GB2316170A - The detection of volatile substances - Google Patents
The detection of volatile substances Download PDFInfo
- Publication number
- GB2316170A GB2316170A GB9715279A GB9715279A GB2316170A GB 2316170 A GB2316170 A GB 2316170A GB 9715279 A GB9715279 A GB 9715279A GB 9715279 A GB9715279 A GB 9715279A GB 2316170 A GB2316170 A GB 2316170A
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- United Kingdom
- Prior art keywords
- gaseous medium
- plasma
- volatile substance
- detecting
- excited
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- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Plasma & Fusion (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
An apparatus for detecting the presence of volatile substances in a gaseous medium, including means for producing within a sensor chamber a localised electric field the energy density of which is sufficient to excite the gaseous medium to a plasma condition, and means for detecting changes in a parameter of the plasma due to the presence of the volatile substances in the gaseous medium. A gaseous medium flows through a chamber 101 where it is irradiated (e.g. by microwaves) to excite it into a plasma state. Optical emissions from the plasma are detected through optical ports 107 to give an indication of the presence of any volatile substances (e.g. organic compounds) in the medium. Alternatively, the indication may be derived from a measurement of the plasma temperature or the efficiency of the coupling of the exciting radiation into the plasma.
Description
The Detection of Volatile Substances The present invention relates to the detection of the presence of volatile substances in gaseous media, and more specifically, to the detection of volatile organic compounds in air, or effluent streams.
Many volatile organic compounds are toxic or carcinogenic and it is highly desirable that they should be detected readily so that remedial action can be taken, such as changing filters designed to remove such compounds from breathing apparatus or effluent ducts from process plant, or changing the operating parameters of processes which involve the volatile organic compounds or produce them as by-products.
Traditional methods of detecting volatile organic compounds in gaseous media are based on infra red absorption spectroscopy or gas chromatography. Such methods tend to be slow and require cumbersome equipment.
Whereas this may be acceptable in the context of process control in fixed chemical plant, it may not be so for use in the field.
In US patent 3 843 257 there is disclosed an apparatus and method for detecting materials in gaseous media in which a gaseous medium is irradiated with microwave energy and optical emissions from the excited gaseous medium are analysed to detect the presence of the said materials in the gaseous medium.
However, the apparatus and method described includes a preliminary stage in which a particulate or liquid component of a first gaseous medium is atomised and mixed with a carrier gas prior to being subjected to irradiation with microwaves such as to produce an electrical discharge in the carrier gas which causes the emission of optical radiation from the atomised components of the first gaseous medium.
The apparatus therefore is relatively complicated and more suited to laboratory rather than field use.
It is an object of the present invention to provide apparatus for the detection of volatile substances in gaseous media, which is portable, rugged and simple to use.
According to the invention in one aspect there is provided an apparatus for detecting the presence of a volatile substance in a gaseous medium, comprising a chamber, means for enabling a gaseous medium, the presence in which of a volatile substance is to be detected to be passed through the chamber, wherein there is provided means for producing within the chamber a localised region in which the energy density is sufficient to excite the gaseous medium to the plasma state, and means for detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium.
The changes in the state of the plasma due to the presence of the volatile substances may be changes in the temperature of the plasma due to reactions between the gaseous medium and the volatile substance occurring in the plasma; the efficiency of absorption of the radiation by the gaseous medium, or optical emissions from excited states of the volatile substance or reaction products derived from it.
A particular form of volatile substance for the detection of which in a gaseous medium the present invention is suitable, is volatile organic compounds, and a particularly suitable form of radiation is microwave radiation, although other forms of radiation such as laser radiation can be used.
According to the present invention there is provided a method of detecting the presence of a volatile substance in a gaseous medium, comprising the operations or irradiating a localised region of a gaseous medium the presence in which of a volatile substance is to be detected with radiation the energy density of which is sufficient to excite the gaseous medium into the plasma state and detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium.
Preferably, the means for detecting changes in the state of the plasma due to the presence of the volatile substance comprises means for detecting specific optical emissions from excited species arising from the volatile substances in the plasma.
The means for detecting specific optical emissions from excited species arising from the volatile substances in the plasma may comprise at least one photo sensitive device associated with an optical filter adapted to select the specific optical emissions arising from the volatile substance in the plasma.
Alternatively, the means for detecting changes in the condition of the plasma due to the presence of the volatile substance in the plasma may comprise means for measuring the temperature of the plasma.
Another means for detecting changes in the condition of the plasma due to the presence of the volatile substance in the plasma may comprise means for measuring changes in the efficiency of the coupling of the exciting radiation into the plasma.
Preferably, the means for exciting the gaseous medium to the plasma state comprises means for coupling microwave radiation into the chamber and there is included within the chamber a pair of electrodes adapted to produce a region of enhanced electric field in the vicinity of the electrodes so as to produce the localised plasma in the gaseous medium in the chamber.
The invention will now be described, by way of example, with reference to the accompanying drawings, in which,
Figure 1 is a section of a sensor for use in carrying out the present invention, and
Figure 2 is a block diagram of an apparatus including the sensor of Figure 1 for carrying out the present invention;
Figure 3 shows an alternative optical radiation detector for use in a sensor embodying the present invent ion; and
Figure 4 shows another optical radiation detector for use in a sensor embodying the invention.
Referring to Figure 1 of the drawings, a sensor for detecting the presence of volatile organic compounds in a gaseous medium consists of a chamber 101 comprised of two stainless steel end-plates 102 and 103, a cylindrical wall 104 made of a material which is transparent to the radiation which it is anticipated will be emitted by substances for the detection of which the sensor will be used, which is mounted in the end-plates 102 and 103 and rendered gas tight by means of O-ring seals 105. An appropriate material for use when the emitted radiation lies in the optical and ultra-violet regions of the spectrum is quartz. An outer wall 106 forms part of a waveguide by means of which energy is supplied to the chamber 101. The assembly is clamped together by set screws, which are not shown in the drawing. Also included, but not shown in the drawing is means for coupling microwave radiation into the interior of the chamber 101. Mounted in the outer wall 106 are a number of optical ports 107, two of which are shown in the drawing. Each optical port 107 has a lens 108 which focuses light emitted within the chamber 101 into an associated optical fibre 109. Each of the end-plates 102 and 103 has a conical protuberance 110 and 111, respectively, which terminate in a sharp annular tip 112 and 113, respectively. The tips 112 and 113 are screwed into their respective end plates 102 and 103 so that they can be replaced as and when necessary. Suitable materials for the tips 112 and 113 is molybdenum or tungsten, or a similar refractory metal. The conical protuberances 110 and 111 form a pair of electric field enhancing electrodes. The optical ports 107 are so positioned as to observe the gap 120 between the field enhancing electrodes 110 and 111.
The end plate 102 has two entry ports 114 for the gaseous medium the presence in which of volatile organic compounds is to be detected, and an inlet 115 and an outlet 116 for a coolant medium. The tip 112 of the end plate 102 and the end plate 103 have an axial hole 117 by means of which the said gaseous medium is extracted from the chamber 1. Again, the end plate 103 is hollow and there is an inlet 118 and an outlet 119 for a cooling medium. The gap 120 between the tips 111 and 112 of the protuberances 109 and 110 on the end plates 102 and 103 is adjustable between 0.1 and about 5 mm. The assembly provides a pair of electrodes 120.
Referring to Figure 2, in use, the said gaseous medium is passed through the chamber 1 at a pressure in the range .001 to 1 bar, and microwave radiation at a frequency of 2.45 Ghz and power of up to 500 watts is coupled into the chamber 101 in such a manner that the electrode 120 provided by the protuberances 109 and 110 of the end-plates 102 and 103, respectively of the chamber 101 are transverse of the direction of propagation of the microwaves through the chamber 101.
The electrodes 120 concentrate the microwave radiation in the chamber 101 to such an extent that the gaseous medium is excited to the plasma state in the region of the gap 120 between them.
Referring to Figure 2 of the drawings, optical radiation emitted by the plasma in the chamber 101 is collected by the lenses 108 and focused into the optical fibres 109 and then transmitted via optical filters 201 to photo detectors 202. The output signals from the photo detectors 202 are applied to a microprocessor 203 and an indication of the presence of any volatile organic compounds in the gaseous medium is displayed on a visual display unit 204.
The optical filters 201 are arranged to select spectral regions in which emission bands arising from excited species of interest are expected to occur and the photo detectors 202 provide integrated light intensity emissions in those ranges. For example, if the gaseous medium includes a nitrogenous carrier gas, such as air or nitrogen then, if volatile organic compounds also are present, the expected excited species include CN, CH or C2 radicals.
Specifically, for example, toluene can be detected in an air stream by using a narrow band width optical filter, centred at 387nm. Such an optical filter selects emission on the Av=0 vibrational sequence of the Box electronic transition of the CN radical.
Alternatively, if the gaseous medium is oxidising (air or oxygen) the optical filters 201 may be such as to isolate emission bands from excited oxidation products of the volatile organic compounds.
Gases which would not themselves produce detectable radiation can be detected by reacting them with a second gas, to form products which can produce detectable radiation as a result of plasma energisation. For example, if it is desired to detect carbon tetrafluoride in the exhaust from a semi conductor wafer processing plant, then normally no detectable radiation would be produced. However, if the carbon tetrafluoride is mixed with nitrogen then the radical CN would be produced which, as above, does produce detectable radiation.
In another variant of the method, a gaseous medium in which non-radiation producing compounds are to be detected is passed through a plasma generator such as that disclosed in our patent GB 2 273 027 and there converted to species which are capable of being excited to produce optical radiation. These precursor species are then passed through the sensor of the present invent ion, excited to a plasma state and the optical radiation analysed as before.
It is not necessary for the volatile organic compound to be decomposed in the plasma, emission bands from rotationally or vibrationally excited molecules of the volatile organic compound can be detected.
Referring to Figure 3 there is shown a second form of sensor for use in carrying out the present invention.
In the sensor shown in Figure 3, the optical parts 107, lenses 108 and optical fibres 109 are omitted and are replaced by a single photo diode 301 and associated optical fibre 302 which are mounted axially in a bore 303 in the electrode 110. The remainder of the sensor is the same as that described with reference to Figure 1 and the same reference numerals are used.
Referring to Figure 4, there is shown an alternative form of optical port 107, which consists of a housing 401 which is adapted to be mounted in the outer wall 106 of the sensor so as to observe the region 120 between the tips 112 and 113 of the electrodes 110 and 111, as before. Inside the housing 401 is a lens system 402 which includes a number of appropriate optical filters 403, a photodiode 404 and an output socket 405.
In other forms of the apparatus, which are not illustrated, the detectors of optical radiation from the plasma are omitted and replaced by means for measuring the temperature of the plasma as this parameter is affected by the heat of formation of reaction products between the gaseous medium and volatile compounds contained in it, or by means for measuring the efficiency of the coupling of the exciting radiation into the chamber 101, as again, this parameter will be affected by the presence in the gaseous medium of the volatile substance, and products derived from it. This may be done by incorporating a power meter in the waveguide feeding the chamber 101.
A suitable means for measuring the temperature of the plasma is a thermocouple.
Claims (21)
1. An apparatus for detecting the presence of volatile substance in a gaseous medium, comprising a chamber, means for enabling a gaseous medium, the presence in which of a volatile substance is to be detected to be passed through the chamber, wherein there is provided means for producing within the chamber a localised region in which the energy density is sufficient to excite the gaseous medium to the plasma state, and means for detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium.
2. An apparatus according to Claim 1 wherein the means for detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises means for detecting specific optical emissions from excited species in the plasma derived from the volatile substance.
3. An apparatus according to Claim 1 wherein the means for detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises means for measuring the temperature of the plasma.
4. An apparatus according to Claim 3 wherein the means for measuring the temperature of the plasma comprises a thermocouple.
5. An apparatus according to Claim 1 wherein the gaseous medium is excited into the plasma state by means of microwave radiation and the means for detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises means for measuring the efficiency of the coupling of the exciting radiation into the chamber.
6. An apparatus according to any of Claims 1 to 4 wherein the means for irradiating a region of the chamber with radiation the energy density of which is sufficient to excite the gaseous medium to the plasma state comprises a laser.
7. A method of detecting the presence of a volatile substance in a gaseous medium, comprising the operations or irradiating a localised region of a gaseous medium the presence in which of a volatile substance is to be detected with radiation the energy density of which is sufficient to excite the gaseous medium into the plasma state and detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium.
8. A method according to Claim 7 wherein the operation of detecting the changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises the operation of detecting optical emissions from excited product species derived from the volatile substance.
9. A method according to Claim 7 wherein the operation of detecting the changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises the operation of detecting changes in the temperature of the plasma as a result of reactions in the plasma between the gaseous medium and the volatile substance.
10. A method according to Claim 7 wherein the gaseous medium is excited into the plasma state by means of microwave radiation and the operation of detecting changes in a parameter of the plasma due to the presence of the volatile substance in the gaseous medium comprises the operation of detecting changes in the efficiency of the coupling of the exciting radiation into the gaseous medium to maintain the plasma therein.
11. A method according to Claim 8 wherein the excited product species are radicals derived from the volatile substance.
12. A method according to Claim 8 wherein the excited product species are reaction products derived from reactions between the gaseous medium and the volatile substance.
13. A method according to any of Claims 7 to 12 wherein the volatile substance is a volatile organic compound.
14. A method according to any of Claims 7 to 13 wherein the gaseous medium is nitrogenous.
15. A method according to any of Claims 7 to 14 wherein the gaseous medium contains oxygen.
16. A method according to Claim 14 and Claim 15 wherein the gaseous medium is air.
17. A method according to Claims 9, 10 and 11 wherein the excited product species are CH, CN or C2 radicals.
18. A method according to Claim 17 wherein there is included the operation of detecting optical emissions arising from the Av=0 vibrational sequence of the Box electronic transition of the CN radical.
19. A method according to any of Claims 7 to 18 wherein there is included the operation of converting the volatile substance from a first form which does not produce detectable optical radiation when excited to the plasma state to a second gaseous species which does produce detectable optical radiation when excited to the plasma state.
20. An apparatus for detecting the presence of a volatile substance in a gaseous medium substantially as hereinbefore described and with reference to the accompanying drawings.
21. A method of detecting the presence of a volatile substance in a gaseous medium substantially as hereinbefore described and with reference to the accompanying drawings.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9715279A GB2316170B (en) | 1996-08-10 | 1997-07-22 | The detection of volatile substances |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9616841.4A GB9616841D0 (en) | 1996-08-10 | 1996-08-10 | The detection of volatile substances |
GB9715279A GB2316170B (en) | 1996-08-10 | 1997-07-22 | The detection of volatile substances |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9715279D0 GB9715279D0 (en) | 1997-09-24 |
GB2316170A true GB2316170A (en) | 1998-02-18 |
GB2316170B GB2316170B (en) | 2000-11-29 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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GB9715279A Expired - Fee Related GB2316170B (en) | 1996-08-10 | 1997-07-22 | The detection of volatile substances |
Country Status (1)
Country | Link |
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GB (1) | GB2316170B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2383145A (en) * | 2001-10-31 | 2003-06-18 | Alphamosaic Ltd | Data access in a processor using a memory array accessed by coordinate instructions |
US9333460B2 (en) | 2005-10-28 | 2016-05-10 | Edwards Limited | Plasma treatment device |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3843257A (en) * | 1971-11-30 | 1974-10-22 | Monsanto Res Corp | Microwave-excited emission detector |
US4532219A (en) * | 1984-01-27 | 1985-07-30 | Minnesota Mining And Manufacturing Company | High frequency radiation-induced plasma analysis of volatile or non-volatile materials |
GB2273027A (en) * | 1992-11-26 | 1994-06-01 | Atomic Energy Authority Uk | Electrode arrangement in a microwave plasma generator |
WO1995011442A1 (en) * | 1993-10-22 | 1995-04-27 | Massachusetts Institute Of Technology | Continuous, real time microwave plasma element sensor |
US5596405A (en) * | 1995-10-03 | 1997-01-21 | The United States Of America As Represented By The Secretary Of The Navy | Method of and apparatus for the continuous emissions monitoring of toxic airborne metals |
-
1997
- 1997-07-22 GB GB9715279A patent/GB2316170B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3843257A (en) * | 1971-11-30 | 1974-10-22 | Monsanto Res Corp | Microwave-excited emission detector |
US4532219A (en) * | 1984-01-27 | 1985-07-30 | Minnesota Mining And Manufacturing Company | High frequency radiation-induced plasma analysis of volatile or non-volatile materials |
GB2273027A (en) * | 1992-11-26 | 1994-06-01 | Atomic Energy Authority Uk | Electrode arrangement in a microwave plasma generator |
WO1995011442A1 (en) * | 1993-10-22 | 1995-04-27 | Massachusetts Institute Of Technology | Continuous, real time microwave plasma element sensor |
US5596405A (en) * | 1995-10-03 | 1997-01-21 | The United States Of America As Represented By The Secretary Of The Navy | Method of and apparatus for the continuous emissions monitoring of toxic airborne metals |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2383145A (en) * | 2001-10-31 | 2003-06-18 | Alphamosaic Ltd | Data access in a processor using a memory array accessed by coordinate instructions |
GB2383145B (en) * | 2001-10-31 | 2005-09-07 | Alphamosaic Ltd | Data access in a processor |
US9333460B2 (en) | 2005-10-28 | 2016-05-10 | Edwards Limited | Plasma treatment device |
Also Published As
Publication number | Publication date |
---|---|
GB9715279D0 (en) | 1997-09-24 |
GB2316170B (en) | 2000-11-29 |
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Legal Events
Date | Code | Title | Description |
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732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20050722 |