CN102980877A - Internal standard method used in measuring conventional elements easy to form hydrides through atomic fluorescence - Google Patents
Internal standard method used in measuring conventional elements easy to form hydrides through atomic fluorescence Download PDFInfo
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- CN102980877A CN102980877A CN2012105397583A CN201210539758A CN102980877A CN 102980877 A CN102980877 A CN 102980877A CN 2012105397583 A CN2012105397583 A CN 2012105397583A CN 201210539758 A CN201210539758 A CN 201210539758A CN 102980877 A CN102980877 A CN 102980877A
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Abstract
The invention discloses an internal standard method used in measuring conventional elements easy to form hydrides through atomic fluorescence. The internal standard method comprises the following steps of: (1) setting instruments, wherein an atomizer is alternatively radiated by using an internal standard element triggering light source and a triggering light source of an element to be measured (or in time sequence), so as to alternatively trigger atomic fluorescence signals of the internal standard element and the element to be measured, and achieve the purpose of synchronously measuring the two elements; (2) preparing a solution, wherein a certain quantity of internal standard elements are respectively added into a standard solution and a sample solution; (3) drawing a calibration curve, wherein a fluorescence value ratio I analysis/I internal standard of an analysis element and the internal standard element in the standard solution is measured, and a calibration curve is established for the concentration Ci (i is equal to 1, 2, 3,...) of the analysis element in accordance with the I analysis/I internal standard; and (4) under the same condition, measuring a fluorescence value ratio I analysis/I internal standard of the analysis element and the internal standard element in a test sample, and calculating the content Cx of the element to be tested from the calibration curve. By utilizing the method, the defects that the conventional measurement is large in chemical and physical interference, not good in measurement stability and the like are effectively eliminated, and the measurement precision and the accuracy are improved.
Description
Technical field
The invention belongs to instrumental analysis determination techniques field, the internal standard method of using when relating to a kind of element that adopts gaseous state sample introduction atomic fluorescence of zero dispersion instrument to measure easily to form traditionally hydride.
Background technology
Sodium borohydride and element form gaseous hydride under acid condition reaction (CVG) has been used for atomic spectroscopic analysis.Relatively conventional nebulization sampling, the gaseous hydride sample introduction has very high sample feeding efficient and low detection limit.These units that are used for the mensuration of hydride sample introduction have arsenic, antimony, bismuth selenium tellurium, germanium, tin, lead, mercury (being reduced to simple substance).Yet, can form traditionally element arsenic, antimony, bismuth selenium tellurium, germanium, tin, lead, the mercury of volatile matter to these, when use the gaseous hydride sample introduction--when Atomic fluorescence spectrometry is measured, all be faced with some measurement results and be subjected to very large this difficult problem of experiment condition factor influence of fluctuations.These factors comprise when chemical evapn reacts the impact, the fluctuation of some conditions of instrument itself etc. of matrix of interference, the sample of acidity, coexistence elements or the material of unit's cellulose solution.Experiment shows: the existence of above-mentioned factor sometimes or even small fluctuation, can both make the signal of instrument produce great changes, thereby can make that the calibration curve correlativity is bad, the measuring accuracy variation, makes the final sample measurement result produce very large error.
Summary of the invention
The present invention is directed to chemical evapn generation sample introduction---the atomic fluorescence of zero dispersion photometric determination exist when easily forming traditionally the element of hydride disturb large, the affected factor of apparatus measures signal is many, the shortcoming such as cause the correlativity of typical curve bad, the measurement result error is large, the improving one's methods of proposition.
The invention discloses a kind of use scandium, titanium, yttrium, zirconium, rhodium, ruthenium, palladium, osmium, iridium, gold, silver, gallium, indium, germanium, thallium, tin, selenium and tellurium and make internal standard element, measure the method that easily forms traditionally the element of hydride with chemical evapn generation-atomic fluorescence of zero dispersion, it is characterized in that being undertaken by following step:
(1) instrument setting: the hollow cathode lamp with internal standard element and element to be measured replaces the irradiated atoms device, thereby alternately excites the atomic fluorescence signal of internal standard element and element to be measured, reaches two elements or multielement simultaneous determination purpose;
(2) solution preparation: in standard solution and sample solution, add respectively a certain amount of internal standard element;
(3) draw calibration curve: the analytical element in the bioassay standard solution and the fluorescent value of internal standard element compare I
Analyze/ I
Interior mark, with I
Analyze/ I
Interior markTo analytical element concentration C i (i=1,2,3 ...) set up calibration curve;
(4) under similarity condition, the fluorescent value of analytical element and internal standard element compares I in the mensuration sample
Sample/ I
Interior mark, tested constituent content Cx from the sample that calibration curve is asked; Wherein said internal standard element comprises that those chemical evapn can occur react, and are not included in again the element in the testing sample.Preferred following elements scandium, titanium, yttrium, zirconium, rhodium, ruthenium, palladium, osmium, iridium, gold, silver, gallium, indium, germanium, thallium, tin, selenium and tellurium; Described standard solution refers to the standard solution of element to be measured;
Chemical evapn of the present invention refers to that the chemical evapn of the carrying out under the lower arbitrary temperature of room temperature to 99 ℃ reacts.
Assay method of the present invention, the element of mensuration wherein refers to easily form traditionally the element arsenic of hydride, antimony, bismuth, germanium, tin, lead, selenium, tellurium, mercury.
Need to prove: the special hollow cathode modulation that is made into internal standard element of this method indication and the hollow cathode lamp that element to be measured is made into replace the irradiated atoms device, thereby alternately excite the atomic fluorescence signal of internal standard element and element to be measured, reach two elements or how to measure simultaneously purpose.This can realize with the two pass that has had in the market or multiple tracks atomic fluorescence of zero dispersion, also can use other mechanical means to make sequentially irradiated atoms device of two or the branched element hollow cathode lamp to be measured of all having lighted and internal standard element hollow cathode lamp, typical method can be with reference to Chinese invention patent application (03104978.8, sequential scanning be without penetrating loose atomic fluorescence spectrometer).
Internal standard method when gaseous state sample introduction atomic fluorescence of zero dispersion disclosed in this invention is measured element, the good effect that has is:
(1) this method can effectively be improved use chemical evapn generation sample introduction-calibration curve correlativity when atomic fluorescence of zero dispersion is measured element.
Low, the jitter of fluorescence intensity brings the deficiencies such as precision is poor when (2) having improved element determination, can reduce the experiment condition change and the stochastic error that causes, has improved the mensuration preci-sion and accuracy.
The chemistry and the Physical Interference that have existed when (3) effectively having eliminated chemical evapn generation sample introduction.
Detection limit when (4) effectively reducing element determination.
Description of drawings:
Fig. 1 is that this method correction graph and sample size are measured procedure chart.
Embodiment
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
(1) setting of instrument aspect: in the mensuration process, the hollow cathode lamp that the special hollow cathode modulation that is made into internal standard element and element to be measured are made into replaces the irradiated atoms device, thereby alternately excite the atomic fluorescence signal of internal standard element and element to be measured, reach two elements or multielement simultaneous determination purpose;
(2) preparation of solution aspect: in standard solution and solution to be measured, add respectively a certain amount of internal standard element, the fluorescent value ratio of determination and analysis element and internal standard element when standard solution is measured
I Analyze / I Interior mark , with
I Analyze / I Interior mark To analytical element concentration
Ci(i=1,2,3 ...) set up calibration curve; Under similarity condition, the fluorescent value degree ratio of determined element and internal standard element in the mensuration sample
I Sample / I Interior mark , according to measured fluorescent value ratio tested constituent content Cx from the sample that calibration curve is asked;
Described internal standard element comprises that those chemical evapn can occur react, and the element that in testing sample, does not contain.Preferred following elements scandium, titanium, yttrium, zirconium, rhodium, ruthenium, palladium, osmium, iridium, gold, silver, gallium, indium, germanium, thallium, tin, selenium and tellurium; Described standard solution refers to element standard solution to be measured;
The described chemical evapn of this method chemical evapn that refers to the carrying out under room temperature to 99 ℃ lower arbitrary temperature that reacts reacts.
Embodiment 2
1. use the powerful hollow cathode lamp of gold and arsenic as two light sources, on a dual channel atomic fluorescence photometers, adopt pulse power supply that two lamps are alternately lighted, thereby alternately obtain the fluorescence signal of gold and arsenic, measure when reaching gold and arsenic.Aspect solution prepares, be respectively in concentration in the standard solution that contains arsenic of (0,2.0,4.0,6.0,8.0 ng/mL) and the testing sample and add respectively goldstandard 100 ng, it is 5%(v/v that all solution is all controlled the salt acidacidity).Then 1.2%(m/V is adopted in experiment) sodium borohydride solution and standard and sample solution at room temperature carry out continuous chemical steam react (sodium borohydride flow velocity and element solution flow rate are 2.0 ml/min).Measure when carrying out arsenic and gold by the explanation of two pass atom fluorimetry, the fluorescent value of two elements that will record after the mensuration carries out gold by top described method and arsenic fluorescence intensity ratio calculates, draw the internal standard method calibration curve, the content of obtaining arsenic in sample in the above is 5.5ng/mL, with real content coincide fine.If do not use internal standard method, measuring arsenic content is 3.0 ng/mL.
Embodiment 3
Use yttrium hollow cathode lamp and antimony hollow cathode lamp as two light sources, on a dual channel atomic fluorescence photometers, adopt machinery to cut the light method, thereby alternately obtain the fluorescence signal of yttrium and antimony, measure when reaching yttrium and antimony.Aspect solution prepares, be respectively in concentration in the standard solution that contains antimony of (0,1.0,2.0,4.0,6.0,8.0 ng/mL) and the testing sample and add respectively yttrium 100 ng, the acidity that all solution is all controlled nitric acid is 0.20M.Then 1.2%(m/V is adopted in experiment) sodium borohydride solution and standard solution at room temperature carry out the continuous chemical steam and react.Measure when carrying out yttrium and antimony, the fluorescent value of two elements that will record after the mensuration is undertaken calculating with the fluorescence intensity ratio of antimony by top described method, draw just directrix curve of internal standard method, and the content of obtaining antimony in the above is 7.8 ng/mL, coincide fine with true value.And when not using internal standard method, the content of measuring antimony is 5.3 ng/mL.
Embodiment 4
Use the powerful hollow cathode lamp of mercury and rhodium as two light sources, on a dual channel atomic fluorescence photometers, adopt pulse power supply that two lamps are alternately lighted, thereby alternately obtain the fluorescence signal of mercury and rhodium, measure when reaching mercury and rhodium.Aspect solution prepares, be respectively the rhodium that adds respectively 80 ng/ milliliters in the mercurous standard solution of (0,4.0,6.0,8.0,10.0ng/mL) and the testing sample in concentration, the acidity that all solution is all controlled hydrochloric acid is 8%(V/V).Then 1.2%(m/V is adopted in experiment) sodium borohydride solution and standard solution under 98 ℃ of temperature, carry out continuous chemical steam react (flow velocity is 2.0 ml/min).Measure when carrying out mercury by the explanation of two pass atom fluorimetry, the fluorescence intensity ratio that the fluorescent value of two elements that will record after the mensuration carries out gold and rhodium by top described method calculates, draw the internal standard method calibration curve, obtain precision and detection limit and linearly dependent coefficient in the above, the results are shown in Table 1.When using identical conditions, but during without internal standard method (method of the present invention), the result also is listed in the following table in contrast.
The contrast of indices when table 1. this method and conventional method are measured mercury
| ? | Calibration curve correlativity (R 2） | Precision (RSD, %) | Detection limit (ng/mL) |
| Conventional method | 0.9687 | 6.23 | 0.098 |
| This method | 0.9997 | 1.46 | 0.009 |
As can be seen from Table 1, after use this law, the correlativity of calibration curve, precision and detection limit are greatly improved.
Claims (4)
1. the internal standard method a when atom fluorimetry easily forms the hydride element traditionally, it is to measure the method that easily forms traditionally the hydride element with chemical evapn generation-atomic fluorescence of zero dispersion, it is characterized in that being undertaken by following step:
(1) instrument setting: replace or irradiated atoms device in chronological order with the excitation source of internal standard element excitation source and element to be measured, thereby alternately excite the atomic fluorescence signal of internal standard element and element to be measured, reach two elements or multielement simultaneous determination purpose;
(2) solution preparation: in standard solution and sample solution, add respectively a certain amount of internal standard element;
(3) draw calibration curve: the analytical element in the bioassay standard solution and the fluorescent value of internal standard element compare I
Analyze/ I
Interior mark, with I
Analyze/ I
Interior markTo analytical element concentration C i (i=1,2,3 ...) set up calibration curve;
(4) under similarity condition, the fluorescent value of analytical element and internal standard element compares I in the mensuration sample
Sample/ I
Interior mark, tested constituent content Cx from the sample that calibration curve is asked; Wherein said internal standard element comprises that those chemical evapn can occur react the element that does not contain again in testing sample.
2. described assay method according to claim 1, wherein said internal standard element is scandium, titanium, yttrium, zirconium, rhodium, ruthenium, palladium, osmium, iridium, gold, silver, gallium, indium, germanium, thallium, tin, selenium and tellurium; Described standard solution refers to the standard solution of element to be measured.
3. described assay method according to claim 1, wherein said chemical evapn refer to that the chemical evapn of the carrying out under room temperature to 99 ℃ lower arbitrary temperature reacts.
4. assay method according to claim 1, the element of wherein measuring refers to easily form traditionally the element arsenic of hydride, antimony, bismuth, germanium, tin, lead, selenium, tellurium, mercury.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104897634A (en) * | 2015-06-16 | 2015-09-09 | 任志海 | Internal standard method for testing element prone to chemical vapor generation reaction through atomic fluorescence |
| CN106248775A (en) * | 2016-08-31 | 2016-12-21 | 广西壮族自治区地质矿产测试研究中心 | Quantitative detection method for reducing analysis errors of ICP-MS and ICP-AES whole process |
| CN112903652A (en) * | 2021-03-02 | 2021-06-04 | 上海华之光谱仪器有限公司 | Atomic fluorescence thallium measurement instrument |
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|---|---|---|---|---|
| CN101650302A (en) * | 2009-09-14 | 2010-02-17 | 中国一拖集团有限公司 | Test method of micro amount of arsenic or antimony in steel |
| CN202204772U (en) * | 2011-09-02 | 2012-04-25 | 西北有色地质研究院 | Optical device for atom fluorescent signal detection |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650302A (en) * | 2009-09-14 | 2010-02-17 | 中国一拖集团有限公司 | Test method of micro amount of arsenic or antimony in steel |
| CN202204772U (en) * | 2011-09-02 | 2012-04-25 | 西北有色地质研究院 | Optical device for atom fluorescent signal detection |
Non-Patent Citations (1)
| Title |
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| 吴乾丰: "氢化物-无色散原子荧光测定环境样品中微量硒", 《光谱学与光谱分析》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104897634A (en) * | 2015-06-16 | 2015-09-09 | 任志海 | Internal standard method for testing element prone to chemical vapor generation reaction through atomic fluorescence |
| CN106248775A (en) * | 2016-08-31 | 2016-12-21 | 广西壮族自治区地质矿产测试研究中心 | Quantitative detection method for reducing analysis errors of ICP-MS and ICP-AES whole process |
| CN112903652A (en) * | 2021-03-02 | 2021-06-04 | 上海华之光谱仪器有限公司 | Atomic fluorescence thallium measurement instrument |
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