WO2011155815A1 - Reusable miniaturized reference electrode - Google Patents
Reusable miniaturized reference electrode Download PDFInfo
- Publication number
- WO2011155815A1 WO2011155815A1 PCT/MY2010/000298 MY2010000298W WO2011155815A1 WO 2011155815 A1 WO2011155815 A1 WO 2011155815A1 MY 2010000298 W MY2010000298 W MY 2010000298W WO 2011155815 A1 WO2011155815 A1 WO 2011155815A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reference electrode
- sensitive sensors
- chloride
- sensors according
- electrolyte
- Prior art date
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
Definitions
- the present invention relates generally to a reusable miniaturized reference electrode and more specifically to such a reference electrode that can be integrated onto the same board as complimentary circuits.
- Reference electrodes are used in chemical sensors that work based on the principle of potentiometry.
- a measuring electrode is inserted into the solution to be tested and measures the electrical potential between the solution and the measuring electrode resulting from some ionic property of the solution.
- a reference electrode is inserted into the solution and functions to provide a reference potential with respect to the solution which remains effectively at a constant, known value independent of variations in the solution under test.
- the reference electrode also functions to complete an electrical circuit from the potentiometric measuring apparatus, through the measuring electrode, solution under test, reference electrode, and back to the measuring apparatus.
- the potential difference between the reference and measuring electrodes is a function of the activity of certain ions in the solution.
- a common example is a conventional pH meter which uses a pair of electrodes adapted to measure the activity of hydrogen ions in a solution.
- the present invention seeks to ameliorate the aforementioned disadvantages by providing a device that will allow for measurement of chemical properties of a solution in field conditions.
- This invention relates to a double-junction reference electrode that contains chloride but would not cause chloride ion contamination into the analyte.
- the electrode is silver-silver chloride and the internal electrolyte contains a constant concentration of chloride solution, but the chloride ion in the internal chamber is separated from the analyte by a junction bridge and a chloride-free external electrolyte.
- This invention also relates to a double junction reference electrode for use with chloride sensitive sensors comprising: an internal casing enclosing an inner chamber, said inner chamber containing an internal electrolyte wherein the internal casing is an elongated tube with a top cap covering one end and a bottom cap covering the other end; a reference electrode protruding into said inner chamber; an external casing disposed around the said internal casing and enclosing an outer chamber between said internal casing and external casing, said outer chamber containing an external electrolyte wherein the external casing is an elongated tube with an inner diameter larger than the outer diameter of said internal casing and a top plug covering one end and a bottom plug covering the other end; an internal junction bridge passing from the said inner chamber through the bottom cap and into the said outer chamber; an external junction bridge passing from the said outer chamber through the bottom plug to protrude outside the external casing; and an ion path providing for the flow of ions between the inner chamber and the outer chamber wherein the outer electrolyte is at least
- the internal electrolyte can be any of potassium chloride or tris(hydroxymethyl)aminomethane hydrochloric acid at a concentration of 0.1 M containing 20-30% glycerol and saturated with silver chloride.
- the external electrolyte can be any of lithium acetate, imidazolium acetate, imidazolium sulfate, or ammonium sulfate at a concentration of 0.5M.
- the junction bridges can be ceramic sticks with increased porosity and between 1 - 2 mm long and pretreated sequentially with refluxing non-polar solvents, polar solvents and hydrochloric acid at a concentration of 3M.
- the internal casing is made of a polymeric material such as PVC and plugged by a silicone rubber bottom cap.
- the said internal casing is made of glass and the bottom cap is made of sintered wool.
- the external casing is made of a polymeric material such as PVC.
- Figure 1 shows a diagrammatic view of a reference electrode in an embodiment of this invention.
- a reference electrode having an elongated, tubular, preferably cylindrical inner casing (10) having a top cap (12) at one end and a bottom cap (14) at the other, such that the inner casing (10), top cap (12) and bottom cap (14) enclose an inner chamber.
- the top cap (12) is fitted to the top of the inner casing (10) and a section of the top cap (12) protrudes within the internal casing (10) in a tight fit.
- the top cap (12) may be further secured to its contact with the inner wall of the internal casing (10) by an adhesive or the like.
- the bottom cap (14) is fitted to the bottom of the inner casing (10) and a section of the bottom cap (14) protrudes within the internal casing (10) in a tight fit.
- the bottom cap (14) may be further secured to its contact with the inner wall of the internal casing (10) by an adhesive or the like.
- the top cap (12) includes a central through hole providing a passage between the inner chamber and an exterior of the reference electrode for a wire lead (60) to pass therethrough.
- the wire (60) is an insulated electrical cable and is electrically connected to an inner electrode (25) by soldering, crimping, or the like.
- the inner electrode (25) protrudes into the said inner chamber.
- the inner chamber contains an internal electrolyte (20) which can be any of potassium chloride or tris(hydroxymethyl)aminomethane hydrochloric acid at a concentration of 0.1 M containing 20-30% glycerol and saturated with silver chloride.
- the internal casing is made of a polymeric material such as PVC and plugged by a silicone rubber bottom cap (14).
- the said internal casing is made of glass and the bottom cap (14) is made of sintered wool.
- the outer chamber contains an external electrolyte which can be any of lithium acetate, imidazolium acetate, imidazolium sulfate, or ammonium sulfate at a concentration of 0.5M.
- the top plug (42) secures the top of the external casing (40) and is provided with a central opening through which the top cap (12) snugly passes through. A section of the internal casing (10) wrapped around the top cap (12) also protrudes into the central opening of the top plug (42).
- the height of the top cap (12) is at least as tall as the height of the top plug (42).
- the external casing (40) is attached to the top plug (42) by an adhesive or the like.
- the external casing is made of a polymeric material such as PVC.
- An internal junction bridge (25) of ceramic stick passes from the said inner chamber through the bottom cap (14) and into the said outer chamber and provides an ion path for a flow of ions between the inner chamber and outer chamber.
- An external junction bridge (35) of ceramic stick passes from the said outer chamber through the bottom plug (44) and into an outside area external of the outer chamber.
- the external junction bridge (35) provides for an ion path for a flow of ions between the said outer chamber to the said outside area, where the solution to be analyzed is present.
- junction bridges can be ceramic sticks with increased porosity and between 1 - 2 mm long and pretreated sequentially with refluxing non-polar solvents, polar solvents and hydrochloric acid at a concentration of 3M.
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- Molecular Biology (AREA)
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- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
A double junction reference electrode for use with chloride sensitive sensors comprising: an internal casing enclosing an inner chamber containing an internal electrolyte, with a top cap covering one end and a bottom cap covering the other end; a reference electrode protruding into inner chamber; an external casing disposed around the internal casing and enclosing an outer chamber between said internal casing and external casing, outer chamber containing an external electrolyte and a top plug covering one end and a bottom plug covering the other end; an internal junction bridge passing from the inner chamber through the bottom cap and into the outer chamber; an external junction bridge passing from the outer chamber through the bottom plug to protrude outside wherein the outer electrolyte is 5 times the concentration of the inner electrolyte such that there is no chloride ions leakage.
Description
Reusable Miniaturized Reference Electrode
FIELD OF INVENTION The present invention relates generally to a reusable miniaturized reference electrode and more specifically to such a reference electrode that can be integrated onto the same board as complimentary circuits.
BACKGROUND OF INVENTION
Reference electrodes are used in chemical sensors that work based on the principle of potentiometry. To measure a chemical property of a solution, a measuring electrode is inserted into the solution to be tested and measures the electrical potential between the solution and the measuring electrode resulting from some ionic property of the solution. A reference electrode is inserted into the solution and functions to provide a reference potential with respect to the solution which remains effectively at a constant, known value independent of variations in the solution under test. The reference electrode also functions to complete an electrical circuit from the potentiometric measuring apparatus, through the measuring electrode, solution under test, reference electrode, and back to the measuring apparatus. The potential difference between the reference and measuring electrodes is a function of the activity of certain ions in the solution. A common example is a conventional pH meter which uses a pair of electrodes adapted to measure the activity of hydrogen ions in a solution.
Various chemical sensors utilizing reference electrodes have been described, but they are of large size and can only be used once. For a field
deployed chemical sensor system that automatically analyzes chemical species and transmits the data via wireless means, it is necessary that the overall system is miniaturized, robust and requires low power. It is also preferred that the system is reusable.
What is needed in the art is a device that will allow for measurement of chemical properties of a solution in field conditions.
SUMMARY OF INVENTION
The present invention seeks to ameliorate the aforementioned disadvantages by providing a device that will allow for measurement of chemical properties of a solution in field conditions.
This invention relates to a double-junction reference electrode that contains chloride but would not cause chloride ion contamination into the analyte. The electrode is silver-silver chloride and the internal electrolyte contains a constant concentration of chloride solution, but the chloride ion in the internal chamber is separated from the analyte by a junction bridge and a chloride-free external electrolyte.
This invention also relates to a double junction reference electrode for use with chloride sensitive sensors comprising: an internal casing enclosing an inner chamber, said inner chamber containing an internal electrolyte wherein the internal casing is an elongated tube with a top cap covering one end and a bottom cap covering the other end; a reference electrode protruding into said inner chamber; an external casing disposed around the said internal casing and enclosing an outer chamber between said internal casing and
external casing, said outer chamber containing an external electrolyte wherein the external casing is an elongated tube with an inner diameter larger than the outer diameter of said internal casing and a top plug covering one end and a bottom plug covering the other end; an internal junction bridge passing from the said inner chamber through the bottom cap and into the said outer chamber; an external junction bridge passing from the said outer chamber through the bottom plug to protrude outside the external casing; and an ion path providing for the flow of ions between the inner chamber and the outer chamber wherein the outer electrolyte is at least 5 times the concentration of the inner electrolyte such that there is no leakage of chloride ions from within the reference electrode.
The internal electrolyte can be any of potassium chloride or tris(hydroxymethyl)aminomethane hydrochloric acid at a concentration of 0.1 M containing 20-30% glycerol and saturated with silver chloride.
The external electrolyte can be any of lithium acetate, imidazolium acetate, imidazolium sulfate, or ammonium sulfate at a concentration of 0.5M. The junction bridges can be ceramic sticks with increased porosity and between 1 - 2 mm long and pretreated sequentially with refluxing non-polar solvents, polar solvents and hydrochloric acid at a concentration of 3M.
In one embodiment of this invention, the internal casing is made of a polymeric material such as PVC and plugged by a silicone rubber bottom cap.
In another embodiment of this invention, the said internal casing is made of glass and the bottom cap is made of sintered wool.
In one embodiment of this invention, the external casing is made of a polymeric material such as PVC. Other objects and advantages will be more fully apparent from the following disclosure and appended claims.
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 shows a diagrammatic view of a reference electrode in an embodiment of this invention.
DETAILED DESCRIPTION OF INVENTION
It should be noted that the following detailed description is directed to a device for measuring thermal diffusivity of a substance and is not limited to any particular size or configuration but in fact a multitude of sizes and configurations within the general scope of the following description.
Referring to Figure 1 , there is shown a reference electrode having an elongated, tubular, preferably cylindrical inner casing (10) having a top cap (12) at one end and a bottom cap (14) at the other, such that the inner casing (10), top cap (12) and bottom cap (14) enclose an inner chamber. The top cap (12) is fitted to the top of the inner casing (10) and a section of the top cap (12) protrudes within the internal casing (10) in a tight fit. The top cap (12) may be further secured to its contact with the inner wall of the internal casing (10) by an adhesive or the like.
The bottom cap (14) is fitted to the bottom of the inner casing (10) and a section of the bottom cap (14) protrudes within the internal casing (10) in a tight fit. The bottom cap (14) may be further secured to its contact with the inner wall of the internal casing (10) by an adhesive or the like.
The top cap (12) includes a central through hole providing a passage between the inner chamber and an exterior of the reference electrode for a wire lead (60) to pass therethrough. The wire (60) is an insulated electrical cable and is electrically connected to an inner electrode (25) by soldering, crimping, or the like. The inner electrode (25) protrudes into the said inner chamber. The inner chamber contains an internal electrolyte (20) which can be any of potassium chloride or tris(hydroxymethyl)aminomethane hydrochloric acid at a concentration of 0.1 M containing 20-30% glycerol and saturated with silver chloride.
In one embodiment of this invention, the internal casing is made of a polymeric material such as PVC and plugged by a silicone rubber bottom cap (14).
In another embodiment of this invention, the said internal casing is made of glass and the bottom cap (14) is made of sintered wool.
Still referring to Figure 1 , there is shown an elongated, tubular, preferably cylindrical external casing (40) disposed around the said internal casing (10) with an inner diameter larger than the outer diameter of said internal casing (10) and a top plug (42) covering one end and a bottom plug (44) covering the other end such that the external casing (40), top plug (42) and bottom plug (44) enclose an outer chamber between said internal casing (10) and
external casing (40). The outer chamber contains an external electrolyte which can be any of lithium acetate, imidazolium acetate, imidazolium sulfate, or ammonium sulfate at a concentration of 0.5M. The top plug (42) secures the top of the external casing (40) and is provided with a central opening through which the top cap (12) snugly passes through. A section of the internal casing (10) wrapped around the top cap (12) also protrudes into the central opening of the top plug (42).
The height of the top cap (12) is at least as tall as the height of the top plug (42). The external casing (40) is attached to the top plug (42) by an adhesive or the like.
In one embodiment of this invention, the external casing is made of a polymeric material such as PVC.
An internal junction bridge (25) of ceramic stick passes from the said inner chamber through the bottom cap (14) and into the said outer chamber and provides an ion path for a flow of ions between the inner chamber and outer chamber.
An external junction bridge (35) of ceramic stick passes from the said outer chamber through the bottom plug (44) and into an outside area external of the outer chamber. The external junction bridge (35) provides for an ion path for a flow of ions between the said outer chamber to the said outside area, where the solution to be analyzed is present.
The junction bridges can be ceramic sticks with increased porosity and between 1 - 2 mm long and pretreated sequentially with refluxing non-polar solvents, polar solvents and hydrochloric acid at a concentration of 3M.
While several particularly preferred embodiments of the present invention have been described and illustrated, it should now be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are intended to embrace such changes, modifications, and areas of application that are within the spirit and scope of this invention.
Claims
A double junction reference electrode for use with chloride sensitive sensors comprising:
an internal casing (10) enclosing an inner chamber, said inner chamber containing an internal electrolyte (20) wherein the internal casing (10) is an elongated tube with a top cap (12) covering one end and a bottom cap (14) covering the other end; a reference electrode (25) protruding into said inner chamber; an external casing (40) disposed around the said internal casing (10) and enclosing an outer chamber between said internal casing (10) and external casing (40), said outer chamber containing an external electrolyte (30) wherein the external casing (40) is an elongated tube with an inner diameter larger than the outer diameter of said internal casing (10) and a top plug (42) covering one end and a bottom plug (44) covering the other end; an internal junction bridge (25) passing from the said inner chamber through the bottom cap (14) and into the said outer chamber;
an external junction bridge (35) passing from the said outer chamber through the bottom plug (44) to protrude outside the external casing (40); and
an ion path providing for the flow of ions between the inner chamber and the outer chamber
wherein the outer electrolyte is at least 5 times the concentration of the inner electrolyte such that there is no leakage of chloride ions from within the reference electrode.
A double junction reference electrode for use with chloride sensitive sensors according to claim 1 wherein the internal electrolyte (20) is potassium chloride at a concentration of 0.1 M containing 20- 30% glycerol and saturated with silver chloride.
A double junction reference electrode for use with chloride sensitive sensors according to claim 1 wherein the internal electrolyte (20) is tris(hydroxymethyl)aminomethane hydrochloric acid at a concentration of 0.1 M containing 20-30% glycerol and saturated with silver chloride.
A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 3 wherein the external electrolyte (30) is lithium acetate at a concentration of 0.5M.
A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 3 wherein the external electrolyte (30) is imidazolium acetate at a concentration of 0.5 .
A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 3 wherein the external electrolyte (30) is imidazolium sulfate at a concentration of 0.5M.
A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 3 wherein the external electrolyte (30) is ammonium sulfate at a concentration of 0.5M.
8. A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 7 wherein the said junction bridges (25, 35) are made of ceramic with increased porosity.
9. A double junction reference electrode for use with chloride sensitive sensors according to claim 8 wherein the junction bridges (25, 35) are stick-shaped and between 1 - 2 mm long and pretreated sequentially with refluxing non-polar solvents, polar solvents and hydrochloric acid at a concentration of 3M.
10. A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 9 wherein the said internal casing (10) is made of a polymeric material.
1 1 . A double junction reference electrode for use with chloride sensitive sensors according to claim 10 wherein the said polymeric material is PVC.
12. A double junction reference electrode for use with chloride sensitive sensors according to claim 10 or 1 1 wherein the said bottom cap (14) is made of silicone rubber.
13. A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 9 wherein the said internal casing (10) is made of glass.
14. A double junction reference electrode for use with chloride sensitive sensors according to claim 13 wherein the said bottom cap (14) is made of sintered wool.
15. A double junction reference electrode for use with chloride sensitive sensors according to any of claims 1 to 14 wherein the said external casing (40) is made of a polymeric material.
16. A double junction reference electrode for use with chloride sensitive sensors according to claim 15 wherein the said polymeric material is PVC.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MYPI2010002626 | 2010-06-07 | ||
| MYPI2010002626 MY150794A (en) | 2010-06-07 | 2010-06-07 | Reusable miniaturized reference electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011155815A1 true WO2011155815A1 (en) | 2011-12-15 |
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ID=45098268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/MY2010/000298 WO2011155815A1 (en) | 2010-06-07 | 2010-11-25 | Reusable miniaturized reference electrode |
Country Status (2)
| Country | Link |
|---|---|
| MY (1) | MY150794A (en) |
| WO (1) | WO2011155815A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014204293A1 (en) * | 2013-06-19 | 2014-12-24 | Mimos Berhad | A double junction reference electrode |
| CN114689669A (en) * | 2012-03-26 | 2022-07-01 | 株式会社堀场制作所 | Comparative electrode and electrochemical measuring device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360415A (en) * | 1981-02-02 | 1982-11-23 | Corning Glass Works | Noise suppressing bypass for reference electrode |
| US4401548A (en) * | 1981-02-12 | 1983-08-30 | Corning Glass Works | Reference electrode with internal diffusion barrier |
| US4645583A (en) * | 1985-09-09 | 1987-02-24 | Kuraray Co., Ltd. | Reference electrode |
| JPH09304331A (en) * | 1996-05-17 | 1997-11-28 | Miura Co Ltd | Hardness sensor |
| US20060091009A1 (en) * | 2004-11-02 | 2006-05-04 | Harman John N Iii | Ion selective electrode with integral sealing surface |
-
2010
- 2010-06-07 MY MYPI2010002626 patent/MY150794A/en unknown
- 2010-11-25 WO PCT/MY2010/000298 patent/WO2011155815A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360415A (en) * | 1981-02-02 | 1982-11-23 | Corning Glass Works | Noise suppressing bypass for reference electrode |
| US4401548A (en) * | 1981-02-12 | 1983-08-30 | Corning Glass Works | Reference electrode with internal diffusion barrier |
| US4645583A (en) * | 1985-09-09 | 1987-02-24 | Kuraray Co., Ltd. | Reference electrode |
| JPH09304331A (en) * | 1996-05-17 | 1997-11-28 | Miura Co Ltd | Hardness sensor |
| US20060091009A1 (en) * | 2004-11-02 | 2006-05-04 | Harman John N Iii | Ion selective electrode with integral sealing surface |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114689669A (en) * | 2012-03-26 | 2022-07-01 | 株式会社堀场制作所 | Comparative electrode and electrochemical measuring device |
| WO2014204293A1 (en) * | 2013-06-19 | 2014-12-24 | Mimos Berhad | A double junction reference electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| MY150794A (en) | 2014-02-28 |
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