USRE28374E - Chemiluminescent instrument - Google Patents
Chemiluminescent instrument Download PDFInfo
- Publication number
- USRE28374E USRE28374E US42564173A USRE28374E US RE28374 E USRE28374 E US RE28374E US 42564173 A US42564173 A US 42564173A US RE28374 E USRE28374 E US RE28374E
- Authority
- US
- United States
- Prior art keywords
- reaction chamber
- opening
- conduit
- reactant
- sample
- 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
Links
- 238000006243 chemical reaction Methods 0.000 claims abstract description 173
- 239000000376 reactant Substances 0.000 claims abstract description 82
- 239000000203 mixture Substances 0.000 description 62
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 36
- 239000000470 constituent Substances 0.000 description 22
- 239000008246 gaseous mixture Substances 0.000 description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
- G01N21/766—Chemiluminescence; Bioluminescence of gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K2/00—Non-electric light sources using luminescence; Light sources using electrochemiluminescence
- F21K2/06—Non-electric light sources using luminescence; Light sources using electrochemiluminescence using chemiluminescence
-
- 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
- Y10T436/17—Nitrogen containing
- Y10T436/177692—Oxides of nitrogen
Definitions
- FIG.1 ELECTRONIC 30*AMPLIFIER 20 /a M. Z2 k9 FLOW FLOW MET RING METERING 4 SAMPLE REACTANT MIXTURE M Z4 MIXTURE PUMP Z6 F
- chemiluminiescence of certain reactions has been known for some time and recent investigations have produced instruments capable of utilizing chemiluminescence as an analytical tool.
- One of such instruments uses the chemiluminescence of the reaction between nitric oxide and ozone to determine the concentration of nitric oxide or ozone in gaseous mixtures by blending the gaseous mixture with a known quantity of the other reactant in a well-stirred reactor at extremely low pressures of one torr or less.
- a photosetnsitive device measures the intensity of the resulting chemiluminescence and applies an output signal to a calibrated meter.
- This invention provides a sensitive, accurate, versatile and economical instrument and process for measuring the chemiluminescence of a reaction between a constituent of a gaseous mixture and a gaseous reactant to determine the concentration of the constituent.
- the invention is useful particularly in measuring the concentration of nitric oxide in a gaseous mixture. Nitric oxide concentrations ranging from a few parts per billion thru several parts per hundred can be measured accurately and efiiciently with the invention. Higher pressures are utilized in the invention to improve reproducibility and economic aspects of the instrument. Sensitivity and accuracy are maximized by ignoring the well-stirred reactor techniques of the prior art and emphasizing instead a technique that maintains a substantially stable portion of the reaction as close as possible to a light sensing device.
- An instrument for carrying out the invention comprises a reaction chamber having an opening at one end with a light transmitting element scalingly mounted in the opening.
- a sample conduit for supplying the gaseous mixture to the reaction chamber opens into the reaction chamber at a location proximate to the inner surface of the light transmitting element.
- a reactant conduit supplies to the reaction chamber a gaseous reactant capable of reacting with a constituent of the sample mixture in a manner that produces chemiluminescence.
- An exhaust conduit removes the reaction products from the reaction chamber.
- a light sensing device such as a photomultiplier tube is connected to the reaction chamber where it receives the light passing through the light transmitting element from the chemiluminescent reaction taking place within the chamber.
- the invention is highly suited to measuring the concentration of nitric oxide in a gaseous sample mixture by reacting the nitric oxide with ozone.
- sample mixture enters the reaction chamber through the sample conduit and a gaseous reactant mixture containing at least a prederetemined minimum amount of ozone enters the reaction chamber through the reaction conduit.
- Reaction begins immediately and a portion of the reaction that depends on the concentration of the nitric oxide in the sample mixture occurs within a short distance of the light transmitting element. Continuously flowing the gaseous mixtures into the reaction chamber and measuring the chemiluminescence transmitted through the light transmitting element produces accurate, continuous readouts over a wide range of nitric oxide concentrations.
- Pressure in the reaction chamber must be sufficiently high to avoid excess turbulence and to promote uniform reaction proximate to the light sensing device. Best results are achieved when the absolute pressure in the reaction chamber is maintained above about 5 torr with preferred pressures ranging above 300 torr, because the gases then enter and flow through the reaction chamber with virtually laminar flow.
- the smooth, stable reaction reduces transient mixing variations and the resulting variations in the light reaching the light sensing device. Such higher pressures also increase the reaction rate and thereby maintain a greater portion of the reaction proximate to the light sensing device. The resulting increase in light intensity further improves accuracy and sensitivity.
- Reaction chamber pressure approximating atmospheric pressure can be used if desired.
- An exhaust pump can be connected to an exhaust outlet of the reaction chamber to draw the sample mixture and the reactant mixture through the reaction chamber.
- Metering devices then are included in the sample conduit and the reactant conduit; such metering devices typically are fine capillary tubes that are located a sufficient distance upstream of the reaction chamber to permit dissipation of any turbulence produced thereby. If operation above atmospheric pressure is desired, pumps are included in the sample conduit and the reactant conduit and the exhaust outlet is connected to the atmosphere through an appropriate metering device.
- Optimized flow rates of the sample mixture and the reactant mixture depend on the quantity and nature of the other constituents in the gaseous mixtures, assuming of course that the proportions of the reactants are within a predetermined range.
- Carbon dioxide for example has a quenching effect on the emitted chemiluminescence of the nitric oxide and ozone reaction approximately 23 times that of oxygen, which usually forms the greater portion of the ozone containing reactant mixture.
- the quenching effect is minimized in sample mixtures containing a high proportion of carbon dioxide by providing relatively high flow of the reactant mixture to insure a high ratio of oxygen to carbon dioxide in the reaction chamber.
- the light transmitting element and the light sensing device preferably transmit and measure light in a broad portion of the spectrum including wavelengths between about 6400 Angstroms and 25,000 Angstroms. Improved results can be achieved by measuring light having wavelengths of about MOO-15,000 Angstroms only. Spurious noise is minimized further by measuring light having wavelengths of about l0,000-l4,000 Angstroms only.
- a cylindrical housing serves preferably as the reaction chamber.
- a disc-shaped light transmitting element is mounted sealingly in one end of the cylindrical housing and the other end is closed except for the exhaust outlet.
- the sample conduit extends through the cylindrical wall of the housing and opens into the reaction chamber at a location proximate to the light transmitting element.
- Reactant preferably is introduced into the reaction chamber from a reactant conduit opening adjacent the sample conduit opening or between the sample conduit opening and the exhaust outlet.
- FIG. 1 is a schematic illustrating the basic structural and operational principles of the invention.
- FIG. 2 is a partially sectioned view through a reaction chamber for the instrument in which smoothly curved conduits introt cute both the sample mixture and the reactants into the reaction chamber at a location proximate to the central portion of a light transmitting element.
- FIG. 3 is an elevation of the reaction chamber shown in FIG. 2.
- FIG. 4 is a cross section of an alternate reaction chamber design in which a smoothly curved conduit introduces the sample mixture at a location proximate to the central portion of the light transmitting element and a straight conduit introduces the reactant into the reaction chamber at a location between the sample mixture outlet and the exhaust conduit.
- FIG. 1 is a schematic illustrating the basic structural and operational principles of the invention.
- FIG. 2 is a partially sectioned view through a reaction chamber for the instrument in which smoothly curved conduits introt cute both the sample mixture and the reactants into the reaction chamber at a location proximate to the central portion of a light
- FIG. 5 is a cross section of a reaction chamber in which a straight conduit introduces the sample mixture into the reaction chamber at a location closely adjacent an edge of the light transmitting element and another straight conduit introduces, the reactant at a location diametically across from the mixture outlet and axially removed therefrom toward the exhaust conduit.
- the reaction chamber of FIG. 6 is similar to that of FIG. 5 except that the reactant enters the chamber on the same side as the sample mixture.
- FIG. 7 shows another reaction chamber in which the reactant enters the reaction chamber through an annular conduit that surrounds the sample conduit.
- a gaseous sample mixture containing an unknown quantity of nitric oxide is conducted by conduit 10 to a capillary type of flow metering device 12.
- a sample conduit 14 introduces the sample mixture leaving the flow metering device into a cylindrical reaction chamber 16.
- a conduit 18 conducts a gaseous reactant mixture containing at least a predetermined minimum amount of ozone to a capillary type flow metering device 20 and a reactant conduit 22 introduces the reactant leaving the flow metering device into reaction chamber 16.
- One end of reaction chamber 16 has an outlet fitting 24 attached thereto and a vacuum pump 26 is connected to fitting 24.
- a photomultiplier device 28 is mounted on the other end of reaction chamber 16 and is connected electrically through an amplifier 30 and other appropriate electronic circuitry to a readout device 32.
- Outlet fitting 24 communicates with the interior of reaction chamber 16 through an opening 34 in an end wall thereof (FIG. 2).
- a disc-shaped light transmitting element 38 closes the entire opposite end 35 of the chamber so that outlet fitting 24 is axially removed from element 38.
- the housing of photomultiplier device 28 is threaded into the reaction chamber to maintain element 38 in place.
- Appropriate seals 40 and 42 assure gas tight installation of element 38 in opening 35.
- a flange 44 provides for fastening the assembly of reaction chamber 16 and photomultiplier device 28 to supporting structure (not shown).
- Sample conduit 14 extends through the cylindrical wall of chamber 16 approximately at its longitudinal midpoint and curves smoothly toward light transmitting element 38 so the opening 46 at the end of the sample conduit is proximate to the inner surface of element 38.
- Reactant conduit 22 extends through the cylindrical wall of reaction chamber 16 at a location diametrically opposed to conduit 14 and conduit 22 also curves smoothly toward light transmitting element 38 so the opening 48 at its end also is proximate to the inner surface of element 38.
- Opening 48 is in the same plane as opening 46 and is adjacent to opening 46. Both openings 46 and 48 are located in the central portion of reaction chamber 16 and both are located axially between light transmitting element 38 and exhaust opening 34.
- Reaction chamber 16 typically is about 2 inches in diameter and about 3 inches long.
- Conduits 14 and 22 have an inside diameter of about /6 inch and a wall thickness of about inch.
- Element 38 is a glass optical filter capable of transmitting light in at least the dark red portion of the visible region and the infrared region (above about 6400 Angstrom units). Openings 46 and 48 are about A inch from the inner surface of element 38 and are spaced apart about Mi inch.
- Instrument operation occurs in the following manner.
- Pump 26 is started and capillary metering devices 12 and 20 are selected so the subatmospheric pressure within reaction chamber 16 reaches some predetermined value. Good results are achieved when the predetermined value of pressure is at least about 5 torr.
- a reactant mixture containing about 2 percent ozone and 98 percent oxygen is supplied to reactant conduit 18.
- sample mixture flows into reaction chamber 16 through opening 46, nitric oxide molecules in the sample mixture react with ozone mole cules in the reactant mixture to produce chemiluminescence in an amount proportional to the concentration of the nitric oxide in the gaseous mixture.
- Both the sample mixture and the reactant mixture flow into the reaction chamber with substantially laminar fiow.
- the mixtures blend with each other and pass through the reaction chamber with a minimum of turbulence. This stability provides a high degree of reproducibility and sensitivity.
- Sample conduit 46 in fact directs the sample mixture toward the light transmitting element as the mixture enters the reaction chamber.
- the reaction continues as the reacting compositions move through reaction chamber 16 toward exhaust opening 36 but the intensity of the light received by light sensing device 28 diminishes with the decreasing solid angle subtended by light transmitting element 38.
- Increased reaction rates can be achieved by raising the pressure in the reaction chamber since the higher pressure increases the number of molecules of nitric oxide and ozone in the chamber and thereby increases the probability of molecule collision.
- Highly accurate results with excellent sensitivity are achieved by raising the reaction chamber pressure to at least about 300 torr.
- Such higher pressures permit the gaseous mixture and the reactant to enter the reaction chamber with an improved laminar type flow that diminishes transient variations in the light intensity resulting from nonuniform mixing within the reaction chamber.
- sample conduit 14a is a similar to that of FIG. 2 but a straight reactant conduit 22a terminated a short distance just inside the cylindrical wall of the reaction chamber so that its opening 48a is directed radially inward in a plane located axially btween the sample conduit opening and the exhaust conduit opening.
- Conduit 22a preferably enters the chamber within about one half of the axial length of the. chamber from light transmitting element 38. Comparative tests with a FIG. 4 reaction chamber 3 inches long and having conduit 22a 1.5 inches from element 38 indicate slight increases in measurable light intensity over the FIG. 2 chamber.
- the location of reactant conduit 22b is similar to that of FIG. 4.
- Sample conduit 14b is straight and extends radially into the chamber at a location closely adjacent an edge of light transmitting element 38. Opening 48b of the reactant conduit is diametrically across and axially displaced toward the exhaust opening from the opening of the sample conduit.
- the FIG. 5 arrangement also produced slight increases in measurable light intensity.
- sample conduit 14c extends straight into the reaction chamber and reactant conduit 22d surrounds the sample conduit so the reactant conduit forms an annular opening 48d.
- each of these reaction chambers the sample conduit is proximate to the light sensing assembly to promote reaction proximate thereto.
- Each of the disclosed reaction chamber constructions and similar constructions produces useful results although the best combination of accuracy and sensitivity has been achieved to date with the chambers of FIGS. 2, 4 and 5.
- Flow metering devices 12 and preferably are at least several inches upstream from the respective conduit openings to permit dissipation of any turbulence produced thereby.
- the use of capillary tubes as the metering devices provides stable metering and minimal turbulance.
- Appropriate converters can be included in the sample conduit to convert other oxides of nitrogen into nitric oxide and thereby permit using the invention to provide the total concentration of oxides of nitrogen in the sample mixture.
- Arrozone killer can be included between the reaction chamber and the pump to increase the life of rubber seals and other rubber pump components.
- Other light sensing devices capable of responding to light having the aforementioned wavelengths can be substituted for the photomultiplier device.
- this invention provides improved structures and techniques for accurately and conveniently determining the concentrations of gases such as nitric oxide in a gaseous mixture.
- the invention has greatly improved sensitivity, reproductibility, and economy of construction and operation.
- An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by easuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
- a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber
- the light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant] [2.
- the instrument of claim 1 in which the light transmitting means is a disc located at one end of the cylindrical housing] [3.
- the reactant conduit opens into the reaction chamber at a location axially between the opening of the sample conduit and the opening of the exhaust conduit] 4.
- a reaction chamber for a chemiluminescent reactlon comprising a housing having an opening at one end,
- a sample conduit extending into said housing and having an opening for admitting a sample gas into the housing, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit extending into said housing and having an opening for admitting a reactant gas into the housing separate from said sample conduit
- reaction chamber of claim 13 in which the opening of the sample conduit lies in a plane substantially parallel to the plane of the light transmitting means.
- reaction chamber of claim 13 in which the housing is a circular cylinder closed at one end and the light transmitting means extends perpendicular to the axis of the housing at its opposite end.
- reaction chamber of claim 15 in which the opening of the reactant conduit is proximate to the inner surface of the light transmitting means.
- reaction chamber of claim 12 in which the sample conduit extends radially into the reaction chamber and its opening is adjacent an edge of the light transmitting element.
- An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
- a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit connected to said reactant chamber and having an opening for admitting the gaseous reactant into the reaction chamber separate from said sample conduit opening
- said light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said light transmitting means being a disc located at one end of the cylindrical housing, said reactant conduit opening into the reaction chamber at a location axially between the opening of the sample conduit and the opening of the exhaust conduit.
- An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
- a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber
- An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reactionbotween the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
- a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber separate from said sample conduit,
- said light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said pump means producing a pressure of at least 300 torr in the reaction chamber.
- An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end, i
- a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means
- a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber
- said light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said reactant conduit extending through the cylindrical wall of the housing and opening into the reaction chamber at a location dimetrically opposed to and axially removed from the opening of the sample conduit.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Analytical Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
12. A REACTION CHAMBER FOR A CHEMILUMINESCENT REACTION COMPRISING A HOUSING HAVING AN OPENING AT ONE END, A LIGHT TRANSMITTING MEANS SEALINGLY MOUNTED IN THE OPENING OF THE HOUSING, A SAMPLE CONDUIT EXTENDING INTO SAID HOUSING AND HAVING AN OPENING FOR ADMITTING A SAMPLE GAS INTO THE HOUSING, SAID OPENING BEING PROXIMATE TO THE INNER SURFACE OF THE LIGHT TRANSMITTING MEANS, A REACTANT CONDUIT EXTENDING INTO SAID HOUSING AND HAVING AN OPENING FOR ADMITTING A REACTANT GAS INTO THE HOUSING SEPARATE FROM SAID SAMPLE CONDUIT, AND
AN EXHAUST OUTLET FORMED IN SAID HOUSING AT A LOCATION THAT IS REMOTE FROM SAID SAMPLE CONDUIT OPENING AND SAID REACTANT CONDUIT OPENING.
AN EXHAUST OUTLET FORMED IN SAID HOUSING AT A LOCATION THAT IS REMOTE FROM SAID SAMPLE CONDUIT OPENING AND SAID REACTANT CONDUIT OPENING.
Description
March 25, 1975 Original Filed May 26, 1971 32 READOUT A. D. COLVIN ET AL CHEMILUMINESCENT INSTRUMENT 2 Sheets-Sheet l FIG.1 ELECTRONIC 30*AMPLIFIER 20 /a M. Z2 k9 FLOW FLOW MET RING METERING 4 SAMPLE REACTANT MIXTURE M Z4 MIXTURE PUMP Z6 F|G.2
3a FIG.3
46 Z 44 I I I 32 INVENTORS Alf) 0. (OZV/N ALA/V WAE/V/CK ATTORNEYS March 25, 1975 A. D. COLVIN F-TAL CHEMILUMINESCENT INSTRUMENT Original Filed May 26. 1971 FIG.4
F'IG.6
2 Sheets-Sheet 3 FIG.5
FIC5.'7
INVENTORS Alf/Y .0 (OAW/V AZA/V 1464/? /CC ATTORNEYS United States Patent Re. 28,374 Reissued Mar. 25, 1975 28,374 CHEMILUMINESCENT INSTRUMENT Alex D. Colvin and Alan War-nick, Oak Park, Mich, assignors to Ford Motor Company, Dearborn, Mich. Original No. 3,746,514, dated July 17, 1973, Ser. No. 146,927, May 26, 1971. Application for reissue Dec. 17, 1973, Ser. No. 425,641
Int. Cl. Glllu 27/68 US. Cl. 23-254 R 14 Claims Matter enclosed in heavy brackets appears in the onglnal patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
ABSTRACT OF THE DISCLOSURE Gaseous mixtures containing an unknown quantity of nitric oxide are introduced into a cylindrical reaction chamber at a location proximate to the inner surface of a light transmitting element forming one end of the reaction chamber. Ozone also is introduced into the reaction chamber and the chemiluminescence transmitted through the light transmitting element from the resulting reaction is measured with a photomultiplier tube. Reaction chamber pressure preferably is maintained above about 5 torr.
BACKGROUND OF THE INVENTION This invention relates to that of concurrently filed US. patent application Warnick et al., Ser. No. 146,929.
Recent interest in reducing the quantity of proportion of harmful constituents in the atmosphere has provided considerable impetus to the development of processes and devices for reducing the amounts of such constituents in exhaust gases from vehicle engines, furnaces, and other power generating equipment. Such development has been hindered because an instrument capable of accurately, efliciently and economically measuring very small quantitles of constituents in gaseous mixtures has not been available.
The chemiluminiescence of certain reactions has been known for some time and recent investigations have produced instruments capable of utilizing chemiluminescence as an analytical tool. One of such instruments uses the chemiluminescence of the reaction between nitric oxide and ozone to determine the concentration of nitric oxide or ozone in gaseous mixtures by blending the gaseous mixture with a known quantity of the other reactant in a well-stirred reactor at extremely low pressures of one torr or less. A photosetnsitive device measures the intensity of the resulting chemiluminescence and applies an output signal to a calibrated meter.
Considerable difficulties have been encountered in attempting to utilize that instrument and its technique on a broad basis. Structurally, a large vacuum pump is necessary to produce the extremely low pressures in the reaction chamber and such pumps increase instrument costs to an uneconomical level. The extremely low pressure also accentuate sealing difficulties and necessitate precision manufacturing and assembly procedures. Operationally, transient conditions tend to occur during the wellstirred mixing of the gaseous mixture and the reactant and these transient conditions interfere significantly with reproducibility, sensitivity, and overall accuracy.
SUMMARY OF THE INVENTION This invention provides a sensitive, accurate, versatile and economical instrument and process for measuring the chemiluminescence of a reaction between a constituent of a gaseous mixture and a gaseous reactant to determine the concentration of the constituent. The invention is useful particularly in measuring the concentration of nitric oxide in a gaseous mixture. Nitric oxide concentrations ranging from a few parts per billion thru several parts per hundred can be measured accurately and efiiciently with the invention. Higher pressures are utilized in the invention to improve reproducibility and economic aspects of the instrument. Sensitivity and accuracy are maximized by ignoring the well-stirred reactor techniques of the prior art and emphasizing instead a technique that maintains a substantially stable portion of the reaction as close as possible to a light sensing device.
An instrument for carrying out the invention comprises a reaction chamber having an opening at one end with a light transmitting element scalingly mounted in the opening. A sample conduit for supplying the gaseous mixture to the reaction chamber opens into the reaction chamber at a location proximate to the inner surface of the light transmitting element. A reactant conduit supplies to the reaction chamber a gaseous reactant capable of reacting with a constituent of the sample mixture in a manner that produces chemiluminescence. An exhaust conduit removes the reaction products from the reaction chamber. A light sensing device such as a photomultiplier tube is connected to the reaction chamber where it receives the light passing through the light transmitting element from the chemiluminescent reaction taking place within the chamber.
The invention is highly suited to measuring the concentration of nitric oxide in a gaseous sample mixture by reacting the nitric oxide with ozone. Such sample mixture enters the reaction chamber through the sample conduit and a gaseous reactant mixture containing at least a prederetemined minimum amount of ozone enters the reaction chamber through the reaction conduit. Reaction begins immediately and a portion of the reaction that depends on the concentration of the nitric oxide in the sample mixture occurs within a short distance of the light transmitting element. Continuously flowing the gaseous mixtures into the reaction chamber and measuring the chemiluminescence transmitted through the light transmitting element produces accurate, continuous readouts over a wide range of nitric oxide concentrations.
Pressure in the reaction chamber must be sufficiently high to avoid excess turbulence and to promote uniform reaction proximate to the light sensing device. Best results are achieved when the absolute pressure in the reaction chamber is maintained above about 5 torr with preferred pressures ranging above 300 torr, because the gases then enter and flow through the reaction chamber with virtually laminar flow. The smooth, stable reaction reduces transient mixing variations and the resulting variations in the light reaching the light sensing device. Such higher pressures also increase the reaction rate and thereby maintain a greater portion of the reaction proximate to the light sensing device. The resulting increase in light intensity further improves accuracy and sensitivity. Reaction chamber pressure approximating atmospheric pressure can be used if desired.
An exhaust pump can be connected to an exhaust outlet of the reaction chamber to draw the sample mixture and the reactant mixture through the reaction chamber. Metering devices then are included in the sample conduit and the reactant conduit; such metering devices typically are fine capillary tubes that are located a sufficient distance upstream of the reaction chamber to permit dissipation of any turbulence produced thereby. If operation above atmospheric pressure is desired, pumps are included in the sample conduit and the reactant conduit and the exhaust outlet is connected to the atmosphere through an appropriate metering device.
Optimized flow rates of the sample mixture and the reactant mixture depend on the quantity and nature of the other constituents in the gaseous mixtures, assuming of course that the proportions of the reactants are within a predetermined range. Carbon dioxide for example has a quenching effect on the emitted chemiluminescence of the nitric oxide and ozone reaction approximately 23 times that of oxygen, which usually forms the greater portion of the ozone containing reactant mixture. The quenching effect is minimized in sample mixtures containing a high proportion of carbon dioxide by providing relatively high flow of the reactant mixture to insure a high ratio of oxygen to carbon dioxide in the reaction chamber. Thus, best results are achieved when analyzing automotive exhaust gases (which contain a high proportion of carbon dioxide) by providing about 4 volumes of reactant mixture for each volume of sample mixture, while analyzing atmospheric sample mixtures preferably is conducted with about 4 volumes of sample mixture for each volume of reactant mixture. Analysis of most other mixtures can be performed within these ratios.
For the nitric oxide-ozone reactions, the light transmitting element and the light sensing device preferably transmit and measure light in a broad portion of the spectrum including wavelengths between about 6400 Angstroms and 25,000 Angstroms. Improved results can be achieved by measuring light having wavelengths of about MOO-15,000 Angstroms only. Spurious noise is minimized further by measuring light having wavelengths of about l0,000-l4,000 Angstroms only.
A cylindrical housing serves preferably as the reaction chamber. A disc-shaped light transmitting element is mounted sealingly in one end of the cylindrical housing and the other end is closed except for the exhaust outlet. The sample conduit extends through the cylindrical wall of the housing and opens into the reaction chamber at a location proximate to the light transmitting element. Reactant preferably is introduced into the reaction chamber from a reactant conduit opening adjacent the sample conduit opening or between the sample conduit opening and the exhaust outlet.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustrating the basic structural and operational principles of the invention. FIG. 2 is a partially sectioned view through a reaction chamber for the instrument in which smoothly curved conduits introt duce both the sample mixture and the reactants into the reaction chamber at a location proximate to the central portion of a light transmitting element. FIG. 3 is an elevation of the reaction chamber shown in FIG. 2. FIG. 4 is a cross section of an alternate reaction chamber design in which a smoothly curved conduit introduces the sample mixture at a location proximate to the central portion of the light transmitting element and a straight conduit introduces the reactant into the reaction chamber at a location between the sample mixture outlet and the exhaust conduit. FIG. 5 is a cross section of a reaction chamber in which a straight conduit introduces the sample mixture into the reaction chamber at a location closely adjacent an edge of the light transmitting element and another straight conduit introduces, the reactant at a location diametically across from the mixture outlet and axially removed therefrom toward the exhaust conduit. The reaction chamber of FIG. 6 is similar to that of FIG. 5 except that the reactant enters the chamber on the same side as the sample mixture. FIG. 7 shows another reaction chamber in which the reactant enters the reaction chamber through an annular conduit that surrounds the sample conduit.
DETAILED DESCRIPTION Referring to FIGS. 1-3, a gaseous sample mixture containing an unknown quantity of nitric oxide is conducted by conduit 10 to a capillary type of flow metering device 12. A sample conduit 14 introduces the sample mixture leaving the flow metering device into a cylindrical reaction chamber 16. A conduit 18 conducts a gaseous reactant mixture containing at least a predetermined minimum amount of ozone to a capillary type flow metering device 20 and a reactant conduit 22 introduces the reactant leaving the flow metering device into reaction chamber 16. One end of reaction chamber 16 has an outlet fitting 24 attached thereto and a vacuum pump 26 is connected to fitting 24. A photomultiplier device 28 is mounted on the other end of reaction chamber 16 and is connected electrically through an amplifier 30 and other appropriate electronic circuitry to a readout device 32.
Outlet fitting 24 communicates with the interior of reaction chamber 16 through an opening 34 in an end wall thereof (FIG. 2). A disc-shaped light transmitting element 38 closes the entire opposite end 35 of the chamber so that outlet fitting 24 is axially removed from element 38. The housing of photomultiplier device 28 is threaded into the reaction chamber to maintain element 38 in place. Appropriate seals 40 and 42 assure gas tight installation of element 38 in opening 35. A flange 44 provides for fastening the assembly of reaction chamber 16 and photomultiplier device 28 to supporting structure (not shown).
Instrument operation occurs in the following manner. Pump 26 is started and capillary metering devices 12 and 20 are selected so the subatmospheric pressure within reaction chamber 16 reaches some predetermined value. Good results are achieved when the predetermined value of pressure is at least about 5 torr. A reactant mixture containing about 2 percent ozone and 98 percent oxygen is supplied to reactant conduit 18. As sample mixture flows into reaction chamber 16 through opening 46, nitric oxide molecules in the sample mixture react with ozone mole cules in the reactant mixture to produce chemiluminescence in an amount proportional to the concentration of the nitric oxide in the gaseous mixture.
Both the sample mixture and the reactant mixture flow into the reaction chamber with substantially laminar fiow. In the reaction chamber, the mixtures blend with each other and pass through the reaction chamber with a minimum of turbulence. This stability provides a high degree of reproducibility and sensitivity.
Light from the chemiluminescence passes through element 38 and its intensity is detected by photomultiplier device 28. An electronic signal representing the intensity is transmitted to electronic amplifier 30 which in turn applies an output signal to readout device 32 that is calibrated to read directly in units representing the concentration of nitric oxide in the gaseous mixture.
Accuracy and sensitivity are maximized when a considerable portion of the reaction between the nitric oxide and the ozone occurs proximately to the inner surface of element 38. Sample conduit 46 in fact directs the sample mixture toward the light transmitting element as the mixture enters the reaction chamber. The reaction continues as the reacting compositions move through reaction chamber 16 toward exhaust opening 36 but the intensity of the light received by light sensing device 28 diminishes with the decreasing solid angle subtended by light transmitting element 38.
Increased reaction rates can be achieved by raising the pressure in the reaction chamber since the higher pressure increases the number of molecules of nitric oxide and ozone in the chamber and thereby increases the probability of molecule collision. Highly accurate results with excellent sensitivity are achieved by raising the reaction chamber pressure to at least about 300 torr. Such higher pressures permit the gaseous mixture and the reactant to enter the reaction chamber with an improved laminar type flow that diminishes transient variations in the light intensity resulting from nonuniform mixing within the reaction chamber.
In the reaction chamber of FIG. 4, sample conduit 14a is a similar to that of FIG. 2 but a straight reactant conduit 22a terminated a short distance just inside the cylindrical wall of the reaction chamber so that its opening 48a is directed radially inward in a plane located axially btween the sample conduit opening and the exhaust conduit opening. Conduit 22a preferably enters the chamber within about one half of the axial length of the. chamber from light transmitting element 38. Comparative tests with a FIG. 4 reaction chamber 3 inches long and having conduit 22a 1.5 inches from element 38 indicate slight increases in measurable light intensity over the FIG. 2 chamber.
In the reaction chamber of FIG. 5, the location of reactant conduit 22b is similar to that of FIG. 4. Sample conduit 14b is straight and extends radially into the chamber at a location closely adjacent an edge of light transmitting element 38. Opening 48b of the reactant conduit is diametrically across and axially displaced toward the exhaust opening from the opening of the sample conduit. In comparative tests with the FIG. 2 reaction chamber, the FIG. 5 arrangement also produced slight increases in measurable light intensity.
Both conduits enter the reaction chambers of FIGS. 6 and 7 on the same side. In FIG. 6, the location of sample conduit 14c is similar to that of FIG. 5 while reactant conduict 22c is displaced axially therefrom toward the exhaust opening. In FIG. 7, sample conduit 14d extends straight into the reaction chamber and reactant conduit 22d surrounds the sample conduit so the reactant conduit forms an annular opening 48d.
In each of these reaction chambers, the sample conduit is proximate to the light sensing assembly to promote reaction proximate thereto. Each of the disclosed reaction chamber constructions and similar constructions produces useful results although the best combination of accuracy and sensitivity has been achieved to date with the chambers of FIGS. 2, 4 and 5.
Thus this invention provides improved structures and techniques for accurately and conveniently determining the concentrations of gases such as nitric oxide in a gaseous mixture. The invention has greatly improved sensitivity, reproductibility, and economy of construction and operation.
We claim:
[1. An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by easuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
light tran mitting means sealingly mounted in the opening of the reaction chamber,
a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber,
an exhaust conduit connected to said reaction chamher at a location axially removed from said light transmitting means,
pump means for flowing said sample mixture and said reactant into said reaction chamber, said pump means producing a pressure within said reaction chamber that is sufficiently high to promote a smooth, stable reaction, and
light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant] [2. The instrument of claim 1 in which the light transmitting means is a disc located at one end of the cylindrical housing] [3. The instrument of claim 2 in which the reactant conduit opens into the reaction chamber at a location axially between the opening of the sample conduit and the opening of the exhaust conduit] 4. The instrument of claim [3] 18 in which the sample conduit extends through the cylindrical wall of the housing and opens into the reaction chamber closely adjacent an edge of the light transmitting means.
5. The instrument of claim 4 in which the reactant conduit extends through the cylindrical wall of the housing and opens into the reaction chamber at a location diametrically opposed to and axially removed from the opening of the sample conduit.
6. The instrument of claim 5 in which the pump means is connected to the exhaust conduit, said pump means producing subatmospheric pressure in the reaction chamber for drawing said sample mixture and said reactant into the reaction chamber, and comprising a flow metering means connected to the sample conduit and a flow metering means connected to the reactant conduit.
7. The instrument of claim 6 in which the pump means and flow metering means produce a pressure of at least about 300 torr in the reaction chamber.
[8. The instrument of claim 1 in which the sample conduit opens into the reaction chamber at a location closer to the light transmitting means than the exhaust conduit] [9. The instrument of claim 1 in which the reactant conduit opens into the reaction chamber at a location more removed from the light transmitting means than the sample conduit opening but closer to the light transmitting means than the exhaust conduit opening] [10. The instrument of claim 1 in which the pump means produces a pressure of at least 300 torr in the reaction chamber] [11. The instrument of claim 1 in which the reactant conduit extends through the cylindrical wall of the housing and opens into the reaction chamber at a location diametrically opposed to and axially removed from the opening of the sample conduit.]
12. A reaction chamber for a chemiluminescent reactlon comprising a housing having an opening at one end,
a light transmitting means sealingly mounted in the opening of the housing,
a sample conduit extending into said housing and having an opening for admitting a sample gas into the housing, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit extending into said housing and having an opening for admitting a reactant gas into the housing separate from said sample conduit, and
an exhaust outlet formed in said housing at a location that is remote from said sample conduit opening and said reactant conduit opening.
13. The reaction chamber of claim 12 in which the opening of the sample conduit lies in a plane substantially parallel to the plane of the light transmitting means.
14. The reaction chamber of claim 13 in which the housing is a circular cylinder closed at one end and the light transmitting means extends perpendicular to the axis of the housing at its opposite end.
15. The reaction chamber of claim 14 in which the exhaust outlet is formed in the central portion of the closed end of the housing.
16. The reaction chamber of claim 15 in which the opening of the reactant conduit is proximate to the inner surface of the light transmitting means.
17. The reaction chamber of claim 12 in which the sample conduit extends radially into the reaction chamber and its opening is adjacent an edge of the light transmitting element.
18. An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
light transmitting means sealingly mounted in the opening of the reaction chamber,
a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit connected to said reactant chamber and having an opening for admitting the gaseous reactant into the reaction chamber separate from said sample conduit opening,
an exhaust conduit connected to said reaction chamber at a location axially removed from said light transmitting means,
pump means for flowing said sample mixture and said reactant into said reaction chamber, said pump means producing a pressure within said reaction chamber that is sufiiciently high to promote a smooth, stable reaction, and
light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said light transmitting means being a disc located at one end of the cylindrical housing, said reactant conduit opening into the reaction chamber at a location axially between the opening of the sample conduit and the opening of the exhaust conduit.
19. An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
light transmitting means sealingly mounted in the opening of the reaction chamber,
a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber,
an exhaust conduit connected to said reaction chamber at a location axially removed from said light transmitting means,
pump means for flowing said sample mixture and said reactant into said reaction chamber, said pump means producing a pressure within said reaction chamber that is sufiiciently high to promote a smooth, stable reaction, and
light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said reactant conduit opening into the reaction chamber at a location more removed from the light transmitting means than the sample conduit opening but closer to the light transmitting means than the exhaust conduit opening.
20. An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reactionbotween the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end,
light transmitting means sealingly mounted in the opening of the reaction chamber,
a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber separate from said sample conduit,
an exhaust conduit connected to said reaction chamber at a location axially removed from said light transmitting means,
pump means for flowing said sample mixture and said reactant into said reaction chamber, said pump means producing a pressure within said reaction chamber that is sufliciently high to promote a smooth, stable reaction, and
light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said pump means producing a pressure of at least 300 torr in the reaction chamber.
21. An instrument for determining the concentration of a gaseous constituent in a gaseous sample mixture by measuring the chemiluminescence of a reaction between the constituent and a gaseous reactant comprising a reaction chamber comprising a cylindrical housing having an opening at one end, i
light transmitting means sealingly mounted in the opening of the reaction chamber,
a sample conduit connected to said reaction chamber and having an opening for admitting the gaseous sample mixture into the reaction chamber, said opening being proximate to the inner surface of the light transmitting means,
a reactant conduit connected to said reaction chamber and having an opening for admitting the gaseous reactant into the reaction chamber,
an exhaust conduit connected to said reaction chamber at a location axially removed from said light transmitting means,
pump means for flowing said sample mixture and said reactant into said reaction chamber, said pump means producing a pressure within said reaction chamber that is sufiiciently high to promote a smooth, stable reaction, and
light sensing means connected to said reaction chamber for measuring the light transmitted through the light transmitting means for the chemiluminescent reaction between the constituent in the sample mixture and the reactant, said reactant conduit extending through the cylindrical wall of the housing and opening into the reaction chamber at a location dimetrically opposed to and axially removed from the opening of the sample conduit.
References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
10 UNITED STATES PATENTS OTHER REFERENCES Warren et al., Portable Ethylene Chemiluminescence Ozone Monitor, Rev. Scient. Instr. Vol. 41, pp. 280-282 (1970).
R. E. SERWIN, Examiner U.S. Cl. X.R.
23-253 PC, 254 E; 3S6-2 16; 250-218
Claims (1)
12. A REACTION CHAMBER FOR A CHEMILUMINESCENT REACTION COMPRISING A HOUSING HAVING AN OPENING AT ONE END, A LIGHT TRANSMITTING MEANS SEALINGLY MOUNTED IN THE OPENING OF THE HOUSING, A SAMPLE CONDUIT EXTENDING INTO SAID HOUSING AND HAVING AN OPENING FOR ADMITTING A SAMPLE GAS INTO THE HOUSING, SAID OPENING BEING PROXIMATE TO THE INNER SURFACE OF THE LIGHT TRANSMITTING MEANS, A REACTANT CONDUIT EXTENDING INTO SAID HOUSING AND HAVING AN OPENING FOR ADMITTING A REACTANT GAS INTO THE HOUSING SEPARATE FROM SAID SAMPLE CONDUIT, AND
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US283761D USB283761I5 (en) | 1971-05-26 | ||
| US00146927A US3746514A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent instrument |
| US00146929A US3746513A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent process |
| CA136,872A CA944580A (en) | 1971-05-26 | 1972-03-08 | Chemiluminescent instrument |
| CA137,192A CA956141A (en) | 1971-05-26 | 1972-03-15 | Chemiluminescent process for determining a constituent in a gaseous sample mixture |
| GB1800272A GB1341346A (en) | 1971-05-26 | 1972-04-19 | Chemiluminescent instrument |
| GB1875672A GB1341347A (en) | 1971-05-26 | 1972-04-21 | Method of chemiluminescent measurement |
| FR727219007A FR2139175B1 (en) | 1971-05-26 | 1972-05-26 | |
| DE2225802A DE2225802C3 (en) | 1971-05-26 | 1972-05-26 | Method and device for determining the concentration of a component in a gaseous sample mixture |
| DE19722225696 DE2225696A1 (en) | 1971-05-26 | 1972-05-26 | Chemiluminescence process |
| CA175,715A CA954329A (en) | 1971-05-26 | 1973-07-05 | Chemiluminescent instrument |
| US42564373 USRE28376E (en) | 1971-05-26 | 1973-12-17 | Chemiluminesceht process |
| US42564173 USRE28374E (en) | 1971-05-26 | 1973-12-17 | Chemiluminescent instrument |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14692971A | 1971-05-26 | 1971-05-26 | |
| US14692771A | 1971-05-26 | 1971-05-26 | |
| US42564173 USRE28374E (en) | 1971-05-26 | 1973-12-17 | Chemiluminescent instrument |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE28374E true USRE28374E (en) | 1975-03-25 |
Family
ID=27386482
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US283761D Pending USB283761I5 (en) | 1971-05-26 | ||
| US00146927A Expired - Lifetime US3746514A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent instrument |
| US00146929A Expired - Lifetime US3746513A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent process |
| US42564173 Expired USRE28374E (en) | 1971-05-26 | 1973-12-17 | Chemiluminescent instrument |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US283761D Pending USB283761I5 (en) | 1971-05-26 | ||
| US00146927A Expired - Lifetime US3746514A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent instrument |
| US00146929A Expired - Lifetime US3746513A (en) | 1971-05-26 | 1971-05-26 | Chemiluminescent process |
Country Status (5)
| Country | Link |
|---|---|
| US (4) | US3746514A (en) |
| CA (2) | CA944580A (en) |
| DE (2) | DE2225802C3 (en) |
| FR (1) | FR2139175B1 (en) |
| GB (2) | GB1341346A (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3973910A (en) * | 1973-02-05 | 1976-08-10 | Thermo Electron Corporation | Method of measuring the N-nitrosoamine content of a sample |
| US3996002A (en) * | 1973-02-05 | 1976-12-07 | Thermo Electron Corporation | Method and apparatus for measuring the n-nitroso compound content of a sample |
| US3888630A (en) * | 1973-12-26 | 1975-06-10 | Borg Warner | Breath testing method |
| US3904371A (en) * | 1974-03-04 | 1975-09-09 | Beckman Instruments Inc | Chemiluminescent ammonia detection |
| US3882028A (en) * | 1974-05-17 | 1975-05-06 | Thermo Electron Corp | Multiple chamber chemiluminescent analyzer |
| US3963928A (en) * | 1974-05-17 | 1976-06-15 | Thermo Electron Corporation | Multiple chamber chemiluminescent analyzer |
| BR7407833A (en) * | 1974-09-20 | 1976-08-17 | Petroleo Brasileiro Sa | DETECTOR AND PROCESS FOR DETERMINING CHEMICAL COMPOUNDS BY KIMILUMINESCENCE WITH AZONIUM |
| US4193963A (en) * | 1974-09-20 | 1980-03-18 | Petroleo Brasileiro S.A.-Petrobras | Apparatus for the determination of chemical compounds by chemiluminescence with ozone |
| US4843016A (en) * | 1974-10-07 | 1989-06-27 | Thermedics Inc. | Detection system and method |
| US4778764A (en) * | 1974-10-07 | 1988-10-18 | Thermedics Inc. | Detection system and method |
| US3973911A (en) * | 1975-02-06 | 1976-08-10 | University Of Illinois Foundation | Sulfur oxide determination |
| US3996008A (en) * | 1975-09-17 | 1976-12-07 | Thermo Electron Corporation | Specific compound detection system with gas chromatograph |
| US3996009A (en) * | 1975-09-17 | 1976-12-07 | Thermo Electron Corporation | Specific compound detection system |
| NL7604197A (en) * | 1976-04-21 | 1977-10-25 | Philips Nv | DEVICE FOR DETERMINING GAS-FORMULA COMPONENTS. |
| SE421835B (en) * | 1978-06-19 | 1982-02-01 | W Wladimiroff | INSTRUMENT FOR CHEMICAL OR BIOLUMINISCENT ANALYSIS |
| DE2920215A1 (en) * | 1979-05-18 | 1980-11-20 | Siemens Ag | CHEMILUMINESCENCE ANALYZER REACTION CHAMBER |
| US4657744A (en) * | 1985-07-02 | 1987-04-14 | Sensors, Inc. | Chemiluminescent gas analyzer for measuring the oxides of nitrogen |
| US4822564A (en) * | 1985-07-02 | 1989-04-18 | Sensors, Inc. | Chemiluminescent gas analyzer for measuring the oxides of nitrogen |
| US5092220A (en) * | 1987-07-08 | 1992-03-03 | Thermedics Inc. | Nitric oxide detection with hydrogen and ozone |
| US4886358A (en) * | 1988-05-31 | 1989-12-12 | The United States Of America As Represented By The Secretary Of The Navy | Organic vapor assay by Raman spectroscopy |
| US4978854A (en) * | 1989-08-16 | 1990-12-18 | The United States Of America As Represented By The Secretary Of The Navy | Bioluminescent detector |
| DE3940035C2 (en) * | 1989-12-04 | 1999-03-04 | Fisher Rosemount Gmbh & Co Ges | Device for mixing two reactive gas components in a chemiluminescence detection device |
| JP3104383B2 (en) * | 1992-02-27 | 2000-10-30 | 株式会社島津製作所 | Chemiluminescence concentration measuring device |
| DE4236944A1 (en) * | 1992-11-02 | 1994-05-05 | Andreas P Dr Termin | Device and method for determining the NO content |
| US5633170A (en) * | 1995-03-14 | 1997-05-27 | Neti; Radhakrishna M. | Method and apparatus for nitrogen oxide analysis |
| US5856194A (en) | 1996-09-19 | 1999-01-05 | Abbott Laboratories | Method for determination of item of interest in a sample |
| US5795784A (en) * | 1996-09-19 | 1998-08-18 | Abbott Laboratories | Method of performing a process for determining an item of interest in a sample |
| US5859429A (en) * | 1997-08-20 | 1999-01-12 | Abbott Laboratories | Optical system with test/calibration |
| JP2002022662A (en) * | 2000-07-07 | 2002-01-23 | Hamamatsu Photonics Kk | Luminous-reaction measuring apparatus |
| JP4611562B2 (en) * | 2001-04-12 | 2011-01-12 | 浜松ホトニクス株式会社 | Luminescent reaction measuring device |
| DE102009023224A1 (en) | 2009-05-29 | 2010-12-02 | Avl Emission Test Systems Gmbh | Arrangement for the controlled supply and delivery of a gas mixture into an analysis chamber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3245758A (en) * | 1963-09-30 | 1966-04-12 | Theodor H Benzinger | Calorimetry for photochemical reactions |
| US3285703A (en) * | 1963-05-31 | 1966-11-15 | Nippon Oxygen Co Ltd | Photosensitive means for determining trace oxygen by measuring chemiluminescence |
| US3287089A (en) * | 1964-05-28 | 1966-11-22 | Richard L Wilburn | Chemiluminescence sampler |
| US3520660A (en) * | 1966-09-09 | 1970-07-14 | Nasa | Light detection instrument |
| US3615241A (en) * | 1970-02-27 | 1971-10-26 | Nasa | Firefly pump-metering system |
| US3647387A (en) * | 1970-03-19 | 1972-03-07 | Stanford Research Inst | Detection device |
-
0
- US US283761D patent/USB283761I5/en active Pending
-
1971
- 1971-05-26 US US00146927A patent/US3746514A/en not_active Expired - Lifetime
- 1971-05-26 US US00146929A patent/US3746513A/en not_active Expired - Lifetime
-
1972
- 1972-03-08 CA CA136,872A patent/CA944580A/en not_active Expired
- 1972-03-15 CA CA137,192A patent/CA956141A/en not_active Expired
- 1972-04-19 GB GB1800272A patent/GB1341346A/en not_active Expired
- 1972-04-21 GB GB1875672A patent/GB1341347A/en not_active Expired
- 1972-05-26 DE DE2225802A patent/DE2225802C3/en not_active Expired
- 1972-05-26 DE DE19722225696 patent/DE2225696A1/en active Pending
- 1972-05-26 FR FR727219007A patent/FR2139175B1/fr not_active Expired
-
1973
- 1973-12-17 US US42564173 patent/USRE28374E/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3285703A (en) * | 1963-05-31 | 1966-11-15 | Nippon Oxygen Co Ltd | Photosensitive means for determining trace oxygen by measuring chemiluminescence |
| US3245758A (en) * | 1963-09-30 | 1966-04-12 | Theodor H Benzinger | Calorimetry for photochemical reactions |
| US3287089A (en) * | 1964-05-28 | 1966-11-22 | Richard L Wilburn | Chemiluminescence sampler |
| US3520660A (en) * | 1966-09-09 | 1970-07-14 | Nasa | Light detection instrument |
| US3615241A (en) * | 1970-02-27 | 1971-10-26 | Nasa | Firefly pump-metering system |
| US3647387A (en) * | 1970-03-19 | 1972-03-07 | Stanford Research Inst | Detection device |
Non-Patent Citations (1)
| Title |
|---|
| Warren et al., "Portable Ethylene Chemiluminescence Ozone Monitor," Rev. Scient. Instr. Vol. 41, pp. 280-282 (1970). * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA956141A (en) | 1974-10-15 |
| FR2139175A1 (en) | 1973-01-05 |
| FR2139175B1 (en) | 1973-07-13 |
| DE2225802A1 (en) | 1972-12-14 |
| CA944580A (en) | 1974-04-02 |
| DE2225802B2 (en) | 1978-03-30 |
| USB283761I5 (en) | |
| DE2225802C3 (en) | 1978-11-30 |
| GB1341346A (en) | 1973-12-19 |
| US3746513A (en) | 1973-07-17 |
| GB1341347A (en) | 1973-12-19 |
| US3746514A (en) | 1973-07-17 |
| DE2225696A1 (en) | 1972-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| USRE28374E (en) | Chemiluminescent instrument | |
| US3528779A (en) | Chemiluminescent method of detecting ozone | |
| Fontijn et al. | Homogeneous chemiluminescent measurement of nitric oxide with ozone. Implications for continuous selective monitoring of gaseous air pollutants | |
| US4193963A (en) | Apparatus for the determination of chemical compounds by chemiluminescence with ozone | |
| US3904371A (en) | Chemiluminescent ammonia detection | |
| SU1408319A1 (en) | Chemoluminescent gas analyzer for nitrogen oxides | |
| US5935519A (en) | Apparatus for the detection of sulfur | |
| US4775633A (en) | Detection of hydrazine compounds in gaseous samples by their conversion to nitric oxide-yielding derivatives | |
| US3984688A (en) | Monitor for detection of chemiluminescent reactions | |
| Piper et al. | Rate coefficients for atomic nitrogen (2D) reactions | |
| US3963928A (en) | Multiple chamber chemiluminescent analyzer | |
| US4070155A (en) | Apparatus for chromatographically analyzing a liquid sample | |
| US4066409A (en) | Method and apparatus for chromatographically analyzing a liquid sample | |
| US3692485A (en) | Nitric oxide detection | |
| US3213747A (en) | Process for detecting phosphorous and/or sulphur in a gas | |
| Navas et al. | Air analysis: determination of hydrogen peroxide by chemiluminescence | |
| USRE28376E (en) | Chemiluminesceht process | |
| GB2163553A (en) | Method and apparatus for chemiluminescence analysis | |
| RU2493556C1 (en) | Method and apparatus for determining concentration of nitrogen oxide(no) in gaz medium | |
| Clyne et al. | Reactions of chlorine oxide radicals. Part 3.—Kinetics of the decay reaction of the ClO (X 2 Π) radical | |
| Krost et al. | Flame chemiluminescence detection of nitrogen compounds | |
| Fraser et al. | Gas phase chemiluminescence of arsine mixed with ozone | |
| US3708265A (en) | Colorimeter for determining the concentration of a pollutant gas in an air sample | |
| US5271894A (en) | Chemiluminescent analyzer | |
| US4081247A (en) | Method and apparatus for the chemiluminescent detection of HCl |