EP0290711A1 - Méthode et dispositif pour la mesure de la concentration dans un mélange gazeux - Google Patents
Méthode et dispositif pour la mesure de la concentration dans un mélange gazeux Download PDFInfo
- Publication number
- EP0290711A1 EP0290711A1 EP87890178A EP87890178A EP0290711A1 EP 0290711 A1 EP0290711 A1 EP 0290711A1 EP 87890178 A EP87890178 A EP 87890178A EP 87890178 A EP87890178 A EP 87890178A EP 0290711 A1 EP0290711 A1 EP 0290711A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- primary ions
- separate determination
- molecules
- examined
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/062—Ion guides
- H01J49/063—Multipole ion guides, e.g. quadrupoles, hexapoles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/145—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using chemical ionisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/24—Nuclear magnetic resonance, electron spin resonance or other spin effects or mass spectrometry
Definitions
- the invention relates to a method for determining the concentration of individual types of molecules in gas mixtures, the gas mixture to be examined being subjected to a selective pretreatment and then the product of this pretreatment being examined by mass spectrometry, and a device for carrying out such a method.
- the object of the present invention is to improve a method or a device of the type mentioned at the outset in such a way that the disadvantages of the known arrangements are avoided and that in particular the concentration of individual types of molecules of the same molecular mass in gas mixtures to be investigated without being measured or the preparation of the gas mixture for measurement-related large delays can be determined.
- the gas mixture to be examined is ionized under at least extensive vacuum by means of primary ions under single-pulse conditions, the primary ions used having an internal energy of slight, preferably der 2 eV, above that required to produce the productions that represent the molecule type of interest, and have a translational impact energy of such magnitude in the respective center of gravity system that the kinetic effect on the ionization is negligible compared to the influence of the internal energy, preferably an impact energy below 10 eV, and that the mass spectrometric analysis is carried out on the productions.
- the device for determining the concentration of individual types of molecules in gas mixtures, with an arrangement for the selective pretreatment of the gas mixture to be examined and a mass spectrometer arrangement for examining the product of this pretreatment is characterized according to the invention in that the pretreatment arrangement is an ion source for primary ions, has a reaction chamber adjoining the ion source with a feed line for the gas mixture to be examined and a pump for at least extensive evacuation, that the mass spectrometer arrangement is arranged on the side of the reaction chamber that is essentially remote from the ion source, that the ion source has primary ions with an internal energy of slightly, preferably ⁇ 2 eV, above what is required to produce the productions that represent the particular type of molecule of interest, and a translational impact energy below 10 eV, and that the reaction space is one octo pole arrangement, at which an RF guide potential is present, is surrounded.
- the pretreatment arrangement is an ion source for primary ions
- the mass spectrometer arrangement is arranged on
- the selective pretreatment of the gas mixture to be examined is thus carried out directly in accordance with the invention the ionization with primary ions of certain internal energy (ionization potential) is carried out with limited translational impact energy, which avoids the disadvantages of the GCMS systems described at the outset and also enables the concentrations of molecules of the same molecular mass to be determined separately in a simple and quick manner.
- the present invention is based on the knowledge that by selecting a primary ion type whose ionization potential (internal energy) is only slightly above that of the species to be ionized, the neutral molecules can be converted into ions without being ionized in fragments. For example, CH3OH + Xe+ only CH3OH+ + Xe or off C2H5OH + Xe+ only C2H5OH+ + Xe.
- the separate determination of molecular concentrations of the same molecular masses is made possible by selective ionization.
- the primary ions used have an internal energy which is slightly, preferably thanks 2 eV, above that which is necessary for producing a production with simultaneous H-abstraction. This ionization under H-abstraction expands the abundance of possibilities for distinguishing molecules of the same molecular mass by the selective ionization process in the subsequent mass spectrometric examination.
- the primary ions used have an internal energy in the range from 4.5 to 6.8 eV for the separate determination of organometallic compounds.
- organometallic compounds When determining organometallic compounds, the probabilities of possible interference with hydrocarbons Compounds of the same molecular mass are getting bigger, so that the identification of the molecules due to the characteristic isotope distributions with the number of atoms in the molecule is becoming increasingly difficult.
- the aforementioned choice of the primary ions used selectively ionizes the organometallic compounds whose ionization energies are in this range without simultaneous ionization of the hydrocarbon compounds, so that simple mass spectrometric detection is possible.
- krypton ions can be used as primary ions, which optimally meet the requirements for internal energy.
- Xenon+ ions can be used as primary ions according to another advantageous embodiment of the invention.
- the method according to the invention thus enables rapid analysis (real-time analysis) of gas mixtures, ie determination of the individual molecular components in gas mixtures, which is of great interest for many applications in industry and research, such as: Study of rapid chemical reactions to elucidate the reaction kinetics; Measurement of short-lived metastable intermediates and radicals in chemical reactions or catalytically active media;
- the ionization required for the use of the mass spectrometer ie the conversion of all neutral molecules to be investigated into ions, takes place in that a positively or negatively charged, intense ion beam of precisely defined internal energy interacts with the molecules to be ionized.
- a primary ion type whose internal energy is only slightly higher than the ionization potential of the species to be ionized, the molecules are converted to ions without question elements to be ionized.
- the corresponding translational collision energy between the primary ions and the gas particles must be kept so small that the kinetic effects on the ionization are small compared to the influence of the internal energy.
- the device has an ion source 1 of any type, of no interest here, whose essential specification in the present context is that the primary ions generated and emerging in the direction z from the ion source have an internal energy of slightly, preferably ⁇ 2 eV , above which are required for the production of the respective molecular species of interest, and in the respective primary ion / molecule focus system have a translational impact energy of such a magnitude that the kinetic effect on the ionization is negligible compared to the influence of the internal energy, preferably a translational impact energy below of 10 eV.
- a closed electron impact ion source can be used, through which a primary gas A flows. This is ionized by electrons in processes e ⁇ + A ⁇ A+ 2 e ⁇ , making primary ions A+ available.
- reaction chamber 2 adjoining the ion source 1 and a mass spectrometer arrangement 3, preferably a quadrupole mass spectrometer, connecting the reaction ions 2 to the reaction chamber 2 in the main direction of movement z are provided.
- the reaction chamber 2, to which the gas mixture to be examined is fed via a connection 4 can be surrounded by an octopole arrangement 5 with a high-frequency 8-pole field acting perpendicular to the main direction of movement z of the primary ions, which serves to collect, hold or guide the primary ions which have a very low kinetic energy.
- a pump for at least largely evacuating the reaction space 2 is designated by 10;
- various other additional devices such as diaphragms or lenses for the ion beam or further vacuum pumps and seals and the like, which are partly essential for the function of the arrangement in normal operation, are not shown, since they are of secondary importance in connection with the present invention are.
- the octopole arrangement 5 is here divided into three individual regions 7, 8, 9, which are - from the ion source 1 to the mass spectrometer arrangement - in the longitudinal direction - i.e. in the main direction of movement z of the primary ions emerging from the ion source 1 in a beam 3 seen - lie on the negative direct voltage potential that rises in each case with respect to the previous region.
- an E field is generated in the axial direction, which for rapid and complete removal of the productions in the direction of the mass spectrometer ensures fast analysis with high accuracy.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0122687A AT404882B (de) | 1987-05-14 | 1987-05-14 | Verfahren und einrichtung zur konzentrationsmessung an gasgemischen |
AT1226/87 | 1987-05-14 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0290711A1 true EP0290711A1 (fr) | 1988-11-17 |
EP0290711B1 EP0290711B1 (fr) | 1991-05-02 |
EP0290711B2 EP0290711B2 (fr) | 1998-07-15 |
Family
ID=3509337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87890178A Expired - Lifetime EP0290711B2 (fr) | 1987-05-14 | 1987-07-20 | Méthode pour la mesure de la concentration dans un mélange gazeux |
Country Status (6)
Country | Link |
---|---|
US (1) | US4975576A (fr) |
EP (1) | EP0290711B2 (fr) |
JP (1) | JPH0821364B2 (fr) |
AT (1) | AT404882B (fr) |
DE (1) | DE3769792D1 (fr) |
WO (1) | WO1988009052A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19607155A1 (de) * | 1996-02-26 | 1997-09-04 | Atomika Instr Gmbh | Verfahren zur simultanen Erzeugung mehrerer Ionensorten mit unterschiedlichen Ionisierungspotentialen |
US6982416B2 (en) | 2000-12-15 | 2006-01-03 | V & F Analyse - Und Messtechnik Ges. M.B.H. | Method and device for evaluating the state of organisms and natural products and for analyzing a gaseous mixture comprising main constituents and secondary constituents |
EP3418714A1 (fr) | 2017-06-19 | 2018-12-26 | V&F Analyse- und Messtechnik GmbH | Dispositif et procédé d'acheminement partiel d'un échantillon de liquide comprenant plusieurs composants et procédé de détermination en ligne et d'analyse desdits composants |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0647847A1 (fr) * | 1993-09-14 | 1995-04-12 | Elpatronic Ag | Utilisation d'un spectromètre de masse à ionisation de récipients |
US5670378A (en) * | 1995-02-23 | 1997-09-23 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method for trace oxygen detection |
US5767513A (en) * | 1997-03-31 | 1998-06-16 | The United States Of America As Represented By The Secretary Of The Air Force | High temperature octopole ion guide with coaxially heated rods |
US6239429B1 (en) | 1998-10-26 | 2001-05-29 | Mks Instruments, Inc. | Quadrupole mass spectrometer assembly |
AT413081B (de) * | 2000-03-03 | 2005-11-15 | V & F Analyse & Messtechnik | Verfahren und vorrichtung zur überführung realer, reaktiver gasgemische in einen stabilen, inerten gaszustand |
US6902938B1 (en) * | 2000-10-10 | 2005-06-07 | Jeol Usa, Inc. | Chemical analysis method for multiplexed samples |
US8912000B2 (en) * | 2008-07-17 | 2014-12-16 | Schlumberger Technology Corporation | Downhole mass spectrometric hydrocarbon determination in presence of electron and chemical ionization |
EP2421024A1 (fr) | 2010-08-18 | 2012-02-22 | Ionicon Analytik Gesellschaft m.b.h. | Procédé d'ionisation pour analyseur universel de gaz |
EP3474311A1 (fr) | 2017-10-20 | 2019-04-24 | Tofwerk AG | Réacteur ion-molécule |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4234791A (en) * | 1978-11-13 | 1980-11-18 | Research Corporation | Tandem quadrupole mass spectrometer for selected ion fragmentation studies and low energy collision induced dissociator therefor |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3555272A (en) * | 1968-03-14 | 1971-01-12 | Exxon Research Engineering Co | Process for chemical ionization for intended use in mass spectrometry and the like |
DE2028805C3 (de) * | 1970-06-11 | 1974-05-22 | Franklin Gno Corp., West Palm Beach, Fla. (V.St.A.) | Verfahren und Einrichtung zum Feststellen eines Gasbestandteils |
US4005291A (en) * | 1972-01-04 | 1977-01-25 | Massachusetts Institute Of Technology | Ionization method for mass spectrometry |
US4378499A (en) * | 1981-03-31 | 1983-03-29 | The Bendix Corporation | Chemical conversion for ion mobility detectors using surface interactions |
-
1987
- 1987-05-14 AT AT0122687A patent/AT404882B/de not_active IP Right Cessation
- 1987-07-20 DE DE8787890178T patent/DE3769792D1/de not_active Expired - Lifetime
- 1987-07-20 EP EP87890178A patent/EP0290711B2/fr not_active Expired - Lifetime
-
1988
- 1988-05-04 JP JP63503794A patent/JPH0821364B2/ja not_active Expired - Lifetime
- 1988-05-04 US US07/313,977 patent/US4975576A/en not_active Expired - Lifetime
- 1988-05-04 WO PCT/AT1988/000026 patent/WO1988009052A1/fr unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4234791A (en) * | 1978-11-13 | 1980-11-18 | Research Corporation | Tandem quadrupole mass spectrometer for selected ion fragmentation studies and low energy collision induced dissociator therefor |
Non-Patent Citations (2)
Title |
---|
ANALYTICAL CHEMISTRY, Band 58, Nr. 12, Oktober 1986, Seiten 2421-2425, American Chemical Society, Washington, US; H.T. KALINOSKI et al.: "Supercritical fluid extraction and direct fluid injection mass spectrometry for the determination of trichothecene mycotoxins in wheat samples" * |
JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, Band 73, Nr. 3, 28. November 1986, Seiten 197-235, Elsevier Science Publishers B.V., Amsterdam, NL; I. SZABO: "New ion-optical devices utilizing oscillatory electric fields.I.Principle of operation and analytical theory of multipole devices with two-dimensional electric fields" * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19607155A1 (de) * | 1996-02-26 | 1997-09-04 | Atomika Instr Gmbh | Verfahren zur simultanen Erzeugung mehrerer Ionensorten mit unterschiedlichen Ionisierungspotentialen |
US6982416B2 (en) | 2000-12-15 | 2006-01-03 | V & F Analyse - Und Messtechnik Ges. M.B.H. | Method and device for evaluating the state of organisms and natural products and for analyzing a gaseous mixture comprising main constituents and secondary constituents |
EP3418714A1 (fr) | 2017-06-19 | 2018-12-26 | V&F Analyse- und Messtechnik GmbH | Dispositif et procédé d'acheminement partiel d'un échantillon de liquide comprenant plusieurs composants et procédé de détermination en ligne et d'analyse desdits composants |
WO2018234245A1 (fr) | 2017-06-19 | 2018-12-27 | V&F Analyse- Und Messtechnik Gmbh | Dispositif et procédé pour transformer partiellement un échantillon liquide renfermant plusieurs composants, et procédé de détermination et d'analyse en ligne de ces composants |
Also Published As
Publication number | Publication date |
---|---|
WO1988009052A1 (fr) | 1988-11-17 |
JPH0821364B2 (ja) | 1996-03-04 |
JPH01503503A (ja) | 1989-11-22 |
ATA122687A (de) | 1990-02-15 |
US4975576A (en) | 1990-12-04 |
AT404882B (de) | 1999-03-25 |
EP0290711B2 (fr) | 1998-07-15 |
EP0290711B1 (fr) | 1991-05-02 |
DE3769792D1 (de) | 1991-06-06 |
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