Hydrolysis sampling method and device for tetrakistrifluorophosphine nickel

Abstract

The present invention discloses a method and device for hydrolysis sampling of nickel tetrakistrifluorophosphine, the method comprising the steps of (i) connection and airtightness detection of components; (ii) injection of concentrated nitric acid into the sampling device; (iii) nitrolysis conversion of nickel tetrakistrifluorophosphine and the like; the device comprises a vacuum container connected to the sample bottle through a pipeline and valve No. Ⅰ, the vacuum container is connected to the sampling device through a pipeline and valve No. Ⅱ, and the sampling device is placed in a freezing container. Under the normal operation of the system, the present invention converts the gaseous sample into a liquid ion form, avoiding the problem that the large molecular weight gas cannot be analyzed by the mass spectrometer for abundance, and at the same time solves the problem of environmental pollution and personal safety caused by the extremely toxic PF3 that may be generated after the gaseous sample enters the mass spectrometer; the work of online sampling and hydrolysis can be completed under the premise of ensuring the normal operation of the test system.

Description

Technical Field

[0001] The invention belongs to the technical field of analysis, and in particular relates to a hydrolysis sampling method and a device for tetrakistrifluorophosphine nickel. Background Art

[0002] Conduct nickel tetrakistrifluorophosphine (Ni(PF 3 ) 4 When studying the nickel abundance analysis technology of ), one of the key technologies is to sample the nickel tetrakistrifluorophosphine. The sampling method has an important impact on the accuracy of the analysis results and the safety of the test personnel.

[0003] The sampling method currently used is the frozen sampling method. The gaseous nickel tetrakis trifluorophosphine obtained by this method is usually limited by the molecular weight of the mass spectrometer injection, which is not convenient for analysis. At the same time, since nickel tetrakis trifluorophosphine itself is toxic, PF may be present during the analysis of gaseous samples. 3 Therefore, it is necessary to establish a hydrolysis sampling method to convert gaseous nickel tetrakis trifluorophosphine into liquid. Summary of the invention

[0004] The present invention is proposed to overcome the shortcomings of the prior art and aims to provide a method for hydrolyzing and sampling tetrakistrifluorophosphine nickel.

[0005] The present invention is achieved through the following technical solutions:

[0006] A method for hydrolyzing and sampling tetrakistrifluorophosphine nickel comprises the following steps:

[0007] (i) Component connection and airtightness testing

[0008] Connect various components, pipelines and valves, and perform tightness measurement and vacuum leak detection;

[0009] (ii) Concentrated nitric acid is injected into the sampling device

[0010] Inject concentrated nitric acid into the sampling device, then connect the sampling device to the device, and evacuate the upper air layer of the sampling device;

[0011] (iii) Nitrolysis of tetrakis(trifluorophosphine) nickel

[0012] Open valve No. Ⅰ, introduce the nickel tetrakistrifluorophosphine gas to be analyzed into the vacuum container, open valve No. Ⅱ, and put the sampling device into the freezing container to freeze. After all the nickel tetrakistrifluorophosphine samples have entered the sampling device, take the sampling device out of the freezing container and slowly thaw it at room temperature. After thawing, open the evacuation valve and evacuate the gas. After completion, a hydrolysis sample of nickel tetrakistrifluorophosphine is obtained in the sampling device.

[0013] In the above technical solution, during the connection and airtightness test of the components in step (i), the sampling device is not connected to the device.

[0014] In the above technical solution, the volume ratio of the nickel tetrakistrifluorophosphine to concentrated nitric acid is in the range of 1 mg: (1-2) mL.

[0015] In the above technical solution, the concentrated nitric acid is chemically pure concentrated nitric acid with a mass fraction of 98%.

[0016] In the above technical solution, after the sampling device (4) is connected to the device in step (ii), a vacuum leak detection is performed on the connection part. After the vacuum leak detection is qualified, step (iii) is entered.

[0017] In the above technical solution, in step (iii), when to open valve II is determined based on the indication of the pressure gauge; the indication of the pressure gauge is the pressure change value generated when all the nickel tetrakis trifluorophosphine gas to be analyzed enters the vacuum air.

[0018] In the above technical solution, the standard for completion of thawing in step (iii) is that no bubbles are generated in the sampling device.

[0019] A hydrolysis sampling device for tetrakistrifluorophosphine nickel comprises a vacuum container connected to a tetrakistrifluorophosphine nickel sample bottle through a pipeline and a No. I valve, the vacuum container is connected to the sampling device through a pipeline and a No. II valve, and the sampling device is placed in a freezing container.

[0020] In the above technical solution, a vacuum port and a pressure gauge are arranged on the top of the vacuum container, and a vacuum valve is arranged on the vacuum port.

[0021] In the above technical solution, the sampling device is made of transparent material.

[0022] The beneficial effects of the present invention are:

[0023] The present invention provides a method and device for hydrolysis sampling of nickel tetrakistrifluorophosphine. By using this method, a gaseous sample is converted into a liquid ion form under the normal operation of the system, thereby avoiding the problem that a large molecular weight gas cannot be analyzed by a mass spectrometer for abundance analysis, and at the same time solving the problem that extremely toxic PF may be generated after the gaseous sample enters the mass spectrometer. 3 This method can complete the online sampling and hydrolysis work under the premise of ensuring the normal operation of the test system. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 2 is a schematic diagram of the structure of the hydrolysis sampling device of tetrakis trifluorophosphine nickel of the present invention;

[0025] in:

[0026] 1 Valve No. Ⅰ 2 Pressure gauge

[0027] 3 Vacuum container 4 Sampling device

[0028] 5 Freezer container 6 Valve II

[0029] 7 Pump down the valve.

[0030] For ordinary technicians in this field, other relevant drawings can be obtained based on the above drawings without any creative work. DETAILED DESCRIPTION

[0031] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention is further described below with reference to the accompanying drawings and through specific implementation methods.

[0032] Example 1

[0033] like Figure 1 As shown, a hydrolysis sampling device of tetrakistrifluorophosphine nickel comprises a vacuum container 3 connected to a tetrakistrifluorophosphine nickel sample bottle via a pipeline and a No. Ⅰ valve 1, the vacuum container 3 is connected to a sampling device 4 via a pipeline and a No. Ⅱ valve 6, and the sampling device 4 is placed in a freezing container 5; an evacuation port and a pressure gauge 2 are arranged on the top of the vacuum container 3, and an evacuation valve 7 is arranged on the evacuation port.

[0034] The pipeline connected to the nickel tetrakisphosphine trifluoroacetate sample bottle adopts a conventional gas cylinder connection method.

[0035] The sampling device 4 is made of transparent material. In this embodiment, the sampling device 4 is a transparent hydrolysis tube made of P10 and has only one inlet.

[0036] Example 2

[0037] A method for hydrolysis sampling of nickel tetrakistrifluorophosphine, based on the device of Example 1, comprises the following steps:

[0038] (i) Component connection and airtightness testing

[0039] according to Figure 1 As shown, the remaining components except the sampling device 4 and the freezing container 5 are connected, and the valves are in the closed state. After the connection is completed, the sealing measurement and vacuum leak detection are carried out. If the sealing is good and the vacuum leak detection is qualified, proceed to the next step.

[0040] The leak detection standard is to evacuate the air until the pressure gauge 2 displays less than 5 Pa, close all valves, and observe for a period of time. If there is no change on the pressure gauge, the sealing is good and the vacuum leak detection is qualified.

[0041] (ii) Concentrated nitric acid is injected into the sampling device

[0042] Inject 1 mL to 2 mL of concentrated nitric acid into the sampling device 4, then connect the sampling device 4 to the device, perform vacuum leak detection on the connection part, and after the vacuum leak detection is qualified, evacuate the upper air of the sampling device 4;

[0043] The method for extracting the upper layer of air from the sampling device 4 is as follows: open valve II 6 and evacuation valve 7, extract from this passage, and close valve II 6 and evacuation valve 7 after the extraction is completed. The operation of extracting the upper layer of air from the sampling device 4 is performed at room temperature, and the extraction time is very short. The purpose of this evacuation operation is to facilitate the subsequent introduction of nickel tetrakistrifluorophosphine.

[0044] The ratio between the mass of Ni(PF3)4 to be analyzed and the added volume of concentrated nitric acid is 1 mg: (1-2) mL, and generally a large excess of concentrated nitric acid is required.

[0045] (iii) Nitrolysis of tetrakis(trifluorophosphine) nickel

[0046] Open valve 1 and place 1 mg of Ni(PF 3 ) 4 The gas is introduced into a 1L vacuum container 3, the indication of the pressure gauge 2 is 5.9Pa, the No. I valve 1 is closed, the No. II valve 6 in front of the sampling device 4 filled with concentrated nitric acid is opened, and the sampling device 4 is placed in a freezing container 5, and liquid nitrogen is added to the freezing container 5 to freeze the sampling device 4, then the tetrakistrifluorophosphine nickel sample and the nitric acid are frozen and collected in the sampling device 4 together; according to the change in the indication of the pressure gauge 2, it is judged whether the tetrakistrifluorophosphine nickel sample has completely entered the sampling device 4, after all of it has entered, the sampling device 4 is taken out from the freezing container 5, and slowly thawed at room temperature, after a period of time, when no bubbles are generated in the sampling device 4, the evacuation valve 7 above the vacuum container 3 is opened, the gas is evacuated, and the evacuation is considered to be completed when the pressure gauge 2 reaches about 5Pa.

[0047] Since the volumes of the pipeline and the vacuum container are fixed, the amount of sample collected can be determined by calculating the pressure difference before and after the tetrakistrifluorophosphine nickel.

[0048] When the sampling device 4 is slowly thawed at room temperature, valve II 6 remains in an open state, and the gas generated by the reaction of the nickel tetrakistrifluorophosphine sample and nitric acid is released into the vacuum container 3 and then extracted through the evacuation valve 7. The extracted gas is treated by the exhaust gas treatment device and then discharged into the atmosphere.

[0049] The sampling device 4 that has completed sampling does not need to be frozen if subsequent testing is performed immediately, but needs to be frozen again if subsequent testing is not performed immediately.

[0050] The hydrolysis process is carried out in a frozen state, which effectively controls the reaction rate and avoids the dangers caused by rapid exothermic temperature rise and rapid pressure changes caused by excessive reaction.

[0051] (iv) ICP-MS test

[0052] 1mg Ni(PF 3 ) 4 The sample was mixed with excess concentrated HNO 3 The complete reaction yielded 0.44 g / L Ni(NO 3 ) 2 The obtained Ni(NO 3 ) 2 After dilution 10,000 times, the concentration of Ni is about 44 μg / L, which meets the injection conditions of the ICP-MS instrument, and ICP-MS can be used for nickel abundance analysis.

[0053] After hydrolysis, nickel tetrakistrifluorophosphine (Ni(PF 3 ) 4 ) is converted to Ni(NO 3 ) 2 The solution avoids the toxicity of gaseous nickel tetrakistrifluorophosphine and the possible generation of PF during gaseous sample analysis. 3 The hydrolyzed samples can be analyzed by ICP-MS.

[0054] The raw material sample of nickel tetrakistrifluorophosphine (the sample without nickel isotope separation) was hydrolyzed by this method and subjected to ICP detection. The results showed that the various isotope abundance values ​​of nickel were close to the various isotope abundance values ​​of nickel consulted in the NiSt database, with a similarity of 99.9%, which fully demonstrated the accuracy of the method of the present invention.

[0055] Working principle of the present invention:

[0056] The present invention combines gaseous tetrakis trifluorophosphine nickel with excess concentrated HNO 3 Reaction, nitrolysis conversion, Ni(PF 3 ) 4 Converted to Ni(NO 3 ) 2 , the diluted Ni(NO 3 ) 2 After the solution is obtained, the nickel abundance analysis can be carried out using ICP-MS instrument.

[0057] By using the hydrolysis sampling method of tetrakis trifluorophosphine nickel of the present invention, gaseous tetrakis trifluorophosphine nickel can be converted into liquid ion form and then subjected to mass spectrometry abundance analysis, because the use of a mass spectrometer is not suitable for analyzing gaseous substances with large molecular weight (>400), and converting the gaseous sample into a liquid sample will not affect the accuracy of the abundance analysis. The method of the present invention performs nitrolysis conversion on the gaseous sample and converts the extremely toxic PF 3 Timely extraction ensures the safety of analysts and avoids environmental pollution.

[0058] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for hydrolysis sampling of nickel tetrakis trifluorophosphine, Features: The invention comprises a vacuum container (3) connected to a nickel tetrakistrifluorophosphine sample bottle via a pipeline and a No. Ⅰ valve (1), the vacuum container (3) is connected to a sampling device (4) via a pipeline and a No. Ⅱ valve (6), and the sampling device (4) is placed in a freezing container (5); The top of the vacuum container (3) is provided with an evacuation port and a pressure gauge (2), and the evacuation port is provided with an evacuation valve (7); The sampling device (4) is made of transparent material; The hydrolysis sampling method of nickel tetrakis trifluorophosphine comprises the following steps: (i) Component connection and airtightness testing Connect various components, pipelines and valves, and perform tightness measurement and vacuum leak detection; (ii) Concentrated nitric acid is injected into the sampling device Inject concentrated nitric acid into the sampling device, then connect the sampling device to the device, and evacuate the upper air layer of the sampling device; (iii) Nitrolysis of tetrakis(trifluorophosphine) nickel Open valve No. Ⅰ, introduce the nickel tetrakistrifluorophosphine gas to be analyzed into the vacuum container, open valve No. Ⅱ, and put the sampling device into the freezing container to freeze. After all the nickel tetrakistrifluorophosphine samples have entered the sampling device, take the sampling device out of the freezing container and slowly thaw it at room temperature. After thawing, open the evacuation valve and evacuate the gas. After completion, a hydrolysis sample of nickel tetrakistrifluorophosphine is obtained in the sampling device.

2. The hydrolysis sampling method of tetrakis trifluorophosphine nickel according to claim 1, Features: During the connection and airtightness test of the components in step (i), the sampling device is not connected to the device.

3. The hydrolysis sampling method of tetrakis trifluorophosphine nickel according to claim 1, Features: The volume ratio of the nickel tetrakistrifluorophosphine to concentrated nitric acid is in the range of 1 mg: (1-2) mL.

4. The hydrolysis sampling method of tetrakis trifluorophosphine nickel according to claim 1, Features: The concentrated nitric acid is chemically pure concentrated nitric acid.

5. The hydrolysis sampling method of tetrakis trifluorophosphine nickel according to claim 1, Features: In the step (ii), after the sampling device (4) is connected to the device, a vacuum leak detection is performed on the connection part. After the vacuum leak detection is qualified, the process proceeds to step (iii).

6. The hydrolysis sampling method of tetrakis trifluorophosphine nickel according to claim 1, Features: In the step (iii), the time to open valve II is determined according to the indication of the pressure gauge; the indication of the pressure gauge is the pressure change value generated when all the nickel tetrakis trifluorophosphine gas to be analyzed enters the vacuum air.

7. The hydrolysis sampling method of tetrakistrifluorophosphine nickel according to claim 1, Features: The standard for the completion of thawing in step (iii) is that no bubbles are generated in the sampling device.

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