CN116773641A - Method for directly sampling and measuring alcohol ether and trace elements in ester high-purity solvent or hydrogen peroxide - Google Patents
Method for directly sampling and measuring alcohol ether and trace elements in ester high-purity solvent or hydrogen peroxide Download PDFInfo
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- CN116773641A CN116773641A CN202210229880.4A CN202210229880A CN116773641A CN 116773641 A CN116773641 A CN 116773641A CN 202210229880 A CN202210229880 A CN 202210229880A CN 116773641 A CN116773641 A CN 116773641A
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- ethylene glycol
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 53
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002904 solvent Substances 0.000 title claims abstract description 25
- 239000011573 trace mineral Substances 0.000 title claims abstract description 23
- 235000013619 trace mineral Nutrition 0.000 title claims abstract description 23
- 150000002148 esters Chemical class 0.000 title claims abstract description 16
- 238000005070 sampling Methods 0.000 title claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000005495 cold plasma Effects 0.000 claims abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 230000010354 integration Effects 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims description 35
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000012086 standard solution Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 238000009616 inductively coupled plasma Methods 0.000 claims description 10
- -1 glycol ethers Chemical class 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 claims description 5
- JJDGTGGQXAAVQX-UHFFFAOYSA-N 6-methyl-1-(6-methylheptoxy)heptane Chemical compound CC(C)CCCCCOCCCCCC(C)C JJDGTGGQXAAVQX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 claims description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 claims description 2
- OZPOTRRLBSVXKP-UHFFFAOYSA-N 1-ethoxypropan-2-yl formate Chemical compound CCOCC(C)OC=O OZPOTRRLBSVXKP-UHFFFAOYSA-N 0.000 claims description 2
- VIOQEHXYEOORLQ-UHFFFAOYSA-N 1-methoxypropan-2-yl formate Chemical compound COCC(C)OC=O VIOQEHXYEOORLQ-UHFFFAOYSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- NVWVLSVNDUHYMG-UHFFFAOYSA-N 2-ethoxyethanol;formic acid Chemical compound OC=O.CCOCCO NVWVLSVNDUHYMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- YXIDSOCDWLQVAZ-UHFFFAOYSA-N ethane-1,2-diol;formic acid Chemical compound OC=O.OCCO YXIDSOCDWLQVAZ-UHFFFAOYSA-N 0.000 claims description 2
- YBNGJDURAFFPPT-UHFFFAOYSA-N formic acid;2-methoxyethanol Chemical compound OC=O.COCCO YBNGJDURAFFPPT-UHFFFAOYSA-N 0.000 claims description 2
- NHVPKUVVLGHSBZ-UHFFFAOYSA-N formic acid;propane-1,2-diol Chemical compound OC=O.CC(O)CO NHVPKUVVLGHSBZ-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000012495 reaction gas Substances 0.000 abstract description 5
- 238000011002 quantification Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010812 external standard method Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 57
- 239000011734 sodium Substances 0.000 description 41
- 239000011133 lead Substances 0.000 description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 8
- 238000012937 correction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- HVSACIINGLQLCS-UHFFFAOYSA-N 2-methoxyethyl formate Chemical compound COCCOC=O HVSACIINGLQLCS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001793 charged compounds Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021654 trace metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- RESSOZOGQXKCKT-UHFFFAOYSA-N ethene;propane-1,2-diol Chemical compound C=C.CC(O)CO RESSOZOGQXKCKT-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The application relates to a method for directly sampling and measuring trace elements in alcohol ether and ester high-purity solvents or hydrogen peroxide. Wherein the microelements comprise alkali metal elements, alkaline earth metal elements, heavy metal elements or Al; in the detection condition, alkali metal elements, alkaline earth metal elements and partial heavy metal elements are matched with a reaction mode to detect under the condition of cold plasma, and the reaction gas H 2 The flow rate is 2mL/min, partial heavy metal is detected by matching with a collision mode under the condition of thermal plasma, and the flow rate of collision gas He is 3mL/min; radio frequency power: cold plasma 750W, hot plasma 1550W; integration time: 0.1 to 1S. The application can perform direct sample injection measurement without pretreatment to enrich metal elements, avoids the possible pollution problem in the pretreatment process, adopts a standard addition method to perform quantification, and solves the problem of interference of matrix effect in an external standard method.
Description
Technical Field
The application belongs to the technical field of chemical analysis, and relates to a method for detecting trace elements in alcohol ether and an ester solvent thereof or hydrogen peroxide, in particular to a method for directly detecting trace elements in alcohol ether and an ester high-purity solvent thereof or hydrogen peroxide by sample injection without pretreatment.
Background
The alcohol ether solvent mainly refers to glycol ether prepared by ring-opening alkylation of ethylene oxide, propylene oxide, methanol and other alcohols, and propylene glycol ether; the alcohol ether ester solvent mainly refers to a product prepared by esterification of the ethylene (propylene) glycol ether and acid. The solvent contains two functional groups with strong solubility in the molecular structure, namely hydroxyl and ether bond, and has good dissolving capacity for polar or nonpolar substances, and is widely applied to industrial manufacturing.
The electronic alcohol ether solvent and hydrogen peroxide are used as a new type of environment protecting wet electronic chemical, and are mainly used as cleaning agent or stripping liquid in LCD manufacture and semiconductor industry. In recent years, the requirements for wet electronic chemicals are increasing at home and abroad, the requirements for quality indexes of the wet electronic chemicals are also becoming stricter, and the content of trace metal impurities becomes one of key contents which the wet electronic chemical industry needs to break through. The metal impurities in wet electronic chemicals can harm the electrical performance of electronic components, different types of impurities have different damages to devices and circuits, and trace amounts of metal impurities (mug/L) can seriously affect the product quality of semiconductors. For example, alkali metals (Na, ca, K) can cause component leakage, resulting in low breakdown; when heavy metal impurities such as Cu, fe, cr, pb adhere to the surface of a silicon wafer, the P-N junction withstand voltage is lowered, and IC electrical performance is affected.
As the requirements for metal impurity levels in wet electronics become more stringent, corresponding analytical detection techniques are necessary. Typical techniques for trace metal detection include graphite furnace atomic absorption spectrometry, inductively coupled plasma emission spectrometry, and inductively coupled plasma mass spectrometry, where the following problems exist: 1) The detection limit of the inductively coupled plasma spectrometry cannot meet the detection requirement of an electronic-grade reagent, trace metals are enriched by pretreatment of a sample, and pollution is likely to be caused in the process even in an ultra-clean environment; 2) The graphite furnace atomic absorption spectrometry cannot analyze multiple elements simultaneously, a light source lamp is required to be replaced when different elements are measured, and the time for analyzing the multiple elements is long.
Disclosure of Invention
The application aims to solve the technical problems and provides a method for directly detecting trace elements in alcohol ether and ester high-purity solvents or hydrogen peroxide without pretreatment. In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the application provides a method for directly detecting trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof by sample injection, which comprises the following steps:
A. standard solution preparation and standard curve drawing by standard addition method
Weighing a certain amount of sample standard substance to be measured in a reagent bottle, quantitatively adding the sample standard substance into a mixed standard solution containing trace element specific isotopes with a certain concentration into the reagent bottle at least five times, detecting once by adopting an inductively coupled plasma mass spectrometer, drawing a standard curve by taking the concentration as an abscissa and the count value of each element per second as an ordinate, and fitting a regression equation and a linear correlation coefficient;
B. sample detection: and detecting the sample to be detected by directly feeding the sample to be detected into the inductively coupled plasma mass spectrometer, and comparing the sample with a standard curve.
Wherein the microelements comprise alkali metal elements, alkaline earth metal elements, heavy metal elements or Al elements;
the detection conditions are as follows:
detection mode: detecting alkali metal elements, alkaline earth metal elements and partial heavy metal elements in a reaction mode under the condition of cold plasma, and reacting gas H 2 The flow rate is 2mL/min, partial heavy metal is detected by matching with a collision mode under the condition of thermal plasma, and the flow rate of collision gas He is 3mL/min;
carrier gas flow rate aspect: 0.7L/min under cold plasma condition and 0.42L/min under hot plasma condition;
radio frequency power: cold plasma 750W, hot plasma 1550W;
integration time: 0.1 to 1S, preferably 0.3 to 0.5S.
In the application, the alcohol ether and the ester high-purity solvent thereof are glycol ether or propylene glycol ether and formic acid or acetic acid ester high-purity solvent thereof.
Glycol ethers include, but are not limited to, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol isooctyl ether, including, but not limited to, propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol butyl ether;
ethylene glycol formic acid or acetate includes, but is not limited to, ethylene glycol methyl ether formic acid or acetate, ethylene glycol ethyl ether formic acid or acetate, ethylene glycol propyl ether formic acid or acetate, ethylene glycol butyl ether acetate; the propylene glycol formic acid or acetate includes, but is not limited to, propylene glycol methyl ether formate, propylene glycol methyl ether acetate, propylene glycol ethyl ether formate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate.
Preferably, the alkali metal element comprises Na, K; the alkaline earth metal element comprises Ca and Mg; the heavy metal elements include Cr, mn, fe, ni, cu, pb.
Wherein, the isotope selection of Na 23 Isotope selection of Na, K 39 Isotope selection of K, fe 56 Isotope selection of Fe, pb 208 Pb。
Preferably, in the step a, the preparation method of the standard solution is as follows:
1-1000 mL of sample standard to be measured is weighed and placed in a reagent bottle, a mixed standard solution containing 1-10000 mug/mL of trace element specific isotope is added into the reagent bottle at least five times, the addition amount of each time is one ten thousandth of the volume of the sample standard to be measured, and each time of adding the standard is detected by adopting an inductively coupled plasma mass spectrometer.
The preferred operation is as follows: weighing 100mL of sample standard to be measured in a reagent bottle, adding the sample standard to be measured into the reagent bottle at least five times, adding 10 mu L of mixed standard solution containing 10 mu g/mL of trace element specific isotopes into the reagent bottle each time, detecting once by adopting an inductively coupled plasma mass spectrometer each time when the standard is added, and respectively preparing the solution with addition amounts of 1, 2, 3, 4 and 5 mu g/L.
The number of sample addition is determined according to the number of addition of the standard quantity, the more and the clearer the standard curve is, the fewer the number of sample addition is, and the curve model can be performed.
100mL corresponds to 10 mug/mL and is determined according to the standard sample of the configuration solution, 100mL can be optimized for 1-5 mug/L and 6-10 mug/L, and the standard curve is drawn to increase the scalar according to the curve forming form, so that the data curve is more perfect.
Compared with the prior art, the application has the following beneficial effects:
the application can directly sample and determine the electronic grade low carbon alcohol ether and the acetate high purity solvent, without pretreatment to enrich metal elements, and avoids the possible pollution problem in the pretreatment process. The application adopts the standard addition method to carry out quantification, solves the problem of interference of matrix effect in the external standard method, and avoids other pollution caused by introducing an internal standard by using the internal standard method.
In the test process, the application eliminates related mass spectrum interference by utilizing a cold plasma technology and a collision reaction tank technology, and can rapidly switch among detection modes, so that multi-element simultaneous analysis can be performed, and the analysis efficiency is improved.
Therefore, the detection method is simple, convenient and quick, can meet the requirements of detection accuracy and precision, and is suitable for quick determination of sodium, iron and lead in batch electronic-grade low-carbon alcohol ether and acetate high-purity solvents.
Drawings
FIG. 1 is a graph of the correction of sodium fitted using standard addition in example 1 of the present application: the ordinate in the graph represents the count value per second of the sodium element, and the abscissa represents the concentration of the sodium element.
Fig. 2 is a graph of the correction of iron fitted using standard addition in example 1 of the present application: in the graph, the ordinate represents the iron element count value per second, and the abscissa represents the iron element concentration.
Fig. 3 is a graph of lead correction fitted using standard addition in example 1 of the present application: the ordinate in the graph represents the count value per second of the lead element, and the abscissa represents the concentration of the lead element.
FIG. 4 shows the response values of sodium and iron element detection and H in example 2 of the present application 2 Flow rate versus He flow rate.
FIG. 5 shows apparent concentrations of sodium and iron elements and H in example 2 of the present application 2 Flow velocity relationship diagram.
Fig. 6 is a graph showing the relationship between the lead element detection response value and He flow rate in example 2 of the present application.
Fig. 7 is a graph showing the apparent concentration of lead element versus He flow rate in example 2 of the present application.
Detailed Description
The following examples are given to illustrate the present application in detail, but the scope of the present application is not limited to the following examples.
Example 1
In the embodiment, propylene glycol methyl ether is taken as an example, sodium, iron and lead in the propylene glycol methyl ether are directly detected, and an inductively coupled plasma mass spectrometry method for directly detecting trace elements in alcohol ether and ester solvents thereof by sample injection is provided. And respectively carrying out fitting of correction curves and determination of detection limits on propylene glycol methyl ether by using a standard addition method and a standard curve method.
1. Main instrument and reagent
Agilent 7900ICP-MS (Agilent corporation), ICP-MS MassHunter (Agilent corporation), FST-VV-20 ultrapure water machine (Prime Li Feier), FA2004B electronic balance (Shanghai Tianmei balance instruments Co., ltd.); sodium, iron, lead mixed standard solution (10. Mu.g/mL, agilent) ultrapure water (resistivity 18.25 M.OMEGA.cm).
2. Determination of analysis conditions
1.1 selection of isotopes: the selection principle of the isotope is to select the isotope with large natural abundance, small interference and large detection sensitivity. Respectively under the same instrument condition 55 Fe、 56 Fe、 57 Fe、 206 Pb、 207 Pb、 208 Pb detection and data display 56 Fe、 208 The detection sensitivity of Pb is high, the linear relation of the correction equation is good, and the detection accuracy and precision are in a proper range. In addition, since Na has only one mass number, the selection 23 Na was detected.
1.2 determination of instrument parameters: and the control variable method is adopted to respectively optimize the parameters of the instrument such as radio frequency power, carrier gas flow rate, integration time and the like.
1.3 matching of detection patterns to elements: the method utilizes a cold plasma technology and a collision reaction tank technology to remove mass spectrum interference in the detection process of each element. The cold plasma technology is to reduce the plasma temperature to inhibit the interference of multi-atom ions formed by Ar, C, N, O ionization, and the collision reaction tank technology is to collide or react the multi-atom ions by using collision/reaction gas to achieve the purpose of eliminating the interference. Na, fe being susceptible to multi-atomic ion interference, e.g. 7 Li 16 O pair 23 Na， 40 Ar 16 O pair 56 Fe, because Na, fe ionization energy is lower, still obtain fully ionization under the cold plasma condition, and the polyatomic ion interference reduces under this condition, and the testing result is more accurate. Pb mass number is 208, is not easy to be interfered by polyatomic ions, and does not need to be detected under the condition of cold plasma. The method detects Na, fe and Pb in different detection modes, and the data show that the equivalent concentration of Na, fe in a Cool mode and Pb in a He mode background is lower, and the detection accuracy and the detection sensitivity are higher.
1.4 determination of the collision reaction gas flow rate: the interference of the multi-atomic ions of Na and Fe is reduced in the Cool mode, and the interference is further removed by combining the collision reaction tank technology. The Na and the Fe are detected by combining the reaction mode and the collision mode respectively, and the gas flow rate in a more suitable mode is selected, and the data show that the Na and the Fe are more suitable for detection in the reaction mode; pb was detected using He mode and the collision gas flow rate was selected.
3. Sample measurement: and directly introducing the propylene glycol methyl ether solution to be tested into ICP-MS, and measuring under the analysis conditions.
4. Selection of quantitative analysis method
Standard curve method: taking 5 PFA reagent bottles, weighing 100mL of ultrapure water in the bottles, respectively transferring 10, 20, 30, 40 and 50 mu L of mixed standard solution (with the concentration of 10 mu g/mL) containing sodium, iron and lead into five reagent bottles by using a pipette, and preparing a series of standard solutions with the addition amounts of 1, 2, 3, 4 and 5 mu g/L respectively by neglecting the change of the volume due to the small volume of the transferred standard solution. And drawing a standard curve by taking the concentration as an abscissa and the response value of each element as an ordinate, and fitting a regression equation and a linear correlation coefficient. Propylene glycol methyl ether samples were diluted one-fold with ultrapure water and tested by sample injection.
Standard addition method: weighing 100mL of propylene glycol methyl ether sample into a PFA reagent bottle, adding a mixed standard solution (with the concentration of 10 mug/mL) containing sodium, iron and lead into the same reagent bottle for five times, adding 10 mug/mL each time, adding a mark for one time for detection, adding a mark for detection again, and adding the scalar of the finally prepared solution to 1 mug/L, 2 mug/L, 3 mug/L, 4 mug/L and 5 mug/L respectively. And drawing a standard curve by taking the concentration as an abscissa and the response value of each element as an ordinate, and fitting a regression equation and a linear correlation coefficient.
The same sample was continuously measured 10 times, the concentration corresponding to the standard deviation of the signal value of 3 times of the sample was used as the detection limit of each element, and the detection limits of the two quantification methods were compared, and the results are shown in Table 1.
Table 1 comparison of detection limits for two quantification methods
As can be seen from the above table, the standard addition method is more suitable for the detection of trace metals in propylene glycol methyl ether because the detection limits of the elements measured by the standard addition method are smaller than those measured by the standard curve method. The correction curves of sodium, iron and lead fitted by the standard addition method are shown in fig. 1-3, and regression equations of the correction curves of the elements are as follows:
na: y=190311.5805x+144557.2533, the linear correlation coefficient is 0.9997;
fe: y=45112.0080x+9645.4333, the linear correlation coefficient being 0.9996;
pb: y=11674.5295x+988.9667, a linear correlation coefficient of 0.9998,
where y represents the count value per second CPS of each element detection, and x represents the concentration (μg/L) of each element.
Example 2
Sodium, iron and lead contents in propylene glycol methyl ether are detected in different detection modes, wherein the detection modes are a Cool mode, a He mode and a No Gas mode respectively, apparent concentrations of sodium, iron and lead in the same sample in different detection modes are compared, and the results are shown in Table 2:
TABLE 2 apparent concentrations of elements in different detection modes
The apparent concentration is the sum of the background equivalent concentration and the true concentration, and the lower the background equivalent concentration, the lower the apparent concentration and the closer to the true concentration. As can be seen from the above table, the sodium and iron were measured in the Cool mode, the lead was measured in the He mode, and the apparent concentration of each element was low, and the result showed that the background equivalent concentration of each element was low in this mode, and the apparent concentration was close to the true concentration.
The interference in sodium and iron detection under the condition of cold plasma is improved, and the interference is further reduced by combining a collision reaction tank technology. Sodium and iron are detected in collision mode and reaction mode respectively, as shown in figure 4, and the detection response values of sodium and iron element are reversed along with collision in both modesShould decrease with increasing gas flow rate, and at H 2 The response values of sodium and iron elements are higher in the reaction mode, and the detection sensitivity is higher, so that sodium and iron are detected in the cold plasma condition combined reaction mode, and H is inspected 2 Influence of flow rate on detection of each element. As shown in figure 5, the apparent concentration of each element of sodium and iron is along with H 2 The flow rate is increased and decreased and becomes gentle at 2mL/min, which shows that the background interference of the detection of each element is almost reduced to the minimum value, and the apparent concentration is close to the true concentration, so that 2mL/min is selected as the optimal reaction gas flow rate for the detection of sodium and iron elements. In addition, the influence of the He flow rate on the lead detection is examined, as shown in fig. 6 and 7, the lead detection response value has a tendency of increasing and then decreasing with the He flow rate, reaches the maximum value at 3mL/min, decreases with the increase of the He flow rate, and becomes gentle at 3mL/min, so that 3mL/min is selected as the optimal collision gas flow rate for Pb detection.
As is clear from example 2, sodium and iron were detected in the coo mode in accordance with the reaction mode, reaction gas H 2 The flow rate was 2mL/min, lead was detected in He mode, and He flow rate was 3mL/min.
Example 3
And (3) carrying out experiments on the standard recovery rate and precision of each element in the method.
Taking three PFA reagent bottles, respectively weighing 100mL of propylene glycol methyl ether (92.6 g), respectively transferring 10, 20 and 30 mu L of standard mixed solution of sodium, iron and lead into the reagent bottles by using a pipetting gun with the measuring range of 10-100 mu L, shaking uniformly, preparing samples with the adding amounts of 1, 2 and 3 mu g/L respectively, and carrying out sample injection measurement. The recovery of the addition was calculated from the addition amount and the measured amount (the content in the original sample was subtracted), and the results are shown in Table 3. The method has the standard recovery rates of sodium, iron and lead respectively in the ranges of 98.7 to 103.6 percent, 94.2 to 101.6 percent and 85.4 to 92.2 percent, and the result shows that the method has higher accuracy.
Table 3 recovery of each element by marking
Three PFA reagent bottles were taken and added with propylene glycol methyl ether samples, respectively, and marked as sample 1, sample 2 and sample 3. The sodium, iron and lead in the samples were measured by the method of the application, each sample was measured for 7 times continuously, and the average value of the content of each element in the sample and the RSD are shown in Table 4. The RSD of each element in the method is less than or equal to 8.97%, and the result shows that the method has good detection precision.
Table 4 elemental content and precision experiments (n=7)
Example 4
The method is applied to other high-purity alcohol ether reagents and high-purity ether ester reagents, wherein the selected high-purity reagents comprise ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether formate. Fitting experiments of calibration curves were performed on each high purity reagent using the standard addition method described in example 1, and standard recovery and precision experiments as described in example 3 were performed under the calibration curves, with results shown in fig. 5 to 7.
TABLE 5 linear correlation coefficients of other high purity alcohol ether reagent calibration curves
TABLE 6 other high purity reagent labeling recovery
TABLE 7 content and accuracy of the elements of other high purity reagents (n=7)
As shown in the table above, the linear correlation coefficient, the standard recovery rate and the precision of Na, fe and Pb element detection in the high-purity reagents of ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether acetate and ethylene glycol methyl ether formate are all in the proper range, so that the method is suitable for measuring the metal elements in the high-purity alcohol ether reagent and the high-purity ether ester reagent.
The effectiveness of the process of the present application is illustrated by the above examples taking propylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether acetate, and ethylene glycol methyl ether formate as examples. Other non-enumerated solvents such as ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and their formic acid or acetates are similar in nature to the above solvents and can be directly deduced by the method of the present application.
The method is simple and quick, the precision and the accuracy can meet the detection requirements of sodium, iron and lead content in the electronic-grade low-carbon alcohol ether reagent, and technicians engaged in related work can detect the electronic-grade low-carbon alcohol ether reagent by using the method.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the embodiments, and various equivalent modifications and substitutions can be made by those skilled in the art without departing from the spirit of the present application, and these equivalent modifications and substitutions are intended to be included in the scope of the present application as defined in the appended claims.
Claims (8)
1. A method for directly sampling and measuring trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof is characterized by comprising the following steps:
A. standard solution preparation and standard curve drawing by standard addition method
Weighing a certain amount of sample standard substance to be measured in a reagent bottle, quantitatively adding the sample standard substance into a mixed standard solution containing trace element specific isotopes with a certain concentration into the reagent bottle at least five times, detecting once by adopting an inductively coupled plasma mass spectrometer, drawing a standard curve by taking the concentration as an abscissa and the count value of each element per second as an ordinate, and fitting a regression equation and a linear correlation coefficient;
B. sample detection: the sample to be detected is directly injected into an inductively coupled plasma mass spectrometer for detection and is compared with a standard curve,
wherein the trace elements comprise alkali metal elements, alkaline earth metal elements, heavy metal elements or Al elements;
the detection conditions are as follows:
detection mode: detecting alkali metal elements, alkaline earth metal elements and partial heavy metal elements in a reaction mode under the condition of cold plasma, and reacting gas H 2 The flow rate is 2mL/min, partial heavy metal is detected by matching with a collision mode under the condition of thermal plasma, and the flow rate of collision gas He is 3mL/min;
radio frequency power: cold plasma 750W, hot plasma 1550W;
integration time: 0.1 to 1S.
2. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 1, which is characterized in that:
wherein the alcohol ether and the ester high-purity solvent thereof are glycol ether or propylene glycol ether and formic acid or acetate high-purity solvents thereof.
3. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 2, which is characterized in that:
wherein the glycol ethers comprise ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether and ethylene glycol isooctyl ether, and the propylene glycol ethers comprise propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol butyl ether;
the ethylene glycol formic acid or acetate comprises ethylene glycol methyl ether formic acid or acetate, ethylene glycol ethyl ether formic acid or acetate, ethylene glycol propyl ether formic acid or acetate and ethylene glycol butyl ether acetate; the propylene glycol formic acid or acetate comprises propylene glycol methyl ether formate, propylene glycol methyl ether acetate, propylene glycol ethyl ether formate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate.
4. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 1, which is characterized in that:
wherein the alkali metal element comprises Na and K;
the alkaline earth metal element comprises Ca and Mg;
the heavy metal element comprises Cr, mn, fe, ni, cu, pb.
5. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 1, which is characterized in that:
wherein, the isotope selection of Na 23 Isotope selection of Na, K 39 Isotope selection of K, fe 56 Isotope selection of Fe, pb 208 Pb。
6. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 1, which is characterized in that:
in the step A, the preparation method of the standard solution is as follows:
1-1000 mL of sample standard to be measured is weighed and placed in a reagent bottle, a mixed standard solution containing 1-10000 mug/mL of trace element specific isotope is added into the reagent bottle at least five times, the addition amount of each time is one ten thousandth of the volume of the sample standard to be measured, and each time of adding the standard is detected by adopting an inductively coupled plasma mass spectrometer.
7. The method for directly detecting trace elements in alcohol ether and ester high-purity solvents or hydrogen peroxide thereof by sample injection according to claim 4, which is characterized in that:
in the step A, the preparation method of the standard solution is as follows:
weighing 100mL of sample standard to be measured in a reagent bottle, adding the sample standard to be measured into the reagent bottle at least five times, adding 10 mu L of mixed standard solution containing 10 mu g/mL of trace element specific isotopes into the reagent bottle each time, detecting once by adopting an inductively coupled plasma mass spectrometer each time when the standard is added, and respectively preparing the solution with addition amounts of 1, 2, 3, 4 and 5 mu g/L.
8. The method for directly sampling and determining trace elements in alcohol ether and ester high-purity solvent or hydrogen peroxide thereof according to claim 1, which is characterized in that:
wherein the integration time is 0.2S-0.5S.
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