flow diagram of the Ge element of one embodiment of the invention.As shown in the figure, this hydride generation sample injection method comprises the following steps:
S110, at testing sample after inorganization clearing up, obtains digestion solution;
S120, adds solid acid and the soluble-salt containing phosphate anion, obtains testing sample solution with after pure water constant volume in digestion solution;
Wherein, the mass concentration of solid acid in testing sample solution is 0% ~ 10%.Solid acid can be at least one in trichloroacetic acid, sulfaminic acid, oxalic acid and tartrate.The mass concentration of soluble-salt in testing sample solution is 0.5% ~ 30%.Soluble-salt containing phosphate anion can be at least one in dihydric phosphate, hydrophosphate and phosphate; Dihydric phosphate can be KH
2pO
4, NaH
2pO
4, NH
4h
2pO
4in at least one; Hydrophosphate can be K
2hPO
4, Na
2hPO
4, (NH
4)
2hPO
4in at least one.But when the mass concentration of solid acid is 0%, soluble-salt is only dihydric phosphate.
S130, extracts testing sample solution respectively by sampling pump and alkaline solution of potassium borohydride mixes, and the Ge element after the two mixing in testing sample solution reacts with potassium borohydride in acid condition and generates germanium hydrogen and hydrogen;
Wherein, extract testing sample solution and alkaline solution of potassium borohydride respectively by sampling pump to carry out blend step and comprise: be kept in accessing ring by the first peristaltic pump pumps testing sample solution; The alkaline solution of potassium borohydride synchronously extracted by the testing sample solution in the first peristaltic pump promotion accessing ring and the second peristaltic pump is mixed in threeway mixing module.
S140, the germanium hydrogen generated and hydrogen enter the atomizer of atomic fluorescence in gas-liquid separator after separation of liquid component, namely complete hydride generation sample introduction process.
Wherein, the atomizer step that the germanium hydrogen generated and hydrogen enter atomic fluorescence in gas-liquid separator after separation of liquid component comprises: the germanium hydrogen generated and hydrogen and reacted mixed liquor are sent into gas-liquid separator by threeway mixing module and carried out gas-liquid separation, germanium hydrogen after separation and hydrogen enter the atomizer of atomic fluorescence, wherein the top of gas-liquid separator is communicated with the atomizer of atomic fluorescence, the bottom of gas-liquid separator is communicated with waste liquid cup, and the upper portion side wall of gas-liquid separator is communicated with argon gas source.
Be sulfaminic acid below with solid acid, soluble-salt is KH
2pO
4for example, illustrate the hydride generation sample introduction process of Ge element:
(1) testing sample is after inorganization clearing up, and obtains 2mL digestion solution;
(2) in digestion solution, 0.20g sulfaminic acid and 1.00g KH is added
2pO
4, after also dissolving with pure water constant volume the material added, mix, obtain testing sample solution;
(3) first peristaltic pump pumps testing sample solutions are also kept in accessing ring;
The alkaline solution of potassium borohydride mixing that testing sample solution in (4) first peristaltic pumps promotion accessing rings and the second peristaltic pump synchronously extract;
(5) Ge element after the two mixing in testing sample solution reacts with potassium borohydride in acid condition and generates germanium hydrogen and hydrogen;
(6) germanium hydrogen and hydrogen enter the atomizer of atomic fluorescence in gas-liquid separator after separation of liquid component, namely complete the hydride generation sample introduction process that atomic fluorescence detects.
It is pointed out that soluble-salt is only KH when solid acid concentration is 0%
2pO
4, the hydride generation sample introduction process of Ge element is now as follows:
(1) testing sample is after inorganization clearing up, and obtains 2mL digestion solution;
(2) in digestion solution, 2.50g KH is added
2pO
4, after also dissolving with pure water constant volume the material added, mix, obtain testing sample solution;
(3) first peristaltic pump pumps testing sample solutions are also kept in accessing ring;
The alkaline solution of potassium borohydride mixing that testing sample solution in (4) first peristaltic pumps promotion accessing rings and the second peristaltic pump synchronously extract;
(5) Ge element after the two mixing in sample solution reacts with potassium borohydride in acid condition and generates germanium hydrogen and hydrogen;
(6) germanium hydrogen and hydrogen enter the atomizer of atomic fluorescence in gas-liquid separator after separation of liquid component, namely complete the hydride generation sample introduction process that atomic fluorescence detects.
In above-described embodiment, solid acid provides the hydrogen ion needed for hydride generation, soluble-salt containing phosphate anion provides the anionic atmosphere required for Ge element generation germanium hydrogen, because reagent used in the present invention is solid, environmental pollution is little, little to human injury, and it is simple to operate, with traditional 20% phosphonate method, there is identical sensitivity, and the consumption solving sulfaminic acid greatly, the higher and sulfaminic acid of higher concentration of analysis cost is very easily because temperature variation crystallization affects the problem of the mensuration of Ge element; Relative to the reagent consumption only using the method for sulfaminic acid can save 90%, and there is not the problem of high concentration sulfaminic acid easy crystallization impact mensuration, there are preferably promotion and application and be worth.
One of ordinary skill in the art will appreciate that: accompanying drawing is the schematic diagram of an embodiment, the module in accompanying drawing or flow process might not be that enforcement the present invention is necessary.
One of ordinary skill in the art will appreciate that: the module in the device in embodiment can describe according to embodiment and be distributed in the device of embodiment, also can carry out respective change and be arranged in the one or more devices being different from the present embodiment.The module of above-described embodiment can merge into a module, also can split into multiple submodule further.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in previous embodiment, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of embodiment of the present invention technical scheme.
Claims (10)
1. a hydride generation sample injection method for Ge element, is characterized in that, comprise the following steps:
At testing sample after inorganization clearing up, obtain digestion solution;
In described digestion solution, add solid acid and the soluble-salt containing phosphate anion, obtain testing sample solution with after pure water constant volume;
Extract described testing sample solution respectively by sampling pump and alkaline solution of potassium borohydride mixes, the Ge element after the two mixing in testing sample solution reacts with potassium borohydride in acid condition and generates germanium hydrogen and hydrogen;
The germanium hydrogen generated and hydrogen enter the atomizer of atomic fluorescence in gas-liquid separator after separation of liquid component, namely complete hydride generation sample introduction process.
2. the method for claim 1, is characterized in that, describedly extracts described testing sample solution and alkaline solution of potassium borohydride respectively by sampling pump and carries out blend step and comprise:
Be kept in accessing ring by testing sample solution described in the first peristaltic pump pumps;
Promote by described first peristaltic pump the alkaline solution of potassium borohydride that testing sample solution in described accessing ring and the second peristaltic pump synchronously extract to mix in threeway mixing module.
3. method as claimed in claim 2, it is characterized in that, the atomizer step that described generated germanium hydrogen and hydrogen enter atomic fluorescence in gas-liquid separator after separation of liquid component comprises:
The germanium hydrogen generated and hydrogen and reacted mixed liquor are sent into gas-liquid separator by described threeway mixing module and are carried out gas-liquid separation, germanium hydrogen after separation and hydrogen enter the atomizer of atomic fluorescence, the top of wherein said gas-liquid separator is communicated with the atomizer of described atomic fluorescence, the bottom of described gas-liquid separator is communicated with waste liquid cup, and the upper portion side wall of described gas-liquid separator is communicated with argon gas source.
4. the method for claim 1, is characterized in that, described solid acid is at least one in trichloroacetic acid, sulfaminic acid, oxalic acid and tartrate.
5. the method for claim 1, is characterized in that, the described soluble-salt containing phosphate anion is at least one in dihydric phosphate, hydrophosphate and phosphate.
6. the method for claim 1, is characterized in that, the mass concentration of described solid acid in testing sample solution is 0% ~ 10%.
7. the method for claim 1, is characterized in that, the mass concentration of described soluble-salt in testing sample solution is 0.5% ~ 30%.
8. method as claimed in claim 5, it is characterized in that, described dihydric phosphate is KH
2pO
4, NaH
2pO
4, NH
4h
2pO
4in at least one.
9. method as claimed in claim 5, it is characterized in that, described hydrophosphate is K
2hPO
4, Na
2hPO
4, (NH
4)
2hPO
4in at least one.
10. method as claimed in claim 5, it is characterized in that, when the mass concentration of described solid acid is 0%, described soluble-salt is only dihydric phosphate.
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Cited By (3)
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| CN109142320A (en) * | 2018-07-31 | 2019-01-04 | 天津港东科技股份有限公司 | Hydride reaction new method occurs for Germanium |
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Application publication date: 20150527 |