GB2267348A - Electrochemical oxygen sensor - Google Patents
Electrochemical oxygen sensor Download PDFInfo
- Publication number
- GB2267348A GB2267348A GB9211125A GB9211125A GB2267348A GB 2267348 A GB2267348 A GB 2267348A GB 9211125 A GB9211125 A GB 9211125A GB 9211125 A GB9211125 A GB 9211125A GB 2267348 A GB2267348 A GB 2267348A
- Authority
- GB
- United Kingdom
- Prior art keywords
- oxygen
- electrode
- sensing electrode
- sensor
- chamber
- 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.)
- Withdrawn
Links
- 239000001301 oxygen Substances 0.000 title abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 4
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 14
- -1 hydroxide ions Chemical class 0.000 abstract description 7
- 210000004027 cell Anatomy 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 231100000756 time-weighted average Toxicity 0.000 description 1
Classifications
-
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
An oxygen sensor comprises two chambers communicating via a narrow electrolyte passage 11, a sensing electrode 2 in one chamber, a reference electrode 9 which may be in either chamber, and a counter electrode 8 in the other chamber. Oxygen being sensed passes through a diffusion membrane 4 to the sensing electrode 2. A potentiostat applies a small negative potential to the sensing electrode relative to the reference electrode. A current flowing externally between the counter electrode and the sensing electrode is a measure of the level of oxygen in the medium outside the membrane 4. The electrodes may be platinum and the electrolyte sulphuric acid. In operation, oxygen is converted to hydroxide ions at the sensing electrode. The hydroxide ions pass through the narrow, capillary passage 11 to the counter electrode 8 where they are reconverted to oxygen which diffuses out of the cell through membrane 10. <IMAGE>
Description
Sensor for Oxygen or other Gas
This invention relates to a sensor for oxygen or other gas.
Oxygen sensors find wide use in industry, medicine and numerous other applications where continuous monitoring of oxygen level is necessary or desirable. Among the most popular types of oxygen sensor has been the electrochemical or galvanic type, which is relatively inexpensive to make and, because it is small and has a low power requirement, it is portable and convenient to use.
The galvanic oxygen sensor is frequently referred to as the Clark oxygen sensor, after its inventor. In its basic form, the Clark oxygen sensor comprises a cathode, usually of silver and acting as the oxygen sensing electrode, coupled galvanically to a consumable anode or counter electrode, also usually of silver: the two electrodes are in contact with an electrolyte of potassium chloride solution. The cathode or oxygen sensing electrode is covered by a membrane, through which oxygen diffuses from the exterior medium. The rate of oxygen diffusion is proportional to the partial pressure of the oxygen in the exterior medium, and so the electrical current generated by the cell is proportional to, and therefore provides a measure of, the amount of oxygen in the medium being monitored.
The main disadvantages of the Clark oxygen sensor are its short life and its requirement for frequent maintenance.
The lifetime is limited by the corrosion of the anode or counter electrode and, because the cell runs continuously, its lifetime is of the order of 6 to 12 months. Also the electrolyte is continuously consumed and needs changing at regular intervals: this process usually involves removal of the membrane, which is liable to be damaged in the process and require replacement.
I have now devised a sensor for oxygen or other selected gas, the sensor having a long life expectancy and being maintenance free, because the cell components are stable and are not consumed.
In accordance with this invention there is provided an electrochemical sensor, comprising two chambers communicating via a narrow electrolyte passage and having a sensing electrode in one chamber, a counter electrode in the other chamber, a reference electrode in either chamber, a diffusion barrier through which the sensing electrode is accessible from an exterior medium, means for applying a predetermined potential to the sensing electrode relative to the reference electrode, and means for monitoring an external current flow from the counter electrode to the sensing electrode.
In an oxygen sensor to be described herein, the sensing electrode is of a material (e.g. platinum) electrocatalytically sensitive to oxygen. Oxygen reaching the sensing electrode is reduced to hydroxide ions which then pass to the counter electrode, where the reverse electrochemical reaction takes place and oxygen is evolved. In effect, the sensor pumps oxygen from one chamber to the other, reducing it to hydroxide ions at the sensing electrode and evolving it from the hydroxide ions at the counter electrode, without any net gain or loss of mass. The narrow passage between the two chambers (e.g. a capillary) prevents the oxygen evolved at the counter electrode from passing back to the sensing electrode.
The sensor can be used in two broad types of oxygen measurement applications, either immersed in water or aqueous fluids to monitor the quantity of dissolved oxygen, or in air or gas to monitor the level of oxygen therein.
An embodiment of this invention will now be described by way of example only and with reference to the accompanying drawing, the single figure of which is a diagrammatic section through one embodiment of gas sensor, in the form of an oxygen sensor, in accordance with this invention.
Referring to the drawing, there is shown an example of oxygen sensor, comprising a body 1 having upper and lower chambers communicating with each other through a capillary bore 11. In the upper chamber there is a cathode or sensing electrode 2, a diffusion membrane 3 over and in contact with the electrode 2, and an optional porous membrane 4 e.g. of PTFE over the diffusion membrane 3, for protection and to exclude water if the cell is to be immersed. An annular member 5 is clamped down onto the body 4 by means of fixing screws (not shown) and compresses a rubber sealing ring 6 against the membrane to make a seal, so that the only access to the sensing electrode 2 is by diffusion through the membrane 3.
The lower chamber houses a reference electrode 9, an anode or counter electrode 8, and a porous membrane 10, all secured in place by a twist washer 7 which fits tightly into the open side of the chamber. The porous membrane allows oxygen, generated at the anode or counter electrode 8, to escape from the lower chamber.
The capillary 11 is filled with electrolyte e.g.
sulphuric acid, preferably soaked into an inert absorbing material such as silica gel: the arrangement prevents significant quantities of oxygen passing into the upper chamber from the lower chamber.
Each of the three electrodes may comprise a porous plastics material such as PVC soaked in the electrolyte e.g.
sulphuric acid and coated on one side with platinum. The sensing electrode 2 would have its platinum side uppermost: the reference and counter electrodes 9,8 would be arranged so that their platinum sides do not contact each other, e.g. the reference electrode 9 may have its platinum side uppermost and the counter electrode 8 may have its platinum side lowermost.
Platinum connecting wires (not shown) extend from the exterior of the cell to the respective electrodes.
An external power source is connected between the sensing electrode 2 and the reference electrode 9 to apply a small negative potential to the sensing electrode 2 relative to the reference electrode 9, e.g. of 1 volt. This external source preferably comprises a potentiostat, which permits negligible current to flow through the reference electrode whilst maintaining the predetermined potential. The potentiostat circuit need only occupy a very small space and has a low power requirement.
A current flow is established between the counter electrode 8 and the sensing electrode 2 via an external circuit, the counter electrode 8 taking up a potential about 1 volt positive relative to the reference electrode 9. This current is proportional to the rate of diffusion of oxygen to the sensing electrode 2. An thermistor is included within the body 1 to measure the internal temperature of the cell and provide compensation for the measured current, since the rate of diffusion of oxygen through the membrane 3 increases with temperature. The signal from the thermistor may also be used to provide a temperature readout.
The sensing electrode 2 is electrocatalytically sensitive to oxygen. Hydroxide ions (OH-) are generated at a rate proportional to the rate of incoming oxygen, and these hydroxide ions pass through the capillary 11 to the counter electrode 8 acting as an anode, where the reverse electrochemical reaction takes place and oxygen is evolved: this oxygen diffuses out through the membrane 10. Thus, the cell in effect pumps oxygen from one chamber to the other without any net gain or loss of mass.
The reference electrode 9 may be disposed in the upper chamber, below the sensing electrode 2, instead of in the lower chamber.
The entire sensor can be housed in a probe e.g. for dissolved oxygen measurement, or within a hand-held instrument for gas sensing. Electrical connections between the sensor and instrumentation can provide for a continuous display of oxygen level, a temperature display, and other microprocessor generated functions such as time-weighted averages.
Claims (8)
1) An electrochemical sensor, comprising two chambers communicating via a narrow electrolyte passage and having a sensing electrode in one chamber, a counter electrode in the other chamber, a reference electrode in either chamber, a diffusion barrier through which the sensing electrode is accessible from an exterior medium, means for applying a predetermined potential to the sensing electrode relative to the reference electrode, and means for monitoring an external current flow from the counter electrode to the sensing electrode.
2) A sensor as claimed in claim 1, in which the potential applying means comprises a potentiostat.
3) A sensor as claimed in claim 1 or 2, in which the sensing electrode comprises platinum.
4) A sensor as claimed in any preceding claim, in which the reference electrode comprises platinum.
5) A sensor as claimed in any preceding claim, in which the counter electrode comprises platinum.
6) A sensor as claimed in any preceding claim, in which the electrolyte comprises acid.
7) A sensor as claimed in claim 6, in which the electrolyte comprises sulphuric acid.
8) An electrochemical sensor substantially as herein described with reference to the accompanying drawing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9211125A GB2267348A (en) | 1992-05-26 | 1992-05-26 | Electrochemical oxygen sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9211125A GB2267348A (en) | 1992-05-26 | 1992-05-26 | Electrochemical oxygen sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9211125D0 GB9211125D0 (en) | 1992-07-08 |
| GB2267348A true GB2267348A (en) | 1993-12-01 |
Family
ID=10716029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9211125A Withdrawn GB2267348A (en) | 1992-05-26 | 1992-05-26 | Electrochemical oxygen sensor |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2267348A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265750B1 (en) * | 1999-07-15 | 2001-07-24 | Teledyne Technologies Incorporated | Electrochemical gas sensor and method of making the same |
| US7664607B2 (en) | 2005-10-04 | 2010-02-16 | Teledyne Technologies Incorporated | Pre-calibrated gas sensor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1473250A (en) * | 1974-05-07 | 1977-05-11 | Energetics Science | Method and device for the detection and measurement of no2 gases |
| EP0084935A1 (en) * | 1982-01-11 | 1983-08-03 | Hitachi, Ltd. | Gas detection device |
| GB2180653A (en) * | 1985-09-13 | 1987-04-01 | Licentia Gmbh | Electrochemical cell |
| GB2181557A (en) * | 1985-09-20 | 1987-04-23 | Bacharach Inc | Electrochemical gas detector |
| EP0239297A2 (en) * | 1986-03-27 | 1987-09-30 | Land Combustion Limited | Electrochemical sensors |
-
1992
- 1992-05-26 GB GB9211125A patent/GB2267348A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1473250A (en) * | 1974-05-07 | 1977-05-11 | Energetics Science | Method and device for the detection and measurement of no2 gases |
| EP0084935A1 (en) * | 1982-01-11 | 1983-08-03 | Hitachi, Ltd. | Gas detection device |
| GB2180653A (en) * | 1985-09-13 | 1987-04-01 | Licentia Gmbh | Electrochemical cell |
| GB2181557A (en) * | 1985-09-20 | 1987-04-23 | Bacharach Inc | Electrochemical gas detector |
| EP0239297A2 (en) * | 1986-03-27 | 1987-09-30 | Land Combustion Limited | Electrochemical sensors |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265750B1 (en) * | 1999-07-15 | 2001-07-24 | Teledyne Technologies Incorporated | Electrochemical gas sensor and method of making the same |
| US7664607B2 (en) | 2005-10-04 | 2010-02-16 | Teledyne Technologies Incorporated | Pre-calibrated gas sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9211125D0 (en) | 1992-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |