CN107024469B - Method for distinguishing propionaldehyde from acetone - Google Patents
Method for distinguishing propionaldehyde from acetone Download PDFInfo
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- CN107024469B CN107024469B CN201710208269.2A CN201710208269A CN107024469B CN 107024469 B CN107024469 B CN 107024469B CN 201710208269 A CN201710208269 A CN 201710208269A CN 107024469 B CN107024469 B CN 107024469B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
- H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
- H01J49/0072—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by ion/ion reaction, e.g. electron transfer dissociation, proton transfer dissociation
Abstract
The invention provides a chemical ionization mass spectrometry detection method for distinguishing propionaldehyde from acetone, which comprises the following steps: (1) processing the metal by a physical and chemical method to generate mononuclear metal ions; (2) loading the mononuclear metal ions obtained in the step (1) into a reaction tube by using buffer gas; (3) sending a gas sample to be detected into the reaction tube in the step (2), and reacting the gas sample with the mononuclear metal ions in the reaction tube to generate an ionization product; (4) and (4) detecting the ionization product obtained in the step (3) by a detector, and distinguishing propionaldehyde and acetone gas according to a detection result. The method makes mononuclear metal ions generated by the transition metal react with the propionaldehyde and the acetone as reagent ions, not only product ions with different characteristic masses respectively corresponding to the propionaldehyde and the acetone are generated, but also the reaction efficiency is extremely high, and the purposes of efficiently ionizing and distinguishing the propionaldehyde and the acetone can be achieved.
Description
Technical Field
The invention relates to an analysis method for distinguishing propionaldehyde from acetone, in particular to a chemical ionization mass spectrum detection method for distinguishing propionaldehyde from acetone.
Background
Volatile Organic Compounds (VOCs) are an important class of carbon-containing Organic Compounds in the atmosphere, and not only have toxicity and carcinogenicity, but also form precursors of photochemical smog and ozone, and high-sensitivity detection of the VOCs is a topic of special attention. In particular the isomer propionaldehyde (CH)3CH2CHO) and acetone (CH)3COCH3) They play different roles in atmospheric chemistry as important oxygen-containing VOCs (OVOCs) in the atmosphere, and hence, propanal and acetone, which are important for the resolution of isomers, are important in atmospheric VOC detection. The chemical ionization mass spectrum has the characteristics of high selectivity, soft ionization and the like, and has important advantages in mixture detection. Wherein is represented by H3O+Proton Transfer Reaction Mass Spectrometry (PTR-MS), which is a reagent ion, has been widely used for detection of atmospheric trace VOCs due to its advantages of high sensitivity, short response time, direct sample introduction, and the like. However, if PTR-MS is used to detect propionaldehyde and acetone, acetone and propionaldehyde have the same molecular formula (C)3H6O), and H)3O+The product ions after the reaction are the same and are all protonsProduct ion C of formation3H7O+Therefore, PTR-MS cannot be resolved. Although the objective of distinguishing between aldehyde and ketone isomers can be achieved by combining PTR-MS with gas chromatography techniques, this is at the expense of detection time. Therefore, in order to solve the problem, a new and suitable reagent ion needs to be developed to be used as a chemical ionization source for detecting atmospheric VOCs, so as to be used for detecting and analyzing propionaldehyde and acetone, thereby making up the defect that PTR-MS cannot distinguish propionaldehyde from acetone in the aspect of detecting VOCs.
Other reagent ions, such as NO, have also been developed to achieve resolution of propionaldehyde and acetone by chemical ionization mass spectrometry+(de Gouw et al, Atmos. Meas. Teach.2016,9, p. 2909-2 +(
Et al, int.J.Mass Spectrum.1997, 165/166, p.25-37). When they were reacted with propionaldehyde and acetone, the respective reaction channels were different. In particular, NO+Carrying out hydrogen anion transfer reaction with propionaldehyde and carrying out methyl anion transfer reaction and addition reaction with acetone; o is2 +The catalyst and propionaldehyde produce charge transfer reaction and hydride transfer reaction, and produce methyl anion transfer reaction with acetone. Thus, NO+And O2 +After the reaction with propionaldehyde and acetone, the product ions have obvious difference, and can reflect the parent molecular weight, and can be used for distinguishing propionaldehyde from acetone. However, the above ions have certain defects in VOC detection, such as NO+Does not react with formaldehyde, has small activity on small-molecular OVOC such as methanol and the like, and O2 +Easily cause the cracking of alkane VOC molecules.
In order to find suitable reagent ions, it was found that mononuclear transition metal ions, in addition to the above main group element ions, exhibit a considerable reactivity towards many organic molecules (Operti et al, Mass Spectrum. Rev.2006,25, page 483-513), and are capable of activating not only alkenes, alkynes, aromatics and less reactive alkanesHydrocarbons, in combination with ethers, ketones, aldehydes, nitrogen-containing compounds, sulfur-containing compounds and many small molecule gases (H)2、N2、O2) The compounds also have higher reaction activity in the reaction process and can be used as potential reagent ions for distinguishing propionaldehyde and acetone molecules. However, despite such abundant reactivity of mononuclear transition metal ions, chemical ionization analysis has never been used to resolve propanal acetone molecules. In addition, some metal ions M of the mononuclear pre-transition metals Sc, Ti and V+(Tolbert et al, J.Am.chem.Soc.1984,106, pp. 8117-8122) by reaction with acetone the product ion is MO+The parent ion representing the molecular weight of acetone cannot be formed, and the reactivity with propionaldehyde is rarely studied, thus adversely affecting the resolution of acetone and propionaldehyde.
When chemical ionization is performed on gas straight-chain paraffin with different molecular weights, mononuclear late transition metal ions are used as reagent ions for chemically ionizing the straight-chain paraffin, and the reagent ions and the straight-chain paraffin are subjected to chemical reaction under specific pressure, so that the paraffin is not cracked, and product ions capable of directly reflecting the molecular weight of the paraffin are formed. However, since the properties and structures of acetone and propionaldehyde are completely different from those of straight-chain alkane, and more importantly, how to distinguish acetone and propionaldehyde with the same molecular weight, the distinction by chemical ionization of transition metal ions (preferably post-transition metal ions) has not been reported at present.
Based on this, the inventors found through a large number of experimental studies that transition metal ions, especially late transition metal ions, exhibit significantly different reaction activities when reacting with propionaldehyde and acetone, and thus the inventors successfully applied the chemical ionization method to the separation and detection of gas molecules of isomers by adjusting and screening the reaction conditions, and effectively realized the resolution of acetone and propionaldehyde.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention aims to provide a chemical ionization mass spectrometry detection method for resolving propionaldehyde and acetone, wherein mononuclear transition metal ions are used as reagent ions for resolving propionaldehyde and acetone by chemical ionization, so as to achieve the purpose of high-efficiency ionization and resolving propionaldehyde and acetone.
In order to achieve the purpose, the following technical scheme is specifically adopted:
a chemical ionization mass spectrometry detection method for resolving propionaldehyde and acetone, comprising the steps of:
(1) processing the metal by a physical and chemical method to generate mononuclear metal ions;
(2) loading the mononuclear metal ions obtained in the step (1) into a reaction tube by using buffer gas;
(3) sending a gas sample to be detected into the reaction tube in the step (2) to react with the mononuclear metal ions in the reaction tube to generate an ionization product;
(4) and (4) detecting the ionization product obtained in the step (3) by a detector, and distinguishing propionaldehyde gas and acetone gas according to detection results of different reaction activities.
The method selects mononuclear metal positive ions with proper chemical activity as reagent ions, and the reagent ions and propionaldehyde or acetone are subjected to chemical reaction, so that the product ions corresponding to different characteristics of propionaldehyde and acetone are directly formed while propionaldehyde and acetone are efficiently ionized.
According to the invention, in step (1), the metal is a transition metal element, preferably a post-transition metal element, and the mononuclear metal ion is a mononuclear post-transition metal ion.
According to the present invention, the preferred mononuclear transition metal ions are mononuclear post-transition metal ions. The late transition metal is, for example, one of osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, iridium, or platinum. Which produces mononuclear late transition metal ions, for example mononuclear metal ions of osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, iridium or platinum.
The method preferably uses the post-transition metal ions as the reaction metal ions, shows different reaction activities to the propionaldehyde and the acetone in the process of ionizing the propionaldehyde and the acetone, generates hydrogen anion transfer reaction with the propionaldehyde, generates methyl anion transfer reaction with the acetone, has obvious difference in product ions of the two ions, and can be used for distinguishing the propionaldehyde from the acetone.
According to the invention, in the step (1), the physical and chemical method comprises one of laser sputtering, magnetron sputtering or arc discharge, preferably laser sputtering, for example, the laser frequency can be 1-2000 Hz, preferably 10-200 Hz.
According to the invention, in the step (2), the buffer gas is an inert gas which does not react with propionaldehyde or acetone and ionization products thereof, such as one or more of helium, argon or nitrogen, and the pressure thereof is not less than 1atm, such as 5 atm; the purity is 98% or more, for example, 99.999% helium.
Inert gas which does not react with propionaldehyde or acetone is used as buffer gas, so that the inert gas can be prevented from acting with propionaldehyde and acetone or ionizing products of propionaldehyde and acetone, and impurities are prevented from entering a detector to influence the final detection result.
According to the invention, in step (3), before the gas sample is sent into the reaction tube, the instantaneous pressure of the gas sample to be measured is adjusted; the instantaneous pressure is about 0.01 to 1Pa, preferably 0.1 to 1 Pa.
According to the invention, in the step (3), the gas sample to be tested is propionaldehyde, acetone or a mixture of the two, but before the test, the specific gas is not determined.
According to the invention, in step (4), the detector is a time-of-flight mass spectrometer, a quadrupole mass spectrometer or a fourier transform ion cyclotron resonance mass spectrometer, preferably a time-of-flight mass spectrometer.
According to the present invention, in step (4), the detection result of propionaldehyde is the presence of a peak having one or both of mass-to-charge ratios 57 and 115, and the detection result of acetone is the presence of a peak having one or both of mass-to-charge ratios 43 and 101.
When the mass-to-charge ratio in the detection result is 57 or 115 or both occur, judging that the detection sample is propionaldehyde gas according to the detection result; and when the mass-to-charge ratio is 43 or 101 or both the mass-to-charge ratio and the mass-to-charge ratio appear in the detection result, judging that the detection sample is acetone gas according to the detection result. Therefore, the invention can distinguish the two detection results according to different detection results.
The invention also provides a propionaldehyde gas detection method, which is characterized in that the propionaldehyde gas can be judged when the detection result has one or two peaks with mass-to-charge ratios of 57 and 115 by adopting the steps (1) to (4).
The invention also provides a method for detecting acetone gas, which is characterized in that the acetone gas can be judged when the detection result has one or two peaks with mass-to-charge ratios of 43 and 101 by adopting the steps (1) to (4).
The late transition metal element in the present invention means a metal element in groups 8 to 11 of the periodic table.
The invention has the beneficial effects that:
the invention has the advantages that the mononuclear transition metal positive ion with proper chemical activity is selected as the reagent ion to perform chemical reaction with the propionaldehyde or the acetone, so that the propionaldehyde and the acetone are efficiently ionized, meanwhile, product ions with different characteristics corresponding to the propionaldehyde and the acetone are generated, and the purposes of efficiently ionizing and distinguishing the propionaldehyde and the acetone can be achieved. In practice, the invention can be used for chemical ionization mass spectrometric detection and analysis of isomer propionaldehyde and acetone.
Drawings
FIG. 1 shows the mass spectra obtained from the detection of two gases, propionaldehyde and acetone, in examples 1-12.
Detailed Description
The method and application of the present invention will be described in further detail with reference to specific examples. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the starting materials, instruments and reagents used in the following examples are all commercially available or may be prepared by known methods.
Example 1
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on a translational and rotary late transition metal target osmium to generate osmium mononuclear positive ions;
(2) the generated osmium ions are cooled by a thin tube with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, the product ions and unreacted osmium ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm diameter).
The results are shown in FIG. 1.
Example 2
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double frequency light of a YAG laser is focused on the translation and rotation rear transition metal target rhodium to generate rhodium mononuclear positive ions;
(2) the produced rhodium ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, the product ions and unreacted rhodium ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
Example 3
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on the translational and rotary rear transition metal target gold to generate gold mononuclear positive ions;
(2) the generated gold ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, the product ions and unreacted gold ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (diameter 2 mm).
The results are shown in FIG. 1.
Example 4
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on translational and rotary rear transition metal target palladium to generate palladium mononuclear positive ions;
(2) the generated palladium ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted palladium ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
Example 5
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on translational and rotary rear transition metal target ruthenium to generate ruthenium mononuclear positive ions;
(2) the generated ruthenium ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, the product ions and unreacted ruthenium ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm diameter).
The results are shown in FIG. 1.
Example 6
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on the translational and rotary post-transition metal target silver to generate silver mononuclear positive ions;
(2) the generated silver ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted silver ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (diameter 2 mm).
The results are shown in FIG. 1.
Example 7
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on the translation and rotation rear transition metal target iridium to generate iridium mononuclear positive ions;
(2) the generated iridium ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, the product ions and unreacted iridium ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm diameter).
The results are shown in FIG. 1.
Example 8
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on a translational and rotational late transition metal target platinum to generate platinum mononuclear positive ions;
(2) the generated platinum ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted platinum ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
Example 9
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double frequency light of a YAG laser is focused on the translation and rotation post-transition metal target cobalt to generate cobalt mononuclear positive ions;
(2) the generated cobalt ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted cobalt ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm diameter).
The results are shown in FIG. 1.
Example 10
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on a translation and rotation rear transition metal target nickel to generate nickel mononuclear positive ions;
(2) the generated nickel ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.1-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted nickel ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
Example 11
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on the translational and rotary post-transition metal target copper to generate copper mononuclear positive ions;
(2) the generated copper ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrying belt of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted copper ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
Example 12
The embodiment is completed in a reflection type flight time mass spectrum device provided with a pulse laser sputtering and a fast flow reaction tube, and the specific steps are as follows:
(1) using Nd3+: 532nm pulse laser (10Hz) of double-frequency light of a YAG laser is focused on the translational and rotary rear transition metal target iron to generate iron mononuclear positive ions;
(2) the generated iron ions are cooled by a tubule with the diameter of 2mm and the length of 25mm under a carrier band of high-purity (99.999%) helium He (5atm) controlled by a first pulse valve, and then enter a fast flow reaction tube with the inner diameter of 2mm, the outlet diameter of 1mm and the length of 60 mm;
(3) respectively introducing propionaldehyde and acetone gas into a fast flow reaction tube by using a second pulse valve, wherein the instantaneous pressure of the propionaldehyde or the acetone gas is about 0.01-1 Pa, and the instantaneous total pressure (T298K) in the fast flow reaction tube is about 1500 Pa;
(4) after reaction in the fast flow reaction tube, product ions and unreacted iron ions fly out of the reaction tube and are detected by a reflection time-of-flight mass spectrometer through a conical nozzle (2 mm in diameter).
The results are shown in FIG. 1.
As can be seen from FIG. 1, in examples 1 to 12, the metal ions and propionaldehyde undergo the hydride transfer reaction to directly form C3H5O+Ions, accompanied by secondary reaction product ions C3H5O(C3H6O)+With acetone to directly form C2H3O+Accompanied by secondary reaction product ion C3H5O(C3H6O)+The charge-to-mass ratio of the two product ions is different, the two product ions can be distinguished by mass spectrum, the reaction efficiency is very high and is close to the theoretical collision rate, the purpose of efficiently ionizing and distinguishing propionaldehyde and acetone can be achieved, and the method is used for the chemical ionization mass spectrum detection and analysis of propionaldehyde and acetone in the atmosphere.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A chemical ionization mass spectrum detection method for distinguishing propionaldehyde from acetone is characterized by comprising the following steps:
(1) processing the metal by a physical and chemical method to generate mononuclear metal ions;
(2) loading the mononuclear metal ions obtained in the step (1) into a reaction tube by using buffer gas;
(3) sending a gas sample to be detected into the reaction tube in the step (2) to react with the mononuclear metal ions in the reaction tube to generate an ionization product;
(4) detecting the ionization product obtained in the step (3) by a detector, and distinguishing propionaldehyde and acetone gas according to detection results of different reaction activities;
in the step (1), the metal is selected from one of osmium, cobalt, ruthenium, silver, nickel, gold, palladium, rhodium, iron, iridium or platinum;
in the step (1), the physical and chemical method comprises one of laser sputtering, magnetron sputtering or arc discharge;
in the step (4), the metal ions and propionaldehyde generate hydride transfer reaction to directly form C3H5O+Ions, accompanied by secondary reaction product ions C3H5O(C3H6O)+With acetone to directly form C2H3O+Accompanied by secondary reaction product ion C3H5O(C3H6O)+That is, the detection result of propionaldehyde is the peak with one or two of the mass-to-charge ratios 57 and 115, the detection result of acetone is the peak with one or two of the mass-to-charge ratios 43 and 101, and acetone and propionaldehyde are judged by the difference of the mass-to-charge ratios;
the buffer gas is inert gas which does not react with propionaldehyde or acetone and ionization products thereof; the inert gas is selected from helium, argon or nitrogen.
2. The method of claim 1, wherein the laser frequency is 1 to 2000 Hz.
3. The method according to claim 2, wherein in the step (2), the pressure of the inert gas is not less than 1 atm; the purity of the product is more than 98%.
4. The method according to claim 3, wherein in the step (3), the instantaneous pressure of the gas sample to be measured is adjusted before the gas sample is fed into the reaction tube; the instantaneous pressure is 0.01-1 Pa;
the pressure of the inert gas in the step (2) is 5 atm.
5. The method of claim 4, wherein in step (3), the gas sample to be tested is propionaldehyde, acetone or a mixture of the two, but before testing, the specific gas is not determined.
6. The method of claim 5, wherein in step (4), the detector is time-of-flight mass spectrometry, quadrupole mass spectrometry, or Fourier transform ion cyclotron resonance mass spectrometry.
7. The method according to any one of claims 1 to 6, wherein in the step (4), when the mass-to-charge ratio is 57 or 115 or both of them appear in the detection result, the detection sample is judged to be propionaldehyde gas according to the detection result; and when the mass-to-charge ratio is 43 or 101 or both the mass-to-charge ratio and the mass-to-charge ratio appear in the detection result, judging that the detection sample is acetone gas according to the detection result.
8. A method for detecting propionaldehyde gas, characterized in that, by using steps (1) to (4) as defined in any one of claims 1 to 7, when a peak having one or both of mass-to-charge ratios of 57 and 115 appears as a detection result, it is determined that propionaldehyde gas is present.
9. A method for detecting acetone gas, characterized in that, by using the steps (1) to (4) according to any one of claims 1 to 7, when a peak having one or both of mass-to-charge ratios of 43 and 101 appears as a result of the detection, it is determined that acetone gas is present.
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