Method for simultaneously measuring contents of osmium and ruthenium in carbonylation alloy
The osmium and ruthenium contents in carbonyl alloys were determined by alkali fusion and inductively coupled plasma mass spectrometry, which solved the problem of inaccurate determination in traditional methods and achieved efficient and simple simultaneous analysis.
Patent Information
- Application Number
- CN202510686518.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-27
- Publication Date
- 2025-09-23
AI Technical Summary
In the existing technology, when measuring the osmium and ruthenium content in carbonyl alloys, bromine and other reducing gases are generated, resulting in inaccurate measurements. In addition, traditional methods interfere with osmium.
The sample was dissolved by alkali fusion, and the vapors of osmium tetroxide and ruthenium tetroxide were distilled out through oxidation reaction and absorbed by ascorbic acid solution. Subsequently, the sample was determined by inductively coupled plasma mass spectrometry, and a standard curve was drawn using rhenium as the internal standard element.
The simultaneous and accurate determination of osmium and ruthenium is achieved, the operation process is simplified, and the influence of high-salt matrix on the determination is reduced. It is suitable for the simultaneous analysis of osmium and ruthenium in carbonyl alloys.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of ion analysis and testing, and relates to a method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy. Background Art
[0002] Common methods for enriching osmium and ruthenium include alkaline fusion-water leaching, oxidative distillation, medium-temperature chlorination, oxidative volatilization, and precipitation. The current analytical method for detecting osmium and ruthenium in materials involves alkaline fusion with an alcohol burner, followed by oxidative distillation to volatilize the osmium and ruthenium as tetroxides. Osmium and ruthenium are then separated by absorption using alkali and acid, respectively, and measured using standard addition plasma emission spectrometry. However, some issues have been identified during actual experiments, such as the generation of bromine and other reducing gases, which are toxic and harmful and interfere with the determination of osmium, resulting in inaccurate osmium determination. Summary of the Invention
[0003] The invention belongs to the technical field of mineral detection and relates to a method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy.
[0004] To this end, the present invention adopts the following technical solutions: A method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy comprises the following steps: (1) Sample decomposition: weigh 0.5-2g of sample into a 30mL nickel crucible, add 4g of sodium peroxide, stir evenly, and then cover the surface with 2g of sodium peroxide. Use an alcohol burner to melt the sample. When the sample is bright red and molten, keep it warm for 3-6 minutes, then cool it. After cooling, place the nickel crucible into a beaker filled with 100mL of high-purity water for leaching, and finally place the leached sample into a flask; (2) Steam separation: add 4 g of sodium bismuthate and 16 mL of sodium chloride aqueous solution to the flask, then add 30 mL of ascorbic acid solution to the absorption flask, and connect the flask to the absorption flask. Finally, add 20 mL of saturated potassium permanganate aqueous solution and 120 mL of sulfuric acid solution to the flask and heat it. When a large amount of steam is generated in the steam pipeline, start timing. Remove the absorption flask after 20 minutes and transfer the solution in the absorption flask to a 200 mL volumetric flask. Make up to volume with water. Take 2.00 mL of the solution and put it into a 100 mL volumetric flask. Add 5 mL of hydrochloric acid and make up to volume with water to obtain the solution to be tested. (3) Prepare the calibration curve solution by pipetting 0 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL, and 20.00 mL of the mixed standard solution of osmium and ruthenium into a set of 100 mL volumetric flasks, respectively, adding 2 mL of ascorbic acid solution, adding 5 mL of hydrochloric acid, and diluting to volume with high-purity water, and shaking well; (4) Plasma mass spectrometry: The solution to be tested is measured using an inductively coupled plasma mass spectrometer, with rhenium as the internal standard.
[0005] Furthermore, the sodium peroxide in step (1) is analytically pure.
[0006] Furthermore, the sodium bismuthate in step (2) is analytically pure.
[0007] Furthermore, the concentration of the ascorbic acid solution in step (2) is 30%.
[0008] Furthermore, the concentration of the mixed standard solution of osmium and ruthenium in step (3) is 100 μg / L.
[0009] The beneficial effects of the present invention are: using an alkali fusion method to dissolve the sample, distilling osmium tetroxide and ruthenium tetroxide vapors from the oxidation reaction, which are absorbed by an ascorbic acid solution, and then determining them by inductively coupled plasma mass spectrometry after acidification; the method is simple and easy to operate, changes the influence of traditional high-salt matrices on the determination of osmium and ruthenium, and is suitable for the simultaneous analysis of osmium and ruthenium in carbonyl alloys. DETAILED DESCRIPTION
[0010] The present invention is described in detail below in conjunction with embodiments: A method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy, characterized in that it comprises the following steps: Decompose the sample. Weigh 1g of the sample into a 30mL nickel crucible, add 4g of sodium peroxide (analytical grade) and stir well. Then cover it with 2g of sodium peroxide and use an alcohol burner to melt it. The alcohol burner has a high melting temperature and melts the sample quickly. It takes about eight minutes to dissolve a carbonyl alloy sample. When the sample is in a molten state, shake it slightly every 20s. When the sample is in a bright red molten state, keep it warm for 5min, then cool it for 1min. After cooling, place the nickel crucible containing the molten sample in a 400mL beaker containing 100mL of high-purity water for leaching. The total leaching volume is controlled at 200mL. Finally, place the leached sample in a 1000mL round-bottom flask and wait for distillation.
[0011] (2) Steam separation: add 4g sodium bismuthate (analytical grade) and 16mL of 1g / L sodium chloride aqueous solution to the flask, then add 30mL of 30% ascorbic acid solution to the absorption flask, use the ascorbic acid solution as a reducing agent, and connect the flask to the absorption flask. Finally, add 20mL of saturated potassium permanganate aqueous solution and 120mL of sulfuric acid (1+1) solution to the flask, heat it with a heating jacket, and start timing when a large amount of steam is generated in the steam pipeline. After 20 minutes, remove the absorption flask and transfer the solution in the absorption flask to a 200mL volumetric flask, dilute to volume with water, take 2.00mL of the solution into a 100mL volumetric flask, and add 5mL of hydrochloric acid ( r =1.19 g / mL), dilute to volume with water to obtain the test solution.
[0012] (3) Prepare the calibration curve solution by pipetting 0 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL, and 20.00 mL of the osmium and ruthenium mixed standard solution, adding 2 mL of 30% ascorbic acid solution and 5 mL of hydrochloric acid ( r =1.19g / mL), dilute to volume with high-purity water, and shake well.
[0013] (4) Plasma mass spectrometry determination: First, the mixed standard solution of osmium and ruthenium was determined by inductively coupled plasma mass spectrometry, with rhenium as the internal standard, and a standard curve was drawn. The solution to be tested was determined by inductively coupled plasma mass spectrometry, with rhenium as the internal standard. Specifically, during the operation of the inductively coupled plasma mass spectrometer, the settings of parameters such as the nebulizer flow rate and the test solution lifting volume have a direct impact on the determination of the elements to be tested. The influence of each parameter on the sensitivity was tested. Taking all factors into consideration, the instrument operating parameters were optimized as shown in Table 1.
[0014] Spectral line interference and isotope selection When using ICP-MS to analyze samples, choosing the right spectral line is an important prerequisite for ensuring the accuracy and precision of the analysis. Under normal circumstances, the types of spectral interference in ICP-MS are: ① Background interference. The carrier gas used (Ar2), the impurity gases in the carrier gas (SO2, O2, CO, N2, etc.), and the solvent used to dissolve the sample (HCl, HNO 3) The atomic and molecular ions formed in the plasma environment produce spectral interference on the measured elements, such as Ar + 、ArH + etc.;②Interference between isobaric elements, such as 50 Ti+ and 50 Cr+, etc.; ③ The interference of derivatives formed by metal ions on the measured elements, such as 48 Ti16O + right 64 Cu + Interference; ④ Interference from doubly charged ions, such as 105 Pd + and 209 Bi 2+ Interference, etc.; Generally, when selecting spectral lines, most people choose spectral lines with less interference and higher sensitivity. Carbonyl alloy contains a small amount of elements such as yttrium, indium, cadmium, bismuth, etc., so conventional elements cannot be used as internal standards. After full element spectrum analysis, there is no rhenium element in carbonyl alloy, so we choose 187 Re was used as internal standard.
[0015] According to the analytical method, osmium and ruthenium in carbonyl alloy 15915 were determined in parallel seven times. The relative standard deviation (RSD) of each element was calculated and shown in Table 2.
[0016] Table 2 The results show that the standard deviation of osmium is 0.73%, the relative standard deviation is 4.35%, the standard deviation of ruthenium is 0.75%, the relative standard deviation is 2.02%, and the relative standard deviation of osmium is greater than 3%. This is related to the fact that osmium is easily volatile at room temperature. During the experiment, lowering the steam temperature for condensation can reduce the relative standard deviation of osmium. This method can meet the determination requirements.
[0017] From the above experimental results, it can be seen that it is feasible to use inductively coupled plasma mass spectrometry to simultaneously and directly determine osmium and ruthenium in carbonyl alloys. This method adopts alkali fusion method to dissolve the sample, and the oxidation reaction distills out osmium tetroxide and ruthenium tetroxide vapor, which is absorbed by ascorbic acid solution. After acidification, inductively coupled plasma mass spectrometry is used for determination. It is also suitable for the simultaneous analysis of osmium and ruthenium in carbonyl alloys.
Claims
1. A method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy, characterized in that: The following steps are involved: (1) Sample decomposition: weigh 0.5-2g of sample into a 30mL nickel crucible, add 4g of sodium peroxide, stir evenly, and then cover the surface with 2g of sodium peroxide. Use an alcohol burner to melt the sample. When the sample is bright red and molten, keep it warm for 3-6 minutes, then cool it. After cooling, place the nickel crucible into a beaker filled with 100mL of high-purity water for leaching, and finally place the leached sample into a flask; (2) Steam separation: add 4 g of sodium bismuthate and 16 mL of sodium chloride aqueous solution to the flask, then add 30 mL of ascorbic acid solution to the absorption flask, and connect the flask to the absorption flask. Finally, add 20 mL of saturated potassium permanganate aqueous solution and 120 mL of sulfuric acid solution to the flask and heat it. When a large amount of steam is generated in the steam pipeline, start timing. Remove the absorption flask after 20 minutes and transfer the solution in the absorption flask to a 200 mL volumetric flask. Make up to volume with water. Take 2.00 mL of the solution and put it into a 100 mL volumetric flask. Add 5 mL of hydrochloric acid and make up to volume with water to obtain the solution to be tested. (3) Prepare the calibration curve solution by pipetting 0 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.00 mL, and 20.00 mL of the mixed standard solution of osmium and ruthenium into a set of 100 mL volumetric flasks, respectively, adding 2 mL of ascorbic acid solution and 5 mL of hydrochloric acid, diluting to volume with high-purity water, and shaking well; (4) Plasma mass spectrometry: The solution to be tested is measured using an inductively coupled plasma mass spectrometer, with rhenium as the internal standard.
2. The method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy according to claim 1, wherein: The sodium peroxide in step (1) is analytical grade.
3. The method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy according to claim 1, wherein: The sodium bismuthate in step (2) is analytically pure.
4. The method for simultaneously determining the contents of osmium and ruthenium in a carbonyl alloy according to claim 1, wherein: The concentration of the ascorbic acid solution in step (2) is 30%.
5. The method for simultaneously determining the contents of osmium and ruthenium in carbonyl alloy according to claim 1, wherein: The concentration of the mixed standard solution of osmium and ruthenium in step (3) is 100 μg / L.