CN112881508A - Method for determining anhydrous hydrazine metal content by isotope dilution inductively coupled plasma mass spectrometry - Google Patents
Method for determining anhydrous hydrazine metal content by isotope dilution inductively coupled plasma mass spectrometry Download PDFInfo
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 238000001043 isotope dilution inductively coupled plasma mass spectrometry Methods 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 239000003085 diluting agent Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000009616 inductively coupled plasma Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000112 cooling gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 70
- 239000000523 sample Substances 0.000 description 50
- 239000000243 solution Substances 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 8
- 239000003380 propellant Substances 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 6
- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical compound [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004750 isotope dilution mass spectroscopy Methods 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
Abstract
The invention belongs to the technical field of testing, relates to a substance content determination technology, and particularly relates to a method for determining anhydrous hydrazine metal content by an isotope dilution inductively coupled plasma mass spectrometry. The content of metal elements in anhydrous hydrazine is measured by utilizing isotope dilution inductively coupled plasma mass spectrometry, a certain amount of sample is weighed by a decrement method, a mixed sample is prepared by the same method, and the sample is directly tested on a computer without pretreatment. The method for measuring the metal elements in the anhydrous hydrazine is safe, reliable, short in period, low in cost, high in accuracy and good in precision.
Description
Technical Field
The invention belongs to the technical field of testing, relates to a substance content determination technology, and particularly relates to a method for determining anhydrous hydrazine metal content by an isotope dilution inductively coupled plasma mass spectrometry.
Background
The anhydrous hydrazine is one of the most commonly used liquid propellants which can be stored, can be used independently, can also be used together with unsymmetrical dimethylhydrazine or methylhydrazine to form a mixture, and is used for an on-orbit attitude control power system of spacecrafts such as satellites, spacecrafts, deep space probes and the like, a final power system and a fractional order power system of rockets and the like. In the processes of production, storage, transportation, filling and the like, because the used reactor, container, storage tank and pipeline are made of stainless steel and aluminum alloy materials, soluble metal impurities are introduced, the metal impurities mostly exist in the form of metal salt, and excessive metal impurities can have great influence on the catalytic performance of an engine and a single-component propellant and the storage and transportation performance of the propellant, and finally influence the ignition performance of the propellant and the reliability of a propulsion system. Taking iron as an example, the presence of iron (mainly in ionic form) in anhydrous hydrazine has a great influence on its performance, which can directly lead to decomposition or explosion of anhydrous hydrazine. In addition, salt crystals formed by iron ions and a complex formed by the iron ions and anhydrous hydrazine are deposited on an anhydrous hydrazine propellant bed, so that the activity of the catalyst is seriously reduced, the catalyst is deposited on a filter screen and a medium conveying pipeline, the flow and the indoor roughness of the propellant are influenced, the ignition combustion performance of the propellant and the reliability of a propulsion system are further reduced, and serious or even serious space accidents are caused. Therefore, the content of metal impurities in anhydrous hydrazine must be strictly controlled.
Currently, the iron content is the only quality control index of metal elements, and strict control regulations are provided in quality specifications of anhydrous hydrazine, hydrazine hydrate, hydrazine-70 and the like, for example, GJB98-86, and the iron content of high-purity, unit and standard anhydrous hydrazine is required to be respectively not more than 0.0004%, 0.0005% and 0.002%.
The existing method for measuring the iron content in the anhydrous hydrazine mainly comprises a spectrophotometry and an Atomic Absorption Spectrophotometry (AAS), at least 100mL of sample is required to be used during measurement due to the fact that the iron content in a hydrazine sample is in the ppm level, and a treatment process for preparing residues by carrying out drip distillation on the sample is required.
The isotope dilution mass spectrometry is a chemical measurement method which is determined to be authoritative by means of high-precision determination of the isotope mass spectrometry and accurate measurement of an added diluent and giving an absolute value of an unknown species in a measured sample through strict mathematical operation. So far, no report of measuring metal elements in anhydrous hydrazine by an isotope dilution inductively coupled plasma mass spectrometry is seen at home and abroad.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a method for measuring the metal content of anhydrous hydrazine by an isotope dilution inductively coupled plasma mass spectrometry. The method for measuring the metal elements in the anhydrous hydrazine is safe, reliable, short in period, low in cost, high in accuracy and good in precision.
The method for analyzing the metal elements in the anhydrous hydrazine provided by the invention can be used for analyzing the elements such as Fe, Mg, Cu, Zn and the like, and comprises the following steps:
1) treating a sample to be detected:
sample 1: weighing 0.1-10 g of anhydrous hydrazine by a decrement method, and diluting a sample by 10-100 times by using dilute acid;
sample 2: weighing equivalent anhydrous hydrazine of a sample 1 by a decrement method, adding an isotope diluent standard substance of an element to be detected to enable the isotope abundance ratio of a specific isotope to a reference isotope in a mixed sample to be 0.9-1.1, and diluting the sample by 10-100 times by using dilute acid;
when the element to be detected is Fe, the specific isotope is56Fe, reference isotope of57Fe；
When the element to be detected is Cu, the specific isotope is63Cu with the reference isotope of65Cu；
When the element to be detected is Mg, the specific isotope is24Mg，The reference isotope is26Mg；
When the element to be detected is Zn, the specific isotope is64Zn with the reference isotope of67Zn。
Sample 3: same amount of dilute acid in sample 2.
In order to ensure that the anhydrous hydrazine matrix does not extinguish the plasma, but does not make the content of the element to be detected too low to be detected, the content of the anhydrous hydrazine in the samples 1 and 2 is not higher than 5 percent and the content of the metal to be detected is about 1ppt-1 ppm.
The dilute acid is dilute hydrochloric acid, dilute nitric acid or a mixed acid of the dilute hydrochloric acid and the dilute nitric acid.
2) And measuring the ion current intensity of the elements to be measured in the samples 1, 2 and 3 by using a high-resolution inductively coupled plasma mass spectrometer, and automatically giving the isotope abundance ratio by using an instrument.
Preferably, the measurement conditions of the inductively coupled plasma mass spectrometer are as follows: 1300W of RF power, 11.5-13.5L/min of cooling gas, 1.5-1.6L/min of auxiliary gas, 30-32.5L/min of atomizing gas, the type of atomizer is a glass concentric atomizer, the sample cone/interception cone is a Ni cone, the dead time is 14ns, and the analysis modes are Fe, Mn,70Zn is Deflector Scan, other isotopes are Deflector Jump, residence time/peak Fe,70Zn is 3ms, other isotopes are 1.1ms, the number of scans Fe,70100 Zn and 90 other isotopes, the cycle times of Fe,70Zn is 40, the other isotope is 80, the resolution is Fe,70Zn is 4000 and the other isotope is 300.
3) According to the measured isotope abundance ratio, the content of the element to be measured in the anhydrous hydrazine is obtained by the following formula:
in the formula:
Cx: the content of elements to be detected in anhydrous hydrazine is unit mol kg-1；
CY: content of elements in isotope diluent standard substance, unit mol kg-1；
CB: the amount of the element to be detected in the sample 3, unit mol;
above CX、CY、CBThe unit of (a) may be mg.kg-1、mg·kg-1、mg；
RX: the isotope abundance ratio of the specific isotope of the element to be detected in the sample 1 to the reference isotope, when the element to be detected is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RY: the isotope abundance ratio of the specific isotope in the isotope diluent standard substance to the reference isotope is that when the detected element is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RXY: the isotope abundance ratio of the specific isotope of the element to be detected in the sample 2 to the reference isotope, when the element to be detected is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RiX: the isotope abundance ratio of the isotope i in the sample 1 to the reference isotope, i is respectively taken to other naturally occurring isotopes except the reference isotope;
RiY: the isotope abundance ratio of the isotope i of the element to be detected in the isotope diluent standard substance to the reference isotope, wherein i is respectively taken from other naturally-occurring isotopes except the reference isotope;
Mi: nuclear mass of isotope i;
mX: mass of anhydrous hydrazine in unit g in sample 2;
mY: sample 2Mass of medium isotope diluent standard substance, unit g.
The invention has the following beneficial effects:
the original method adopts the spectrophotometry to measure after the sample pretreatment by using the spot distillation, the test period of the sample is generally 8h, a large amount of analytical reagents are required, the analysis cost is high, and the detection limit of the method is high. The invention provides an analysis method for measuring metal elements in anhydrous hydrazine, which utilizes isotope dilution inductively coupled plasma mass spectrometry to measure the content of the metal elements in the anhydrous hydrazine. A certain amount of samples are weighed by a decrement method, and mixed samples are prepared by the same method, the samples are directly tested on a computer without pretreatment, the analysis period is shortened, the detection limit of the method is reduced, and the detection reliability is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention. Except as otherwise noted, the following examples were carried out using conventional techniques.
Example one
Determining the content of iron element in certain anhydrous hydrazine:
the isotope dilution inductively coupled plasma mass spectrometry method comprises the following steps:
main apparatus and reagents:
a double-focus sector field inductively coupled plasma mass spectrometer (Nu corporation, uk);
analytical balance model MS205DU (mettler tolero corporation);
57a Fe isotope diluent standard substance (IRMM-620),57the mass fraction of Fe is (1.7335 +/-0.0016) · 10-4mol57Fe·kg-1Isotopic abundance:54Fe＜0.01％、56Fe(2.374±0.028)％、57Fe(95.188±0.033)％、58Fe(2.395±0.017)％；
iron isotope standard substance (GBW04446), isotopic abundance:54Fe(5.8363±0.0062)、56Fe(91.7621±0.0066)％、57Fe(2.1219±0.0057)％、58Fe(0.2797±0.0079)％；
nitric acid, Sigma-aldrich, purity not less than 99.999%, total metal content not more than 10.0 ppm;
the determination method comprises the following steps:
1) treating a sample to be detected:
sample 1: the subtractive method is to weigh about 0.1g (to the nearest 0.00001g) of anhydrous hydrazine solution into a 100mL quartz volumetric flask, add 100mL of 0.1mol/L dilute nitric acid for dilution, and weigh the mass using a balance.
Sample 2: weighing 0.1g (accurate to 0.00001g) of anhydrous hydrazine solution into a 100mL quartz volumetric flask by a decrement method, and adding 0.01g57Adding 100ml of 0.1mol/L nitric acid into a Fe isotope diluent standard substance, and weighing the mass by using a balance.
Sample 3: 100mL of 0.1mol/L nitric acid was taken in a 100mL quartz volumetric flask.
2) Respectively measuring a sample 1, a sample 2 and a sample 3 simultaneously by adopting an inductively coupled plasma mass spectrometer54Fe+、56Fe+、57Fe+And58Fe+the ion current intensity is automatically given by the instrument to the iron isotope abundance ratio in each sample.
2) The iron content in anhydrous hydrazine was calculated from the following formula:
in the formula:
CX: the content of the element to be detected in anhydrous hydrazine is mg/kg-1；
CY: the content of elements in isotope diluent standard substance is mg/kg-1；
CB: the amount of the element to be measured in mg in sample 3;
RX: specific isotope of element to be measured in sample 1 and referenceIsotopic abundance ratio of isotope of56Fe；
RY: the isotope abundance ratio of the specific isotope in the isotope diluent standard substance to the reference isotope is that the specific isotope is56Fe；
RXY: the isotope abundance ratio of the specific isotope of the element to be detected in the sample 2 to the reference isotope, wherein the specific isotope is56Fe；
RiY: the isotope abundance ratio of the isotope i of the element to be detected in the isotope diluent standard substance to the reference isotope, wherein i is respectively taken from other naturally-occurring isotopes except the reference isotope;
RiX: the isotope abundance ratio of the isotope i in the sample 1 to the reference isotope, i is respectively taken to other naturally occurring isotopes except the reference isotope;
Mi: nuclear mass of isotope i;
mX: mass of anhydrous hydrazine in unit g in sample 2;
mY(XY): mass of isotope diluent standard substance in sample 2, unit g;
the reference isotope is57Fe。
The measurement results are shown in table 1:
TABLE 1 measurement of iron in anhydrous hydrazine
According to the measured value and the formula, the content C of the iron in the anhydrous hydrazine is calculatedX＝0.466mg·kg-1。
And verifying the result by adopting a spectrophotometry method. The experimental process for spectrophotometry measuring the iron element in the anhydrous hydrazine according to the GJB98-86 specification is as follows:
transferring a certain amount of anhydrous hydrazine sample, volatilizing an anhydrous hydrazine matrix by using a non-volatile residue measuring device, adding dilute sulfuric acid to wash a residue bottle, transferring a washing liquid into a volumetric flask, sequentially adding hydroxylamine hydrochloride solution, aluminum sulfate solution, phenanthroline solution, ammonium hydroxide solution and ammonium acetate-acetic acid solution to enable iron elements in the solution to develop color, and comparing the solution with a series of standard solutions to obtain the content of the iron elements in the sample.
1) Reagent
(1) Thiocyanic acid solution (200g/L)
(2) Ammonium hydroxide solution (1: 1)
(3) Ammonium acetate-acetic acid solution;
(4) isoamyl alcohol-diethyl ether mixed solution;
(5) hydroxylamine hydrochloride solution (100g/L)
(6) Phenanthroline solution (1g/L)
(7) Aluminum nitrate solution (222g/L)
(8) Iron standard solution in water (GBW 08616): (1000. mu.g/mL)
(9) Sulfuric acid: analytically pure, 0.5mol/L and 2.5 mol/L.
2) Sample pretreatment
Taking the standard sample of 3 mug/g as an example, accurately transferring 5mL of anhydrous hydrazine standard sample, slowly injecting the anhydrous hydrazine standard sample into a dropping funnel, sealing the dropping funnel with nitrogen gas, heating the water bath to 90-95 ℃, vacuumizing the dropping funnel by using a vacuum pump, opening a valve of the dropping funnel, and dropping the anhydrous hydrazine standard sample into a residue bottle at a dropping speed which is suitable for maintaining 1mL of hydrazine sample in the bottle, wherein the evaporation time is controlled within 1.5-2 h. After the anhydrous hydrazine standard sample is steamed, continuously vacuumizing for 20min, removing vacuum by using nitrogen, taking down a residue bottle, wiping the residue bottle by using filter paper, and then putting the residue bottle into a 120 ℃ oven to dry for 2 h.
The GJB98-86 method is suitable for anhydrous hydrazine with low iron content, and 100mL of anhydrous hydrazine needs to be evaporated. In the project, the content of the iron element is high, and only a small amount of anhydrous hydrazine needs to be transferred, so that the project group simultaneously researches the pretreatment of the sample by an open residue steaming method. The specific process is as follows: taking a standard sample of 3 mug/g as an example, a sample of about 5mL of anhydrous hydrazine is accurately transferred into a 10mL quartz beaker, and the beaker is placed on a hot plate and heated to slowly volatilize the anhydrous hydrazine to dryness.
Adding 5mL of 0.5mol/L sulfuric acid into a cooled residue bottle or beaker, heating the residue bottle or beaker on a sealed electric furnace until boiling to dissolve the residue, transferring the solution into a 50mL volumetric flask, washing the residue bottle or beaker with 5mL of 0.5mol/L sulfuric acid and 5mL of distilled water respectively, transferring the washing solution into the volumetric flask, dissolving the residual residue in the residue bottle with 2mL of 2.5mol/L sulfuric acid, transferring the washing solution into the volumetric flask, adding 2mL of hydroxylamine hydrochloride solution, 5mL of aluminum nitrate solution and 10mL of phenanthroline solution respectively, adding ammonium hydroxide solution until a large amount of white precipitates appear in the volumetric flask, checking the pH value to be about 5 by using a wide pH test paper, adding 5mL of ammonium acetate-acetic acid solution, diluting the ammonium acetate-acetic acid solution to a scale by using high-purity water, shaking and uniformly measuring.
3) Preparation of working series standard solution
Accurately transferring 0, 0.05, 0.1, 0.2, 0.3, 0.4 and 0.5mL to 7 100mL volumetric flasks of the standard solution for analyzing the iron component in the water, then respectively adding 2mL of hydroxylamine hydrochloride solution, 5mL of aluminum nitrate solution and 10mL of phenanthroline solution, then adding ammonium hydroxide solution until a large amount of white precipitates appear in the volumetric flasks, detecting the pH value to be about 5 by using a wide pH test paper, then adding 5mL of ammonium acetate-acetic acid solution, diluting the solution to a scale by using high-purity water, and shaking up, so that the iron element content in the series of standard solutions is respectively 0, 0.5, 1, 2, 3, 4 and 5 mu g/mL.
4) Testing
And (4) drawing a standard curve by using the prepared series of standard solutions, and measuring the content of the iron element in the sample.
5) Results
The content of iron element in anhydrous hydrazine measured by spectrophotometry is 0.470 mg-kg-1。
The method for determining the metal elements in the anhydrous hydrazine is safe, reliable, short in period, low in cost, high in accuracy and good in precision.
Claims (4)
1. A method for measuring the content of anhydrous hydrazine metal by isotope dilution inductively coupled plasma mass spectrometry is characterized by comprising the following steps:
1) treating a sample to be detected:
sample 1: weighing 0.1-10 g of anhydrous hydrazine by a decrement method, and diluting a sample by 10-100 times by using dilute acid;
sample 2: weighing equivalent anhydrous hydrazine of a sample 1 by a decrement method, adding an isotope diluent standard substance of an element to be detected to enable the isotope abundance ratio of a specific isotope to a reference isotope in a mixed sample to be 0.9-1.1, and diluting the sample by 10-100 times by using dilute acid;
when the element to be detected is Fe, the specific isotope is56Fe, reference isotope of57Fe；
When the element to be detected is Cu, the specific isotope is63Cu with the reference isotope of65Cu；
When the element to be detected is Mg, the specific isotope is24Mg, reference isotope of26Mg；
When the element to be detected is Zn, the specific isotope is64Zn with the reference isotope of67Zn；
Sample 3: the same amount of dilute acid in sample 2;
2) measuring the ion current intensity of elements to be measured in the samples 1, 2 and 3 by using a high-resolution inductively coupled plasma mass spectrometer, and automatically giving the isotope abundance ratio by using an instrument;
3) according to the measured isotope abundance ratio, the content of the element to be measured in the anhydrous hydrazine is obtained by the following formula:
in the formula:
CX: the content of elements to be detected in anhydrous hydrazine is unit mol kg-1；
CY: content of elements in isotope diluent standard substance, unit mol kg-1；
CB: the amount of the element to be detected in the sample 3, unit mol;
above CX、CY、CBThe unit of (a) may be mg.kg-1、mg·kg-1、mg；
RX: specificity of the elements to be measured in sample 1The isotope abundance ratio of the isotope to the reference isotope, when the detected element is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RY: the isotope abundance ratio of the specific isotope in the isotope diluent standard substance to the reference isotope is that when the detected element is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RXY: the isotope abundance ratio of the specific isotope of the element to be detected in the sample 2 to the reference isotope, when the element to be detected is Fe, the specific isotope is56Fe; when the element to be detected is Cu, the specific isotope is63Cu; when the element to be detected is Mg, the specific isotope is24Mg; when the element to be detected is Zn, the specific isotope is64Zn；
RiX: the isotope abundance ratio of the isotope i in the sample 1 to the reference isotope, i is respectively taken to other naturally occurring isotopes except the reference isotope;
RiY: the isotope abundance ratio of the isotope i of the element to be detected in the isotope diluent standard substance to the reference isotope, wherein i is respectively taken from other naturally-occurring isotopes except the reference isotope;
Mi: nuclear mass of isotope i;
mX: mass of anhydrous hydrazine in unit g in sample 2;
mY: mass of isotope diluent standard substance in sample 2, unit g.
2. The method for determining anhydrous hydrazine metal content by isotope dilution inductively coupled plasma mass spectrometry as claimed in claim 1, wherein the anhydrous hydrazine content in samples 1 and 2 is not higher than 5% and the measured metal content is about 1ppt-1 ppm.
3. The method for determining the content of anhydrous hydrazine metal by isotope dilution inductively coupled plasma mass spectrometry as claimed in claim 1, wherein said dilute acid is dilute hydrochloric acid, dilute nitric acid or a mixture thereof.
4. The method for determining the content of anhydrous hydrazine metal by using the isotope dilution inductively coupled plasma mass spectrometry as claimed in claim 1, wherein the measurement conditions of the inductively coupled plasma mass spectrometry are as follows: 1300W of RF power, 11.5-13.5L/min of cooling gas, 1.5-1.6L/min of auxiliary gas, 30-32.5L/min of atomizing gas, the type of atomizer is a glass concentric atomizer, the sample cone/interception cone is a Ni cone, the dead time is 14ns, and the analysis modes are Fe, Mn,70Zn is Deflector Scan, other isotopes are Deflector Jump, residence time/peak Fe,70Zn is 3ms, other isotopes are 1.1ms, the number of scans Fe,70100 Zn and 90 other isotopes, the cycle times of Fe,70Zn is 40, the other isotope is 80, the resolution is Fe,70Zn is 4000 and the other isotope is 300.
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