EP0260469B1 - Einrichtung zur analytischen Bestimmung von organischen Stoffen - Google Patents

Einrichtung zur analytischen Bestimmung von organischen Stoffen Download PDF

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Publication number
EP0260469B1
EP0260469B1 EP87112082A EP87112082A EP0260469B1 EP 0260469 B1 EP0260469 B1 EP 0260469B1 EP 87112082 A EP87112082 A EP 87112082A EP 87112082 A EP87112082 A EP 87112082A EP 0260469 B1 EP0260469 B1 EP 0260469B1
Authority
EP
European Patent Office
Prior art keywords
mass
substances
mass analyzer
analyzer
diaphragm
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
EP87112082A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0260469A2 (de
EP0260469A3 (en
Inventor
Ahmet Dr. Parlar
Friedrich Prof. Dr. Korte
Frederik Prof. Dr. Coulston
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.)
Gesellschaft fur Strahlen- und Umweltforschung Mbh (gsf)
Coulston International Corp
Original Assignee
Gesellschaft fur Strahlen- und Umweltforschung Mbh (gsf)
Coulston International Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gesellschaft fur Strahlen- und Umweltforschung Mbh (gsf), Coulston International Corp filed Critical Gesellschaft fur Strahlen- und Umweltforschung Mbh (gsf)
Priority to AT87112082T priority Critical patent/ATE84377T1/de
Publication of EP0260469A2 publication Critical patent/EP0260469A2/de
Publication of EP0260469A3 publication Critical patent/EP0260469A3/de
Application granted granted Critical
Publication of EP0260469B1 publication Critical patent/EP0260469B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • H01J49/025—Detectors specially adapted to particle spectrometers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons

Definitions

  • the invention relates to a device for the analytical determination of organic substances, which are present in concentrations up to the ppm and ppt range, by means of mass analysis, the substances being transferred from a storage container to a mass analyzer, the storage container directly via a metering device with the Mass analyzer connectable and the mass analyzer is a quadrupole mass spectrometer with a Channeltron electro-multiple and mass correction aperture (see patent application Federal Republic of Germany P 35 10 378.7-52).
  • the object underlying the invention is to e. G. To design the device in such a way that substances which are in the ppm to ppt range can also be directly detected by mass analysis.
  • the invention is particularly suitable for determining the photostability of volatile organic compounds (for example environmental chemicals, concentration / time diagrams, half-lives, reaction rate constants), the photostability of compounds which are difficult to evaporate (environmental chemicals which are counted among the 1,2-diketones; the CO formed with a detection limit of 200 ppt), the workplace concentration of organic chemicals in a production facility (benzene and 1,2-trans-dichlorethylene concentration; detection limit 100 ppt - 5 ppb), the concentration of organic chemicals in closed rooms (Pentachlorophenol detection in offices; 40 ⁇ g / m3 - 55 ⁇ g / m3), analysis of aqueous and solid samples (benzene detection from the Goldach / Erding river; detection limit 10 ppb; and CO2 detection from the carrier material (silica gel, aluminum oxide neutral, Montmorillonide, sands from Tulorosa, Egypt, Orlando and Saudi Arabia after the mineralization experiments under standardized conditions; detection limit for CO2 at least 100 ppt))
  • Areas of application include blood alcohol determination, determination of volatile compounds in urine (e.g. ketones), determination of chlorinated hydrocarbons in fatty tissue, determination of volatile products from sewage sludge, waste slag and fly ash, monitoring of street and city air (all pollutants including nitrogen oxides, sulfur dioxide and organic environmental chemicals in the air), control of the exhaust gases from internal combustion engines and their correct identification and quantification, checking the completeness of the gas phase reaction in the chemical industry (e.g. ammonia synthesis), thermal decomposability of market articles from the semiconductor industry, determination of hydrogen, helium, nitrogen and other gases in various areas of industry and control of thermal decomposition of organic environmental chemicals in waste incineration and pyrolysis processes.
  • the plant shown in FIG. 1 essentially consists of 3 parts, namely a vacuum-controllable recipient part 1, an optimized mass analyzer system 2 and a special separator system 3.
  • the recipient part 1 consists of a spherical glass reactor 4 with variable recipient sizes between 1 - 400 l and additional inserts, for example irradiators 5, for various purposes.
  • the recipient is surrounded by a heating jacket 6, which enables temperature ranges up to 200 ° C.
  • the entire system 1 can be evacuated to 1.3332 ⁇ 10 ⁇ 6 Pa (10 ⁇ 8 Torr) with the help of a turbomolecular pump 7 (here Galileo PT-60).
  • the reaction chamber 8 can be separated from the pump stand by using a viton-sealed slide valve (backing pump 9: Edwards E2 M8).
  • the samples or sample parts with the substances can be brought into the gas phase from the inlet system 10 and their concentration can be determined with the aid of the pressure measurements.
  • the inlet system 10 consists of a noble metal housing with 4 vacuum sealable openings. From the upper side it is provided with a spring-loaded metal rod 11, with the aid of which the volatile samples, which are located in standardizable capillaries, can be released mechanically. Porcelain boats are available for solid samples.
  • a variable gas valve combination 12 (CJT vacuum technology, Ramelsbach) is accommodated below the inlet system 10 and has the task of admitting gaseous samples into the reactor 4 in a controlled manner.
  • the recipient part 1 offers work possibilities in the pressure ranges 133.32 - 1.3332 ⁇ 10 ⁇ 6 Pa (1 - 10 ⁇ 8 Torr) and in different pressure ranges with different recipient volumes using gas or gas mixtures.
  • the mass analyzer 13 is usually operated in the pressure range between 1.3332 ⁇ 10 ⁇ 2 - 1.3332 ⁇ 10 ⁇ 4 Pa (10 ⁇ 4 and 10 ⁇ 6 Torr).
  • the ions both those of the substances to be investigated and the other gas components (impurities), are detected by means of a secondary electron multiplier. If concentrations of the substances in the ppb or ppt range are to be detected, it is not simply sufficient to increase the vacuum range in the mass analyzer 13 accordingly, since in this case the signal / noise ratio makes the measurement impossible. On the other hand, a pure pressure reduction would in turn ensure clean measuring conditions, in the present case, however, it would prevent the detection of the substances, since their concentration in the ion source would be reduced accordingly.
  • the pressure range of the mass analyzer 13 is depressed in ranges of 1.3332 ⁇ 10 ⁇ 7 Pa (10 ⁇ 9 Torr) so that the noise disappears, but by using the channeltron electromultiplier 14 with mass correction aperture 15, the sensitivity of the detection of fabrics improved significantly. There are quasi pure spectra of the substances.
  • the mass correction aperture 15 is not arranged directly at the Canneltron 14, but is inserted between the entrance to the turbomolecular pump 17 and the entrance to the ion pump 16, i. H. underneath the ion pump 16. This position is particularly favorable, since placement above the ion pump could unnecessarily delay the cleaning process.
  • the mass correction orifice 15 serves to regulate and increase the relative residence probabilities or concentrations of the individual molecules in the analyzer 13.
  • its diameter 31 can be adjusted variably either manually or automatically. It has a structure that can correspond to that of an iris diaphragm of an optical camera.
  • the regulator 32 for the mass correction aperture 15/31 can either be operated manually (position of the switch 43 in position 33) or automatically (position in position 34).
  • a processor unit 37 In the case of automatic operation, it is connected to a processor unit 37 via a control unit 35 and an interface 36.
  • This processor unit 37 controls or controls the regulator 39 for the channeltron 14 via a further control unit 38 when the switch 40 is switched to position 41 (automatic). Position 42 is again intended for manual operation.
  • variable mass correction aperture 15 is controlled by the processor unit in cooperation with the Channeltron 14. This measure (opening or closing the passage opening 31) leads to a change in the intensity of the fragment ions of the relevant compounds to be measured. Substance-specific settings of the passage opening 31 are necessary for each pressure range in order to optimize the detection limit. In contrast to all previous devices, in which the passage opening constantly to a value, for. B. for nitrogen, the optimum setting of the mass correction aperture 15 can thus be found automatically for each connection to be detected.
  • FIG. 2 This state of affairs is shown in FIG. 2. It shows the course of the intensity in% compared to the area of the passage opening 31 of the mass correction aperture 15 mm2 / 100 for the compounds benzene (curve 44) and trichlorethylene (curve 45).
  • the pressure is set at 2,933 ⁇ 10 ⁇ 4 Pa (2.2 x 10 ⁇ 6 Torr).
  • Both curves 44 and 45 illustrate that an optimal passage area (maximum), z. B. at approx. 54 mm2 / 100 and approx. 42 mm2 / 100, for the measurement is automatically adjustable.
  • the outside diameter of the mass correction orifice 15 is 48 mm and its thickness is 2 mm.
  • the intensities of the mol and fragment ions are increased by means of the processor unit 37 and the control unit 38 via the output voltages of the Channeltron 14. All peaks belonging to a fragment are registered cumulatively by deliberately reducing the resolution.
  • the separator part 3 between the reactor 4 and the mass analyzer system 2 consists of 3 needle valves 28-20, which can be combined both in series and in parallel.
  • the needle valve 18 is closed under normal conditions, i.e. the pressures in reactor 4 are above 1.3332 ⁇ 10 ⁇ 4 Pa (10 ⁇ 6 Torr) and the concentration of the substances to be investigated is correspondingly high. Then the metering must be carried out continuously via the two reducing needle valves 19, 20, so that both the pressure and the concentration of the substances lie in value ranges suitable for the mass analyzer 13. In the event that these value ranges already prevail in the reactor 4, connection can be made directly via the needle valve 18.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
EP87112082A 1986-09-19 1987-08-20 Einrichtung zur analytischen Bestimmung von organischen Stoffen Expired - Lifetime EP0260469B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87112082T ATE84377T1 (de) 1986-09-19 1987-08-20 Einrichtung zur analytischen bestimmung von organischen stoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3631862 1986-09-19
DE19863631862 DE3631862A1 (de) 1986-09-19 1986-09-19 Einrichtung zur analytischen bestimmung von organischen stoffen

Publications (3)

Publication Number Publication Date
EP0260469A2 EP0260469A2 (de) 1988-03-23
EP0260469A3 EP0260469A3 (en) 1989-12-27
EP0260469B1 true EP0260469B1 (de) 1993-01-07

Family

ID=6309905

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87112082A Expired - Lifetime EP0260469B1 (de) 1986-09-19 1987-08-20 Einrichtung zur analytischen Bestimmung von organischen Stoffen

Country Status (4)

Country Link
EP (1) EP0260469B1 (ja)
AT (1) ATE84377T1 (ja)
DD (1) DD282779A5 (ja)
DE (1) DE3631862A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6333196B1 (en) 1996-02-28 2001-12-25 University Of Houston Catalyst testing process and apparatus

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1669738A3 (en) * 1996-10-09 2007-12-12 Symyx Technologies, Inc. Infrared spectroscopy and imaging of libraries
US6864091B1 (en) 2000-08-31 2005-03-08 Symyx Technologies, Inc. Sampling probe

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261698A (en) * 1980-01-23 1981-04-14 International Business Machines Corporation Trace oxygen detector
FR2485201A1 (fr) * 1980-06-20 1981-12-24 Rech Geolog Miniere Procede de mesure de grande precision des concentrations de gaz et produits volatils en situ et en continu et appareil in situ en oeuvre
US4579144A (en) * 1983-03-04 1986-04-01 Uti Instrument Company Electron impact ion source for trace analysis
DE3510378A1 (de) * 1985-03-22 1986-10-02 Coulston International Corp., Albany, N.Y. Verfahren zur analytischen bestimmung von organischen stoffen
JP2555010B2 (ja) * 1985-06-21 1996-11-20 株式会社日立製作所 質量分析計

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6333196B1 (en) 1996-02-28 2001-12-25 University Of Houston Catalyst testing process and apparatus

Also Published As

Publication number Publication date
DE3631862A1 (de) 1988-03-31
EP0260469A2 (de) 1988-03-23
EP0260469A3 (en) 1989-12-27
DD282779A5 (de) 1990-09-19
ATE84377T1 (de) 1993-01-15
DE3631862C2 (ja) 1993-08-26

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