US3852037A - Selective ionization detector - Google Patents
Selective ionization detector Download PDFInfo
- Publication number
- US3852037A US3852037A US00357496A US35749673A US3852037A US 3852037 A US3852037 A US 3852037A US 00357496 A US00357496 A US 00357496A US 35749673 A US35749673 A US 35749673A US 3852037 A US3852037 A US 3852037A
- Authority
- US
- United States
- Prior art keywords
- alkali
- ionization detector
- detector
- burner nozzle
- alkali glass
- 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
Links
- 239000003513 alkali Substances 0.000 claims abstract description 71
- 239000011521 glass Substances 0.000 claims abstract description 69
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 7
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 13
- 150000002367 halogens Chemical class 0.000 abstract description 13
- 239000012159 carrier gas Substances 0.000 abstract description 5
- 239000011324 bead Substances 0.000 description 18
- 230000035945 sensitivity Effects 0.000 description 11
- 150000001447 alkali salts Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000005949 Malathion Substances 0.000 description 3
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 229960000453 malathion Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- -1 for instance Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
Definitions
- This invention relates to a selective ionization detector for halogen, phosphorus or nitrogen compounds, comprising a diode through which a sample gas under analysis can be fed by means of a carrier or transfer gas, and which comprises an electrode including an alkali source in the form of a heated alkali-containing glass so that the electrode exhibits an increased ion emission upon the occurrence of such specific substances.
- a prior art selective ionization detector of this type which is particularly intended for leak detecting devices or the like includes two coaxially helically wound wires each of which are heatable by means of a filament transformer winding. Between the two wires, which constitute the electrodes of a diode, a d.c. voltage source is connected in series with a measuring device. The innermost wire is wound onto a cylinder of alkali metal glass, for instance, potassium glass. By means of the alkali metal of the glass cylinder a specific sensitizing of the electrode for halogen is effected so that upon passage of halogen-containing gases or vapors between the electrodes a definite increase in the current flowing across the diodes is observed (German patent specification No. 907,223).
- detectors of the above type are prior art in which an electrode and/or a separate supply of alkali metals are heated by means of a flame. These detectors are formed in the same manner as a flame ionization detector, which detector is conventional in gas chromatography.
- a burner nozzle is provided to which a combustible gas (for example, hydrogen) and sample gas mixture is supplied, with the sample gas in gas chromatographic detector applications again being a mixture of carrier gas plus eluted sample components.
- a collecting electrode Above the flame or around the flame there is arranged a collecting electrode. Around the flame an electrode in the form of a spiral is arranged which is coated with a layer of molten alkali salt, preferably sodium sulphate (see U.S. Pat. No. 3,372,994) for sensitizing.
- alkali salts have been provided in supply vessels of apertured or porous materials so that by diffusion over a longer period of time alkali metal compounds are passed to the surface of these supply vessels (German published patent application No. 1,598,] 18). Although this method ensures an alkali supply for days or weeks, the decrease in the detector sensitivity is still disturbingly high. Moreover, these supply vessels are expensive to manufacture.
- the basic feature of the invention resides in the fact that the alkali glass is in a viscous or softened state during detector operation.
- the alkali source therefore consists of glass which softens during operation, whereby it is attained that the surface of the alkali source does not become impoverished as to alkali, since by molecular movement alkali is constantly supplied to the surface.
- an ionization detector according to this invention differs advantageously from a detector according to the German patent specification No. 907,223 where the alkali cylinder remains in its rigid state and therefore an impoverishment of alkali at the surface soon takes place. Since only very small alkaki quantities are consumed, the supply of a single glassdrop is sufficient for many months. The alkali glass drop may then be readily replaced. No manufacturing costs for monocrystals, supply vessels, or the like are encountered.
- the detector may be of the form that includes a burner nozzle to which a combustible gas and sample gas mixture are supplied, that above the burner nozzle an alkali glass body is mounted and is heatable by an electric resistance heater to an extent sufficient for softening of the alkali body.
- the rate of alkali emission very markedly depends on the temperature of the glass.
- the heating of the alkali glass body is effected electrically and not by the flame, it is not necessary to maintain constant the flame temperature, and therefore the combustible gas (H flow, with the otherwise required accuracy.
- the gas flows of hydrogen and oxygen can be adapted to the respective temperature requirements, in particular, of the element desired to be detected.
- the heating of the electric resistance heater is precisely adjustable.
- provision can be made that independently of the precise adjusting means, a fixed heating capacity sufficient for igniting the flame can be switched on by actuation of a push button or the like.
- the resistance heater for the alkali glass body is additionally used for igniting the flame.
- a specificity for particular individual substances can be obtained by a suitable selection of the gas flows and by selection of the appropriate alkali component.
- rubidium-containing glass it is possible to detect nitrogen compounds; while, for substances of high phosphorus content, sodium-containing glass is selective.
- An advantageous selective ionization detector of the type indicated above includes a burner nozzle to which a combustible gas and sample gas mixture are supplied; above the burner nozzle an alkali glass body, heatable up to its softening temperature, is mounted; above the alkali glass body a collecting electrode is arranged; and the collecting electrode and nozzle are connected to a positive electric potential with respect to the alkali glass body.
- ion currents normal flame ionization detector signals
- CH normal hydrocarbon
- the electrons from the normal (hydrocarbon) combustion process flow to the burner nozzle, since the mount of the alkali glass body is at a potential negative relative to the nozzle and the electrons cannot overcome this potential.
- the nozzle and a housing which encloses the nozzle, the alkali glass body, and the collecting electrode are all provided with insulation with respect to ground; a negative voltage is connected to the housing (with respect to ground) and the alkali glass body is electrically connected to the housing, while the collecting electrode is mounted in the housing, but is electrically insulated with respect to the same and is connected to an amplifier at ground, and that the nozzle is electrically connectable alternatively to the housing (i.e., negative) or to ground by means of a switch.
- the detector can be operated by means of operation ofa simple electric switch alternatively as selective ionization detectoror as normal flame ionization detector.
- FIG. 1 schematically illustrates the design of a selective ionization detector incorporating the invention
- FIG. 2 diagrammatically illustrates one possibility of electrical potential distribution in the ionization detector of FIG. 1 in which the latter operates as a flame'ionization detector;
- FIG. 3 diagrammatically illustrates electrical potential distribution in the ionization detector of FIG. 1 in which the latter operates as an ionization detector selectively responding to phosphorus;
- FIG. 4 illustrates a chromatogram recorded with the detector in the mode of operation as shown in FIG. 2;
- FIG. 5 illustrates a chromatogram of the same mixture (on a changed scale) in the mode of operation as shown in FIG. 3, the mixture having a phosphoruscontaining component and a non-phosphoruscontaining component;
- FIG. 6 illustrates an embodiment of the ionization detector, permitting alternatively a mode of operation according to FIG. 2 or one according to FIG. 3.
- the detector according to FIG. 1 is substantially in the form of a prior art flame ionization detector (FID).
- a housing 10 is divided by a partition 12 into a lower and an upper chamber 14, 16, respectively.
- a burner nozzle 18 protrudes, terminating just below an aperture 20 in the partition 12.
- a sample gas is supplied to the nozzle 18 via a conduit 22.
- this conduit 22 is connected with the outlet of a separating column, and the sample gas consists of a mixture of carrier gas plus eluted sample components.
- a combustible gas generally hydrogen, is added to the sample gas via a conduit 24, so that a combustible gas, sample gas mixture issues from the nozzle and during operation commonly burns with a flame 26. Combustion air is intro Jerusalem into the lower chamber 14 via an air supply conduit 28.
- a bead 30 of an alkali-rich glass is mounted, specifically by means of two wires 32 and 34 which are passed through the wall of the housing 10 by means of electrical insulators 36, 38. These wires 32 and 34 simultaneously serve as current leads for an electric resistance heating element 40 arranged therebetween and in heatconducting contact with the bead 30.
- the heating quantity of the electric resistance heating element 40 is precisely adjustable by conventional means not illustrated.
- a collecting electrode 42 Above the bead 30 is positioned a collecting electrode 42.
- the collecting electrode 42 is secured to an electrically conducting holder 44, which is passed downwardly through an aperture 46 of the partition 12 and laterally out of the housing 10 by means of an insulator 48.
- the burnt gases of the flame 26 are exhausted via a connector 50.
- a suction pump When using the detector as a leak detector a suction pump is connected here.
- the electric resistance heating element 40 is so constituted that the alkali glass bead 30, when the detector is in operation, can be maintained in a viscous or softened state. In this state, a constant molecular movement and therefore a concentration compensation takes place in the alkali glass bead, so that fresh alkali metal atoms constantly migrate to the surface of the alkali glass bead, and therefore no impoverishment (of alkali metal) occurs.
- the bracket 52 and/or the wires 32, 34 preferably consist of platinum, on the one hand because platinum has substantially the same coefficient of thermal expansion as glass, and on the other hand due to its chemical inertness.
- the partition 12 ensures in well-known man ner that the insulator 48 and the conduit lead-out are not impaired (i.e., attacked) by combustion residues.
- the just described detector is particularly suited for,
- the sample may be burnt before introduction to the alkali source, which can be effected in a known manner in the first section of a double-level flame ionization detector (FID) or by flameless oxidation.
- FID flame ionization detector
- FIGS. 2 and 3 Another possibility of alternatively obtaining a high selectivity is shown by a comparison of FIGS. 2 and 3.
- FIG. 2 illustrates a circuit in which the normal FlD'signals resulting from the (hydro-carbon) combustion are also obtained.
- the burner nozzle 18 and the alkali source (softened alkali glass bead 30) are connected to a negative potential with respect to ground by a voltage source 54.
- the collecting electrode 42 connects to a grounded amplifier 56, thus practically at ground potential.
- both selective signals for instance, for halogen and phosphorus from the thermionic ion currents which originate from the bead 30, and also normal FID-signals, for instance, from the hydrocarbon components are obtained.
- the relative sensitivity with respect to halogen and phosphorus is in general increased, however, the detector is not sensitive specifically only to these substances. Such a performance of the detector may be desirable. An increase in the sensitivity is obtained for nitrogencontaining compounds if the flame is operated under reducing conditions.
- the collecting electrode 42 again connects to the amplifier 56 with respect to ground.
- the burner nozzle 18 is grounded, and only the alkali glass bead 30 and its mount are maintained at a negative potential (with respect to ground) by the voltage source 54.
- FIG. 6 illustrates an embodiment which permits the alternative operation according to FIG. 2 or according to FIG. 3 in a simple manner.
- Corresponding parts are referenced by the same reference numerals as in the FIGS. l to 3.
- the burner nozzle 18 is insulated with respect to ground by an insulating piece 58.
- Burner nozzle 18, alkali glass body 30 and collecting electrode 42 are enclosed by a cylindrical housing which is mounted for insulation with respect to ground.
- the collecting electrode 42 is mounted in this housing 60 by means of an insulator 62.
- the housing 60 is connected to a negative potential, for instance -l30 volts with respect to ground.
- switch means 63 the burner nozzle 18 can be alternatively connected electrically to the housing 60 and therewith to the negative potential or to ground.
- the alkali glass body 30 and its conduits are electrically connected to the housing 60.
- the detector of the invention described can be used in various manners in order to obtain selectivity for various substances.
- the glass bead 30 can be formed of sodiumcontaining glass and be excited to alkali emission by electric heating, while the flame 26 burns reducingly (O supplied at 40 ml/min; H at 15 ml/min). Then, a selective phosphorus signal is obtained.
- a selective nitrogen (N signal can be obtained by corresponding adjustment of the gas flows (0 at 0 ml/min, H at 5 ml/min) when the glass bead 30 is heated electrically. The hydrogen does not operate a flame.
- the detector can be operated in the following ways:
- the resistance heating 40 is also used for igniting the flame 26 when operation of the detector is started.
- a push button switch (not shown) may be provided by which, independently of the precisely effected adjustment of heating quantity (to element 40), a fixed amount of heating can be applied to the resistance heating element 40 which is fully sufficient to ignite the flame 26.
- a selective ionization detector of the type for detecting halogen, phosphorus and nitrogen compounds comprising a diode through which a sample gas under analysis is fed by means of a transfer gas, and an electrode including an alkali source in the form of a heated alkali-containing glass, so that the electrode exhibits an increased ion emission upon occurrence of such specific substances, the improvement in which:
- said alkali source comprises alkali glass maintained in a heated softened state during operation of the detector.
- said alkali glass is a sodium-enriched glass.
- said alkali glass is a rubidium-enriched glass.
- a selective ionization detector as claimed in claim 4, in which:
- a housing (60) encloses said burner nozzle (18); said alkali glass body (30) and said collecting electrode (42) are mounted by means of insulation (58) with respect to ground; said housing (60) is connected to a negative voltage source with respect to ground; said alkali glass body (30) is electrically connected to said housing (60); said collecting electrode (42) is mounted in the housing (60) but is electrically insulated therefrom and is connected to an amplifier (56) which is grounded; and said burner nozzle (18) is electrically connectable alternatively to the housing (60) or to ground by means of a switch means. 6.
- a selective ionization detector as claimed in claim 1, further comprising:
- a selective ionization detector as claimed in claim 6, in which:
- a separate heating quantity sufficient for igniting the flame can be supplied to said heating means by actuation of a manually operated means.
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material 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)
- Examining Or Testing Airtightness (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2222396A DE2222396B2 (de) | 1972-05-06 | 1972-05-06 | Selektiver lonisationsdetektor |
Publications (1)
Publication Number | Publication Date |
---|---|
US3852037A true US3852037A (en) | 1974-12-03 |
Family
ID=5844308
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00357496A Expired - Lifetime US3852037A (en) | 1972-05-06 | 1973-05-04 | Selective ionization detector |
Country Status (5)
Country | Link |
---|---|
US (1) | US3852037A (enrdf_load_html_response) |
JP (1) | JPS553664B2 (enrdf_load_html_response) |
DE (1) | DE2222396B2 (enrdf_load_html_response) |
GB (1) | GB1435747A (enrdf_load_html_response) |
NL (1) | NL7306217A (enrdf_load_html_response) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2907222A1 (de) * | 1978-02-28 | 1980-01-10 | Varian Associates | Verfahren und vorrichtung zur analyse einer probe |
US4202666A (en) * | 1978-02-24 | 1980-05-13 | Tracor, Inc. | Method and apparatus for preventing the destruction of an alkali source of a nitrogen-phosphorous detector |
US4361810A (en) * | 1980-05-10 | 1982-11-30 | Ratfisch Instrumente | Arrangement for monitoring the concentration of potentially explosive substances in gas streams |
US4508685A (en) * | 1981-06-09 | 1985-04-02 | Carlo Erba Strumentazione S.P.A. | Modified-flame thermionic detector for gas chromatographs and method for the identification of components in sample under analysis |
US4524047A (en) * | 1983-03-02 | 1985-06-18 | Patterson Paul L | Thermionic detector with multiple layered ionization source |
US4663297A (en) * | 1982-09-10 | 1987-05-05 | Yates Jr John T | Temperature programmed spectroscopy techniques |
US4744954A (en) * | 1986-07-11 | 1988-05-17 | Allied-Signal Inc. | Amperometric gas sensor containing a solid electrolyte |
US4801849A (en) * | 1984-05-16 | 1989-01-31 | Office National D Etudes Et De Recherches | Ion source operating by surface ionization in particular for providing an ion probe |
US4839143A (en) * | 1985-02-15 | 1989-06-13 | Allied-Signal Inc. | Selective ionization of gas constituents using electrolytic reactions |
US4877584A (en) * | 1982-09-10 | 1989-10-31 | Yates Jr John T | Temperature programmed spectroscopy techniques |
US5198009A (en) * | 1991-11-22 | 1993-03-30 | The Perkin Elmer Corporation | Method of manufacturing glass beads for use in thermionic gas chromatographic detectors |
EP0594887A1 (de) * | 1992-10-29 | 1994-05-04 | Hans Mueller Prof. Dr. Van Der Haegen | Verfahren zur Erkennung von Kunststoffen sowie deren anschliessende Sortierung |
US20150330956A1 (en) * | 2014-05-16 | 2015-11-19 | Waters Technologies Corporation | Flame Ionization Detection Burner Assemblies for Use in Compressible Fluid-Based Chromatography Systems |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5717309Y2 (enrdf_load_html_response) * | 1977-04-20 | 1982-04-12 | ||
JPS5717308Y2 (enrdf_load_html_response) * | 1977-04-20 | 1982-04-12 | ||
DE2738608C2 (de) * | 1977-08-26 | 1985-02-07 | Siemens AG, 1000 Berlin und 8000 München | Thermoionischer Detektor für die selektive Bestimmung von organischen, Heteroatome enthaltenden Probensubstanzen |
JPS5550155A (en) * | 1978-10-06 | 1980-04-11 | Hitachi Ltd | Heat ionization detector |
JPS56155345U (enrdf_load_html_response) * | 1980-04-19 | 1981-11-19 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3372994A (en) * | 1965-01-08 | 1968-03-12 | Health Education Welfare Usa | Flame ionization detector |
US3425806A (en) * | 1965-03-22 | 1969-02-04 | Us Health Education & Welfare | Method and means for detecting a halogen or phosphorus in a gaseous material |
US3589869A (en) * | 1969-02-17 | 1971-06-29 | Varian Associates | Chemical-ionization detection method and apparatus |
-
1972
- 1972-05-06 DE DE2222396A patent/DE2222396B2/de not_active Ceased
-
1973
- 1973-05-04 JP JP5020673A patent/JPS553664B2/ja not_active Expired
- 1973-05-04 NL NL7306217A patent/NL7306217A/xx not_active Application Discontinuation
- 1973-05-04 US US00357496A patent/US3852037A/en not_active Expired - Lifetime
- 1973-05-04 GB GB2136173A patent/GB1435747A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3372994A (en) * | 1965-01-08 | 1968-03-12 | Health Education Welfare Usa | Flame ionization detector |
US3425806A (en) * | 1965-03-22 | 1969-02-04 | Us Health Education & Welfare | Method and means for detecting a halogen or phosphorus in a gaseous material |
US3589869A (en) * | 1969-02-17 | 1971-06-29 | Varian Associates | Chemical-ionization detection method and apparatus |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4202666A (en) * | 1978-02-24 | 1980-05-13 | Tracor, Inc. | Method and apparatus for preventing the destruction of an alkali source of a nitrogen-phosphorous detector |
US4203726A (en) * | 1978-02-28 | 1980-05-20 | Varian Associates, Inc. | Thermionic detector |
DE2907222A1 (de) * | 1978-02-28 | 1980-01-10 | Varian Associates | Verfahren und vorrichtung zur analyse einer probe |
US4361810A (en) * | 1980-05-10 | 1982-11-30 | Ratfisch Instrumente | Arrangement for monitoring the concentration of potentially explosive substances in gas streams |
US4508685A (en) * | 1981-06-09 | 1985-04-02 | Carlo Erba Strumentazione S.P.A. | Modified-flame thermionic detector for gas chromatographs and method for the identification of components in sample under analysis |
EP0066735B1 (en) * | 1981-06-09 | 1986-10-29 | CARLO ERBA STRUMENTAZIONE S.p.A. | Modified-flame thermionic detector for gas chromatographs and method for the identification of components in sample under analysis |
US4877584A (en) * | 1982-09-10 | 1989-10-31 | Yates Jr John T | Temperature programmed spectroscopy techniques |
US4663297A (en) * | 1982-09-10 | 1987-05-05 | Yates Jr John T | Temperature programmed spectroscopy techniques |
US4524047A (en) * | 1983-03-02 | 1985-06-18 | Patterson Paul L | Thermionic detector with multiple layered ionization source |
US4801849A (en) * | 1984-05-16 | 1989-01-31 | Office National D Etudes Et De Recherches | Ion source operating by surface ionization in particular for providing an ion probe |
US4839143A (en) * | 1985-02-15 | 1989-06-13 | Allied-Signal Inc. | Selective ionization of gas constituents using electrolytic reactions |
US4744954A (en) * | 1986-07-11 | 1988-05-17 | Allied-Signal Inc. | Amperometric gas sensor containing a solid electrolyte |
US5198009A (en) * | 1991-11-22 | 1993-03-30 | The Perkin Elmer Corporation | Method of manufacturing glass beads for use in thermionic gas chromatographic detectors |
DE4237168B4 (de) * | 1991-11-22 | 2006-07-27 | The Perkin-Elmer Corp., Norwalk | Verfahren zur Herstellung einer alkalimetallhaltigen Glasperle zur Verwendung in thermionischen Gaschromatographie-Detektoren |
EP0594887A1 (de) * | 1992-10-29 | 1994-05-04 | Hans Mueller Prof. Dr. Van Der Haegen | Verfahren zur Erkennung von Kunststoffen sowie deren anschliessende Sortierung |
US20150330956A1 (en) * | 2014-05-16 | 2015-11-19 | Waters Technologies Corporation | Flame Ionization Detection Burner Assemblies for Use in Compressible Fluid-Based Chromatography Systems |
US10191020B2 (en) * | 2014-05-16 | 2019-01-29 | Waters Technologies Corporation | Flame ionization detection burner assemblies for use in compressible fluid-based chromatography systems |
US10877006B2 (en) | 2014-05-16 | 2020-12-29 | Waters Technologies Corporation | Flame ionization detection burner assemblies for use in compressible fluid-based chromatography systems |
Also Published As
Publication number | Publication date |
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JPS4949689A (enrdf_load_html_response) | 1974-05-14 |
GB1435747A (en) | 1976-05-12 |
NL7306217A (enrdf_load_html_response) | 1973-11-08 |
DE2222396B2 (de) | 1975-04-30 |
DE2222396A1 (de) | 1973-11-15 |
JPS553664B2 (enrdf_load_html_response) | 1980-01-26 |
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