EP0290711B2 - Méthode pour la mesure de la concentration dans un mélange gazeux - Google Patents

Méthode pour la mesure de la concentration dans un mélange gazeux Download PDF

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Publication number
EP0290711B2
EP0290711B2 EP87890178A EP87890178A EP0290711B2 EP 0290711 B2 EP0290711 B2 EP 0290711B2 EP 87890178 A EP87890178 A EP 87890178A EP 87890178 A EP87890178 A EP 87890178A EP 0290711 B2 EP0290711 B2 EP 0290711B2
Authority
EP
European Patent Office
Prior art keywords
ions
primary ions
separate determination
internal energy
primary
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.)
Expired - Lifetime
Application number
EP87890178A
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German (de)
English (en)
Other versions
EP0290711A1 (fr
EP0290711B1 (fr
Inventor
Werner Dr. Federer
Johannes Dr. Villinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
V & F ANALYSE- UND MESSTECHNIK G.M.B.H.
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V & F Analyse- und Messtechnik GmbH
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    • 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 concentration determination method for individual types of molecules in gas mixtures, wherein the gas mixture to be examined is subjected to a selective pretreatment and then the product of this pretreatment is examined by mass spectrometry.
  • the object of the present invention is a method of the aforementioned Art to improve so that the disadvantages of the known arrangements are avoided and in particular the concentration of individual types of molecules of the same molecular mass in the investigated in a simple manner Gas mixtures without being dependent on the measurement or the preparation of the gas mixture for measurement large delays can be determined.
  • the selective pretreatment of the gas mixture to be examined is therefore directly communicable by ionization with primary ions of certain internal energy (ionization potential) with limited translational impact energy carried out with which the disadvantages of the initially described GCMS systems can be avoided and the concentrations of molecules in a simple and fast manner same molecular mass can be determined separately.
  • AT-A-1680/86 (corresponds to AT-B-384 491) relates in this context a method in which the primary ions of an electron impact ion source with a below 2 eV Energy enters an evacuated reaction chamber and there molecules of a gas mixture to be analyzed ionize which secondary ions are subsequently detected by mass spectrography.
  • a an octopole system connected to the ion source generates a high-frequency field which emits the ion beams prevents divergence. Used to examine the beam coming from the reaction chamber a quadrupole mass spectrometer.
  • EP-A-290 712 which is also prior art under Article 54 (3), describes a similar one Process according to which selective, fragment-free ionization in the reaction chamber - i.e. the generation of a certain type of product ions with the greatest possible efficiency - only small kinetic energies in the Center of gravity ion / molecule allowed.
  • CH 3 OH + e - becomes: C + ; CH 3 + , CH 2 + , CH + ; OH + , O + ; CH 3 OH + Out C 2 H 5 OH + e - becomes: C + ; CH 3 + , CH 2 + , CH + ; OH + ; O + ; CH 3 OH + ; C 2 H 5 OH +
  • 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, CH 3 OH + Xe + only CH 3 OH + + Xe or off C 2 H 5 OH + Xe + only C 2 H 5 OH + + Xe
  • the primary ions used an internal energy have, which is slightly, preferably ⁇ 2eV, above that for producing a production below simultaneous H-abstraction is required.
  • the primary ions used have an internal energy in the range from 4.5 to 6.8 eV.
  • the probabilities of possible interference become with hydrocarbon compounds of the same molecular mass always larger, so that Identification of the molecules by the characteristic isotope distributions with the number of atoms in the molecule is becoming increasingly difficult.
  • the organometallic compounds whose ionization energies are in this range ionize without simultaneous Ionization of the hydrocarbon compounds, so that a simple mass spectrometric detection becomes possible.
  • krypton + ions can be used as primary ions, which optimally meet the stated requirements for internal energy.
  • xenon + ions can be used as primary ions for the separate determination of nitrous oxide and carbon dioxide.
  • the device has an ion source 1 of any type which is not of interest here, the essential specification of which 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 2 eV , above which are required for the production of the respective molecular species of interest, and which have a translational impact energy of such magnitude in the respective primary ion / molecule focus system that the kinetic effect on ionization is negligible compared to the influence of 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 accomplished by electrons in processes e - 2 e + A ⁇ A + + - ionized, which primary ions A + are available.
  • reaction space 2 adjoining the ion source 1 and one in the main direction of movement z of the primary ions supplied by the ion source 1 to the reaction chamber 2 adjoining mass spectrometer arrangement 3 - preferably a quadrupole mass spectrometer - is provided.
  • Reaction chamber 2 to which the gas mixture to be examined can be fed via a connection 4 of an octopole arrangement 5 with one acting perpendicular to the main direction of movement z of the primary ions
  • High-frequency 8-pole field surround which is used for collecting, holding or guiding the very low Serves primary ions having kinetic energy.
  • the in the mass spectrometer arrangement 3 or in corresponding quadrupole on known, not interesting, selected productions to an ion sensor 6, which can also be of a known or customary type and whose function and Effectiveness not interested here.
  • a pump for at least largely evacuating the reaction space 2 is designated by 10; of the For the sake of simplicity of presentation there are various others, partly for the function of the arrangement in the In normal operation, essential additional devices, such as diaphragms or lenses for the ion beam or others Vacuum pumps and seals and the like are not drawn as they are related to the present Invention are of minor importance.
  • the octopole arrangement 5 is here in the longitudinal direction - that is, in the main direction of movement, from the ion source 1 primary ions emerging in a beam - in three individual areas that are electrically isolated from each other 7, 8, 9 divided, which - seen from the ion source 1 to the mass spectrometer arrangement 3 - on each compared to the previous range increasing negative DC potential.
  • the radial guide field generated by the RF potential which contains the ions in the Holds the interior of the octopole arrangement 5, generates an E-field in the axial direction, which for a quick and complete Removal of the productions in the direction of the mass spectrometer ensures and thus a enables fast analysis with high accuracy.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Claims (6)

  1. Procédé de détermination de la concentration de molécules de même masse moléculaire dans des mélanges de gaz, caractérisé en ce que:
    le mélange de gaz à étudier est soumis à un prétraitement d'ionisation sélectif dans des conditions de choc au moyen d'ions primaires dans un vide relativement poussé;
    les ions primaires utilisés
    présentent une énergie interne légèrement supérieure, de préférence ≤ 2 eV, à celle nécessaire pour la création des produits ioniques chaque fois représentatifs de 1 espèce de molécule intéressante; et
    présentent dans chaque système, rapporté au centre de gravité ou système barycentrique, une énergie translatoire de choc d'une intensité telle que l'effet cinétique sur l'ionisation est négligeable par rapport à l'influence de l'énergie interne, de préférence une énergie de choc inférieure à 10 eV,
    et en ce que
    on entreprend l'étude par spectrométrie de masse sur les produits ioniques ayant subi ce prétraitement.
  2. Procédé selon la revendication 1, caractérisé en ce que, pour la détermination séparée des dérivés d'hydrocarbures, les ions primaires utilisés présentent une énergie interne qui est très minime, de préférence ≤ 2 eV, par rapport à celle nécessaire pour la création d'un produit ionique avec abstraction simultanée de H.
  3. Procédé selon la revendication 1, caractérisé en ce que, pour une détermination séparée de dérivés organométalliques, les ions primaires utilisés présentent une énergie interne comprise entre 4,5 et 6,8 eV.
  4. Procédé selon la revendication 2, caractérisé en ce que, pour la détermination séparée de l'oxygène (O2) et de l'alcool méthylique (CH3OH), on emploie comme ions primaires des ions de Krypton+ (Kr).
  5. Procédé selon la revendication 2, caractérisé en ce que, pour la détermination séparée du monoxyde d'azote (NO) et du formaldéhyde (CH2O), on emploie comme ions primaires des ions Krypton+ (Kr).
  6. Procédé selon la revendication 1, caractérisé en ce que, pour la détermination séparée de l'oxyde azoteux (N2O) et du dioxyde de carbone (CO2), on emploie comme ions primaires des ions Xénon+ (Xe).
EP87890178A 1987-05-14 1987-07-20 Méthode pour la mesure de la concentration dans un mélange gazeux Expired - Lifetime EP0290711B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1226/87 1987-05-14
AT0122687A AT404882B (de) 1987-05-14 1987-05-14 Verfahren und einrichtung zur konzentrationsmessung an gasgemischen

Publications (3)

Publication Number Publication Date
EP0290711A1 EP0290711A1 (fr) 1988-11-17
EP0290711B1 EP0290711B1 (fr) 1991-05-02
EP0290711B2 true 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)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
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
DE19607155A1 (de) * 1996-02-26 1997-09-04 Atomika Instr Gmbh Verfahren zur simultanen Erzeugung mehrerer Ionensorten mit unterschiedlichen Ionisierungspotentialen
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
DE50015353D1 (de) 2000-12-15 2008-10-23 V & F Analyse Und Mestechnik G Verfahren und Vorrichtung zur Beurteilung des Zustandes von Organismen und Naturprodukten sowie zur Analyse einer gasförmigen Mischung mit Haupt- und Nebenkomponenten
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
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
EP3474311A1 (fr) * 2017-10-20 2019-04-24 Tofwerk AG Réacteur ion-molécule

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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
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
US4378499A (en) * 1981-03-31 1983-03-29 The Bendix Corporation Chemical conversion for ion mobility detectors using surface interactions

Also Published As

Publication number Publication date
JPH01503503A (ja) 1989-11-22
AT404882B (de) 1999-03-25
US4975576A (en) 1990-12-04
WO1988009052A1 (fr) 1988-11-17
DE3769792D1 (de) 1991-06-06
EP0290711A1 (fr) 1988-11-17
EP0290711B1 (fr) 1991-05-02
JPH0821364B2 (ja) 1996-03-04
ATA122687A (de) 1990-02-15

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