CA2525869C - Nickel carbonyl analyzer - Google Patents
Nickel carbonyl analyzer Download PDFInfo
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- CA2525869C CA2525869C CA2525869A CA2525869A CA2525869C CA 2525869 C CA2525869 C CA 2525869C CA 2525869 A CA2525869 A CA 2525869A CA 2525869 A CA2525869 A CA 2525869A CA 2525869 C CA2525869 C CA 2525869C
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- Prior art keywords
- nickel carbonyl
- ozone
- carbon monoxide
- signal
- sample
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 50
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 NICKEL CARBONYL Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (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)
Abstract
Process and apparatus for measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing the nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal; (b) detecting the strength of the signal; and (c) correlating the signal strength with calibrated nickel carbonyl concentration values; the improvement including premixing the ozone and the carbon monoxide to form a pre-mixture prior to mixing with the nickel carbonyl. Most preferably, the signal is measured by an avalanche silicon diode.
Description
NICKEL CARBONYL ANALYZER
FIELD OF THE INVENTION
This invention relates to apparatus and process for the measurement of the concentration of nickel carbonyl in a gaseous mixture, particularly in the presence of ozone carbon monoxide and with an avalanche silicon photodiode.
BACKGROUND OF THE INVENTION
It is known that nickel carbonyl reacts with ozone in the presence of carbon monoxide to effect chemiluminescence with photon emission at a sharp wavelength X. The conversion of Ni(CO)4 to an excited state of NiO and subsequent photon emission decay is the basis for operation. The suggested reaction scheme, Stedman and Tannaro (Analytical Letters, 9 (1), 80-8, 1976), is as follows:
Ni(CO)4 + 03 -> NiO + CO2 NiO + CO -- Ni + C02 Ni + O3 NiO* + OZ
NiO* -> NiO + hv.
Detection is possible due to the cyclic nature of the process wherein the reaction of each Ni(CO)4 molecule provides, in effect, a continuous chemiluminescence when excess ozone and CO are present. This chemiluminescence in monitored through a narrow band pass filter that is matched to the chemiluminescent wavelength, by a sensitive photomultiplier tube.
It is known that the intensity of the detected emission is directly proportional to the concentration of the nickel carbonyl in the gaseous mixture. Typical nickel carbonyl concentrations of between 100 parts per billion to 2 parts per million offer the most accurate concentration measurements. However, spurious results can be obtained if gaseous impurities, such as hydrogen or organic entities, for example, methanol and ethanol vapour are present.
The basic prior art analytical method comprises mixing the three gaseous components of nickel carbonyl sample gas, carbon monoxide and ozone from individual feed flows simultaneously in a reaction chamber. The chamber has a window through which some of the emitted photons are detected by a photomultiplier detector and counted per unit time. The results are correlated to a calibration chart. In the prior art processes the sample and reactive gases are drawn into the reaction chamber under a negative pressure of about 10-30 Torr.
Unfortunately, the prior art photomultiplier detection tube and counter assembly suffers from having a response decay half life of about 1 year. This problem results in inaccuracy and uncertainty in the results, which in the present case involving poisonous nickel carbonyl is a serious problem. Further, the signal strength, i.e. the number of photons emitted and detected per unit time for relatively low concentrations of nickel carbonyl is not always satisfactory.
Although there is an apparent overwhelming plurality of alternative light sensing detectors, for example, photodiodes, phototransistors, photodarlingtons, photoresistors, integrated circuits, various hybrids and even thermopiles, the specific application needs that have to be considered, include, for example, image size, signal-to-noise ratio, frequency bandwidth, cost, sensitivity, linearity, ambient noise performance, dynamic range, and gain stability.
Surprisingly, we have found that an alternative and more practical light sensitive, detector suitable for the detection of the hv of the aforesaid chemiluminenscence NiO species is based on the photodiode semiconductor chip, which is generally packaged to allow the emitted light to fall onto the sensitive area of the diode.
Most preferably, the semiconductor is in the form of an avalanche silicon photodiode.
Silicon-based photodiodes cover the wide range of wavelengths from 190 to 1100 nm with the lower limit being set by absorption of ultraviolet light in air.
There is, therefore, a need for a nickel carbonyl detector which provides an enhanced signal which enables a more sensitive, stable and accurate measurement of nickel carbonyl concentration to be made.
FIELD OF THE INVENTION
This invention relates to apparatus and process for the measurement of the concentration of nickel carbonyl in a gaseous mixture, particularly in the presence of ozone carbon monoxide and with an avalanche silicon photodiode.
BACKGROUND OF THE INVENTION
It is known that nickel carbonyl reacts with ozone in the presence of carbon monoxide to effect chemiluminescence with photon emission at a sharp wavelength X. The conversion of Ni(CO)4 to an excited state of NiO and subsequent photon emission decay is the basis for operation. The suggested reaction scheme, Stedman and Tannaro (Analytical Letters, 9 (1), 80-8, 1976), is as follows:
Ni(CO)4 + 03 -> NiO + CO2 NiO + CO -- Ni + C02 Ni + O3 NiO* + OZ
NiO* -> NiO + hv.
Detection is possible due to the cyclic nature of the process wherein the reaction of each Ni(CO)4 molecule provides, in effect, a continuous chemiluminescence when excess ozone and CO are present. This chemiluminescence in monitored through a narrow band pass filter that is matched to the chemiluminescent wavelength, by a sensitive photomultiplier tube.
It is known that the intensity of the detected emission is directly proportional to the concentration of the nickel carbonyl in the gaseous mixture. Typical nickel carbonyl concentrations of between 100 parts per billion to 2 parts per million offer the most accurate concentration measurements. However, spurious results can be obtained if gaseous impurities, such as hydrogen or organic entities, for example, methanol and ethanol vapour are present.
The basic prior art analytical method comprises mixing the three gaseous components of nickel carbonyl sample gas, carbon monoxide and ozone from individual feed flows simultaneously in a reaction chamber. The chamber has a window through which some of the emitted photons are detected by a photomultiplier detector and counted per unit time. The results are correlated to a calibration chart. In the prior art processes the sample and reactive gases are drawn into the reaction chamber under a negative pressure of about 10-30 Torr.
Unfortunately, the prior art photomultiplier detection tube and counter assembly suffers from having a response decay half life of about 1 year. This problem results in inaccuracy and uncertainty in the results, which in the present case involving poisonous nickel carbonyl is a serious problem. Further, the signal strength, i.e. the number of photons emitted and detected per unit time for relatively low concentrations of nickel carbonyl is not always satisfactory.
Although there is an apparent overwhelming plurality of alternative light sensing detectors, for example, photodiodes, phototransistors, photodarlingtons, photoresistors, integrated circuits, various hybrids and even thermopiles, the specific application needs that have to be considered, include, for example, image size, signal-to-noise ratio, frequency bandwidth, cost, sensitivity, linearity, ambient noise performance, dynamic range, and gain stability.
Surprisingly, we have found that an alternative and more practical light sensitive, detector suitable for the detection of the hv of the aforesaid chemiluminenscence NiO species is based on the photodiode semiconductor chip, which is generally packaged to allow the emitted light to fall onto the sensitive area of the diode.
Most preferably, the semiconductor is in the form of an avalanche silicon photodiode.
Silicon-based photodiodes cover the wide range of wavelengths from 190 to 1100 nm with the lower limit being set by absorption of ultraviolet light in air.
There is, therefore, a need for a nickel carbonyl detector which provides an enhanced signal which enables a more sensitive, stable and accurate measurement of nickel carbonyl concentration to be made.
2 SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved process for the measurement of gaseous nickel carbonyl concentration.
It is a further object of the present invention to provide an improved apparatus for use in aforesaid process.
Accordingly, in one aspect the invention provides a process for measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing said nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal;
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values, the improvement comprising premixing said ozone and said carbon monoxide to form a pre-mixture prior to mixing with said nickel carbonyl.
In an alternative embodiment, the invention provides an improved process of measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing said nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal;
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values;
the improvement comprising detecting said photon emission signal by means of avalanche silicon photodiode means.
The mixing of the nickel carbonyl, ozone and carbon monoxide may be carried out under a negative pressure, but preferably, under a positive pressure.
In preferred embodiments, the ozone and oxygen are pre-mixed prior to admixture with the nickel carbonyl, and most preferably, wherein the nickel carbonyl stream is mixed with the aforesaid pre-mixed stream not being parallel, thereto, most preferably being mixed at right angles.
It is an object of the present invention to provide an improved process for the measurement of gaseous nickel carbonyl concentration.
It is a further object of the present invention to provide an improved apparatus for use in aforesaid process.
Accordingly, in one aspect the invention provides a process for measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing said nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal;
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values, the improvement comprising premixing said ozone and said carbon monoxide to form a pre-mixture prior to mixing with said nickel carbonyl.
In an alternative embodiment, the invention provides an improved process of measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing said nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal;
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values;
the improvement comprising detecting said photon emission signal by means of avalanche silicon photodiode means.
The mixing of the nickel carbonyl, ozone and carbon monoxide may be carried out under a negative pressure, but preferably, under a positive pressure.
In preferred embodiments, the ozone and oxygen are pre-mixed prior to admixture with the nickel carbonyl, and most preferably, wherein the nickel carbonyl stream is mixed with the aforesaid pre-mixed stream not being parallel, thereto, most preferably being mixed at right angles.
3 In a further aspect, the invention provides an improved apparatus for measuring the concentration of gaseous nickel carbonyl in a sample gaseous mixture comprising ozone, carbon monoxide and said nickel carbonyl, said apparatus comprising (a) flow-though reaction chamber means for containing said sample gaseous mixture;
(b) means for feeding said nickel carbonyl, ozone and carbon monoxide to said chamber to operably effect chemiluminescence and produce a photon emission signal;
(c) detection means for detecting said signal; and (d) measuring means for measuring the strength of said signal; the improvement comprising (e) pre-mixing chamber means for admixing said ozone with said carbon monoxide prior to feeding said ozone and said carbon monoxide to said reaction chamber.
Preferably, the detection means comprises avalanche silicon photodiode means.
The photodiode may have a plurality of planar surfaces or be non-planar, for example, comprise in whole or in part of an inner surface of a cylinder.
The apparatus as hereinabove defined may comprises means for providing a negative or positive pressure within the reaction chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be better understood, preferred embodiments will now be described, by way of example only, with reference to the accompanying drawings, wherein Fig. 1 represents a schematic representation of an apparatus and process according to the prior art;
Fig. 2 represents a schematic representation of an apparatus and process according to the invention;
Fig. 3 is a diagrammatic representation of a cylindrical reaction chamber of use in the practise of the invention; and wherein the same numerals denote the parts.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
(b) means for feeding said nickel carbonyl, ozone and carbon monoxide to said chamber to operably effect chemiluminescence and produce a photon emission signal;
(c) detection means for detecting said signal; and (d) measuring means for measuring the strength of said signal; the improvement comprising (e) pre-mixing chamber means for admixing said ozone with said carbon monoxide prior to feeding said ozone and said carbon monoxide to said reaction chamber.
Preferably, the detection means comprises avalanche silicon photodiode means.
The photodiode may have a plurality of planar surfaces or be non-planar, for example, comprise in whole or in part of an inner surface of a cylinder.
The apparatus as hereinabove defined may comprises means for providing a negative or positive pressure within the reaction chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be better understood, preferred embodiments will now be described, by way of example only, with reference to the accompanying drawings, wherein Fig. 1 represents a schematic representation of an apparatus and process according to the prior art;
Fig. 2 represents a schematic representation of an apparatus and process according to the invention;
Fig. 3 is a diagrammatic representation of a cylindrical reaction chamber of use in the practise of the invention; and wherein the same numerals denote the parts.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
4 Fig. 1 shows generally as 10, a prior art nickel carbonyl detection and concentration measurement apparatus having a reaction chamber 12, individual inlet conduit means 14, 16, 18 for feeding nickel carbonyl sample gas, carbon monoxide and ozone, respectively and common outlet 20. Chamber 12 has a window 22 through which is detected photons emitted by the chemiluminessence condition effected by the reaction of the three components. The strength of the photon signal 24 is detected by a photomultiplier tube 26, which detects a proportion of the photons emitted per unit time as a measurement shown by scale 28 of the nickel carbonyl concentration in reaction chamber 12 when compared to a calibration standard.
The three component gases enter reaction chamber 12, individually, under essentially parallel flow conditions and are mixed under dynamic flow conditions under negative pressure prior to continuous exit of the resultant products of reaction from reaction chamber 12.
It can be appreciated that process conditions that enhance the rate of product of photon emission will not only enhance the strength of the signal, but that such enhanced signal strength provides enhanced stability, which under dynamic flow conditions, provides continuous, desired enhanced accuracy.
With reference to Fig. 2, this shows generally as 50, a rectangular reaction chamber 52 having a nickel carbonyl sample inlet 54 and a carbon monoxide/ozone pre-mix inlet 56, so located as to effect the flow of the pre-mix essentially perpendicular to nickel carbonyl sample flow to effect rate of maximum turbulent mixing approximately central of reaction chamber 52. In the embodiment shown, the gases are under a positive pressure.
Each of rectangular sides 58 of chamber 52 are formed of avalanche silicon photodiodes 60 which collectively receive and detect the vast majority of the emitted photons 24, relative to the single prior art window arrangement of Fig. 1.
To further enhance the rate of mixing of the components in reaction chamber 52, the carbon monoxide and ozone flows are pre-mixed in pre-mix chamber 62 which has CO inlet conduit 64 and ozone inlet conduit 66. Chamber 62 has pre-mix outlet conduit 68 leading to reaction chamber inlet 56.
Fig. 3 shows an alternative reaction chamber in the form of a cylinder 70 having an inner surface 72 formed of the avalanche silicon photodiode.
The three component gases enter reaction chamber 12, individually, under essentially parallel flow conditions and are mixed under dynamic flow conditions under negative pressure prior to continuous exit of the resultant products of reaction from reaction chamber 12.
It can be appreciated that process conditions that enhance the rate of product of photon emission will not only enhance the strength of the signal, but that such enhanced signal strength provides enhanced stability, which under dynamic flow conditions, provides continuous, desired enhanced accuracy.
With reference to Fig. 2, this shows generally as 50, a rectangular reaction chamber 52 having a nickel carbonyl sample inlet 54 and a carbon monoxide/ozone pre-mix inlet 56, so located as to effect the flow of the pre-mix essentially perpendicular to nickel carbonyl sample flow to effect rate of maximum turbulent mixing approximately central of reaction chamber 52. In the embodiment shown, the gases are under a positive pressure.
Each of rectangular sides 58 of chamber 52 are formed of avalanche silicon photodiodes 60 which collectively receive and detect the vast majority of the emitted photons 24, relative to the single prior art window arrangement of Fig. 1.
To further enhance the rate of mixing of the components in reaction chamber 52, the carbon monoxide and ozone flows are pre-mixed in pre-mix chamber 62 which has CO inlet conduit 64 and ozone inlet conduit 66. Chamber 62 has pre-mix outlet conduit 68 leading to reaction chamber inlet 56.
Fig. 3 shows an alternative reaction chamber in the form of a cylinder 70 having an inner surface 72 formed of the avalanche silicon photodiode.
5 Although this disclosure has described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to those particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalence of the specific embodiments and features that have been described and illustrated.
6
Claims (14)
1. An improved process for measuring the concentration of nickel carbonyl in a gaseous nickel carbonyl sample comprising (a) mixing said nickel carbonyl sample with ozone and carbon monoxide under dynamic flow to produce a gaseous mixture with resultant chemiluminescence and photon emission signal;
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values; the improvement comprising premixing said ozone and said carbon monoxide to form a pre-mixture prior to mixing with said nickel carbonyl.
(b) detecting the strength of said signal; and (c) correlating said signal strength with calibrated nickel carbonyl concentration values; the improvement comprising premixing said ozone and said carbon monoxide to form a pre-mixture prior to mixing with said nickel carbonyl.
2. A process as defined in claim 1 wherein said mixing of said nickel carbonyl, ozone and carbon monoxide is effected under a negative pressure.
3. A process as defined in claim 1 wherein said mixing of said nickel carbonyl, ozone and carbon monoxide is effected under a positive pressure.
4. A process as defined in anyone of claims 1, 2 or 3 comprising detecting said photon emission signal by means of avalanche silicon photodiode means.
5. A process as defined in anyone of claims 1 to 4 wherein said nickel carbonyl concentration ranges from 100 parts per billion to 2 parts per million.
6. a process as defined in anyone of claims 1, or 2 to 5, comprising feeding said pre-mixture in a pre-mixture stream not parallel to a stream of said nickel carbonyl sample to produce said gaseous mixture.
7. A process as defined in claim 6 wherein said pre-mixture stream is fed at right angles to said nickel carbonyl sample stream.
8. An improved apparatus for measuring the concentration of gaseous nickel carbonyl in a sample gaseous mixture comprising ozone, carbon monoxide and said nickel carbonyl, said apparatus comprising (a) a flow-though reaction chamber for containing said sample gaseous mixture;
(b) means for feeding said nickel carbonyl, ozone and carbon monoxide to said chamber to operably effect chemiluminescence and produce a photon emission signal;
(c) detection means for detecting said signal; and d) measuring means for measuring the strength of said signal; the improvement comprising (e) a pre-mixing chamber means for admixing said ozone with said carbon monoxide prior to feeding said ozone and said carbon monoxide to said reaction chamber.
(b) means for feeding said nickel carbonyl, ozone and carbon monoxide to said chamber to operably effect chemiluminescence and produce a photon emission signal;
(c) detection means for detecting said signal; and d) measuring means for measuring the strength of said signal; the improvement comprising (e) a pre-mixing chamber means for admixing said ozone with said carbon monoxide prior to feeding said ozone and said carbon monoxide to said reaction chamber.
9.
Apparatus as defined in claim 8 wherein said detection means comprises avalanche silicon photodiode means.
Apparatus as defined in claim 8 wherein said detection means comprises avalanche silicon photodiode means.
10.
Apparatus as defined in claim 8 or claim 9 wherein said detection means comprises a plurality of planar surfaces.
Apparatus as defined in claim 8 or claim 9 wherein said detection means comprises a plurality of planar surfaces.
11.
Apparatus as defined in claim 8 or claim 9 wherein said detection means comprises a non-planar surface.
Apparatus as defined in claim 8 or claim 9 wherein said detection means comprises a non-planar surface.
12.
Apparatus as defined in claim 11 wherein said non-planar surface comprises in whole or a part of an inner surface of a cylinder.
Apparatus as defined in claim 11 wherein said non-planar surface comprises in whole or a part of an inner surface of a cylinder.
13.
Apparatus as defined in anyone of claims 8 to 12 comprising means to provide a negative pressure within said reaction chamber.
Apparatus as defined in anyone of claims 8 to 12 comprising means to provide a negative pressure within said reaction chamber.
14.
Apparatus as defined in anyone of claims 8 to 12 comprising means to provide a positive pressure within said reaction chamber.
Apparatus as defined in anyone of claims 8 to 12 comprising means to provide a positive pressure within said reaction chamber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2525869A CA2525869C (en) | 2005-11-07 | 2005-11-07 | Nickel carbonyl analyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2525869A CA2525869C (en) | 2005-11-07 | 2005-11-07 | Nickel carbonyl analyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2525869A1 CA2525869A1 (en) | 2007-05-07 |
| CA2525869C true CA2525869C (en) | 2014-03-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2525869A Active CA2525869C (en) | 2005-11-07 | 2005-11-07 | Nickel carbonyl analyzer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102020112570A1 (en) | 2020-05-08 | 2021-11-11 | Analytik Jena Gmbh | Device for chemiluminescence analysis |
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2005
- 2005-11-07 CA CA2525869A patent/CA2525869C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102020112570A1 (en) | 2020-05-08 | 2021-11-11 | Analytik Jena Gmbh | Device for chemiluminescence analysis |
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| Publication number | Publication date |
|---|---|
| CA2525869A1 (en) | 2007-05-07 |
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