WO2023026918A1 - 酸素センサ、水質測定装置及び酸素測定方法 - Google Patents

酸素センサ、水質測定装置及び酸素測定方法 Download PDF

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WO2023026918A1
WO2023026918A1 PCT/JP2022/031052 JP2022031052W WO2023026918A1 WO 2023026918 A1 WO2023026918 A1 WO 2023026918A1 JP 2022031052 W JP2022031052 W JP 2022031052W WO 2023026918 A1 WO2023026918 A1 WO 2023026918A1
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negative electrode
oxygen sensor
positive electrode
oxygen
electrolytic solution
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French (fr)
Japanese (ja)
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憲輔 戸田
佑一朗 小松
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Horiba Advanced Techno Co Ltd
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Horiba Advanced Techno Co Ltd
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Priority to CN202280057116.1A priority Critical patent/CN117836619A/zh
Priority to JP2023543840A priority patent/JPWO2023026918A1/ja
Priority to US18/684,372 priority patent/US20240426774A1/en
Publication of WO2023026918A1 publication Critical patent/WO2023026918A1/ja
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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
    • G01N27/416—Systems
    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

Definitions

  • This application relates to an oxygen sensor, a water quality measuring device, and an oxygen measuring method.
  • an oxygen sensor includes an electrolytic solution, a liquid container that contains the electrolytic solution, a permeable membrane having oxygen permeability, and a positive electrode and a negative electrode that are arranged so as to be in contact with the electrolytic solution.
  • the negative electrode contains tin.
  • an oxygen sensor may measure dissolved oxygen in a low-temperature target liquid, for example.
  • a temperature of 0° C. or less there is a possibility that the dissolved oxygen cannot be measured due to the freezing of the electrolyte.
  • the problem is to provide an oxygen sensor, a water quality measuring device, and an oxygen measuring method that can properly measure dissolved oxygen in a low-temperature target liquid.
  • the oxygen sensor includes an electrolyte, a liquid storage part having an opening and containing the electrolyte, a permeable membrane having oxygen permeability and covering the opening, and being in contact with the electrolyte. a positive electrode and a negative electrode, wherein the negative electrode includes tin and the electrolyte includes a polyol.
  • the water quality measuring device is equipped with the oxygen sensor described above.
  • the oxygen measurement method uses the oxygen sensor described above to measure the dissolved oxygen in the target liquid.
  • FIG. 1 is an overall view of a water quality measuring device according to one embodiment.
  • FIG. 2 is a cross-sectional end view taken along line II--II of FIG.
  • FIG. 3 is an enlarged view of area III in FIG.
  • FIG. 4 is a potential-pH diagram (temperature: 25° C.) of the Sn—H 2 O system.
  • FIGS. 1 to 4 An embodiment of an oxygen sensor and a water quality measuring device will be described below with reference to FIGS. 1 to 4.
  • the dimensional ratio of the drawing and the actual dimensional ratio do not necessarily match, and the dimensional ratio between the drawings does not necessarily match.
  • a water quality measuring device 1 includes a detection unit 2 that detects the water quality of a target liquid to be measured, a device main body 3 that can communicate with the detection unit 2, and a detection unit 2 and the device main body. 3 may be provided.
  • the device body 3 may include, for example, an input unit 3a to which information is input, a processing unit 3b to process information, and an output unit 3c to output information, as in the present embodiment.
  • the communication means 4 may be, for example, wired communication means (for example, cable) as in the present embodiment, or may be, for example, wireless communication means. Note that the detection unit 2 and the apparatus main body 3 may be configured integrally.
  • the input unit 3a is not particularly limited, but can be, for example, a button, a touch panel, or the like. Then, for example, information of an instruction to start measurement may be input to the input unit 3a.
  • the processing unit 3b may include, for example, processors such as CPU and MPU, memories such as ROM and RAM, and various interfaces. Specifically, the processing unit 3b includes, for example, an acquisition unit that acquires information from the detection unit 2 and the input unit 3a, a storage unit that stores the information, and a calculation unit that calculates the information (for example, the water quality value). , and a control unit that controls each unit of the water quality measuring device 1 (for example, the output unit 3c).
  • the output unit 3c is not particularly limited, it can be, for example, a display device or the like.
  • the output unit 3c may be, for example, transmission means for outputting (transmitting) a signal to the outside of the water quality measuring device 1.
  • the output unit 3c may output the measurement result (for example, water quality value) or the like.
  • the detection unit 2 includes sensors 5 and 6 that detect the water quality of the target liquid.
  • the detection unit 2 includes at least an oxygen sensor 5 that detects dissolved oxygen in the target liquid.
  • the detection unit 2 may include, for example, at least one other sensor 6 that detects water quality items (eg, pH, conductivity, turbidity, temperature, etc.) other than dissolved oxygen.
  • the oxygen sensor 5 only.
  • the detection unit 2 includes an oxygen sensor 5 and a temperature sensor 6 that detects the temperature of the target liquid.
  • the detection unit 2 may include, for example, a detection unit main body 7 to which the sensors 5 and 6 are attached, and a protection unit 8 that protects the oxygen sensor 5.
  • the sensors 5 and 6 may be arranged at the tip of the detection section 2 as in this embodiment. As a result, the measurement person grips the detection unit main body 7 and dips the tip of the detection unit 2, that is, the sensors 5 and 6 in the target liquid, so that the water quality of the target liquid can be detected.
  • the protection part 8 may be attached to the detection part main body 7 so as to cover the oxygen sensor 5, for example.
  • the protective part 8 is formed with rigidity (for example, made of metal) so as not to be deformed, and has an opening 8a for the subject liquid to enter inside. may be configured as follows.
  • the protection part 8 may be formed in a film shape having elasticity, for example.
  • the temperature sensor 6 may be arranged at a concave position of the detection unit main body 7 as in the present embodiment, for example. As a result, for example, when the detection unit 2 is thrown into a river or the like and used, the temperature sensor 6 can be prevented from hitting the bottom or wall of the river.
  • the oxygen sensor 5 includes an electrolyte 9, a liquid storage portion 10 having an opening 10a at the tip and containing the electrolyte 9 therein, and a liquid storage portion having oxygen permeability. It includes a permeable film 11 covering the opening 10 a of 10 , and a positive electrode 12 and a negative electrode 13 arranged so as to be in contact with the electrolytic solution 9 .
  • the negative electrode 13 contains tin.
  • the negative electrode 13 can be formed by, for example, tin shaving molding, tin extrusion molding, tin vapor deposition or plating on the surface of the conductive member, or the like. From the viewpoint that the higher the tin content, the longer the life, tin shaving molding and tin extrusion molding are more preferable than vapor deposition or plating of tin on the surface of the conductive member. .
  • the oxygen sensor 5 does not require the application of a voltage from an external power source or the like between the positive electrode 12 and the negative electrode 13, and is a galvanic sensor that naturally generates a potential between the positive electrode 12 and the negative electrode 13. It is a battery-powered sensor. Dissolved oxygen can be measured by measuring the potential generated between the positive electrode 12 and the negative electrode 13 .
  • the permeable membrane 11 is a membrane that is permeable to oxygen and impermeable to liquid.
  • the permeable membrane 11 may be, for example, a polyethylene membrane or a fluorine resin membrane such as tetrafluoroethylene-hexafluoropropylene copolymer (FEP).
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • the thickness of the permeable membrane 11 may be, for example, 12.5 to 50 ⁇ m.
  • the oxygen sensor 5 includes a housing 14 formed in a cylindrical shape, a holding portion 15 disposed inside the housing 14 and holding the positive electrode 12 and the negative electrode 13, the positive electrode 12 and An electrode fixing portion 16 for fixing the negative electrode 13 to the housing 14 and a membrane fixing portion 17 for fixing the permeable membrane 11 by sandwiching the outer peripheral portion of the permeable membrane 11 between the housings 14 may be provided.
  • the liquid storage section 10 is composed of the housing 14 and the electrode fixing section 16 .
  • the electrolytic solution 9 is sealed inside the liquid containing portion 10 by the permeable membrane 11 .
  • the liquid containing portion 10 has an opening 10b at the proximal end portion, and the positive electrode 12, the negative electrode 13, and the holding portion 15 close the opening 10b.
  • each of the positive electrode 12 and the negative electrode 13 is arranged inside the liquid container 10 .
  • the oxygen sensor 5 has a sealing portion (for example, an O-ring) 18 to prevent the subject liquid from entering the inside of the liquid containing portion 10 from between the housing 14 and the membrane fixing portion 17, for example. may be provided.
  • the surface area of the negative electrode 13 is preferably 20 times or more the surface area of the positive electrode 12 .
  • the “surfaces” of the electrodes 12 and 13 refer to the portions of the electrodes 12 and 13 that are in contact with the electrolytic solution 9 , and are also referred to as the “liquid contact surfaces” of the electrodes 12 and 13 . Therefore, it is preferable that the negative electrode 13 is formed in a cylindrical shape as in the present embodiment.
  • the surface area of the negative electrode 13 can be increased relative to the surface area of the positive electrode 12, so that the electrochemical reaction can be efficiently caused. Therefore, for example, the measurement accuracy of the oxygen sensor 5 can be improved. Moreover, while the surface area of the negative electrode 13 can be increased, the increase in the volume of the negative electrode 13 can be suppressed.
  • the holding part 15 may be fixed to each of the positive electrode 12 and the negative electrode 13, for example.
  • the holding portion 15 may be arranged inside the negative electrode 13 and the outer peripheral portion of the holding portion 15 may be fixed to the inner peripheral portion of the negative electrode 13 .
  • the holding portion 15 is formed in a cylindrical shape
  • the positive electrode 12 is formed in a columnar shape
  • the positive electrode 12 is arranged inside the holding portion 15, and the outer peripheral portion of the positive electrode 12 is , and fixed to the inner peripheral portion of the holding portion 15 .
  • the electrode fixing part 16 may be fixed to the negative electrode 13 and the housing 14, for example.
  • the electrode fixing portion 16 is formed in a cylindrical shape, the negative electrode 13 is arranged inside the electrode fixing portion 16, and the outer peripheral portion of the negative electrode 13 is the inner peripheral portion of the electrode fixing portion 16.
  • the configuration may be such that it is fixed to Further, for example, as in the present embodiment, the electrode fixing portion 16 is arranged inside the housing 14, and the outer peripheral portion of the electrode fixing portion 16 is fixed to the inner peripheral portion of the housing 14. It's okay.
  • the surface of the positive electrode 12 is preferably arranged closer to the permeable membrane 11 than the surface of the negative electrode 13 . Therefore, as in the present embodiment, it is preferable that the tip of the holding portion 15 protrude from the negative electrode 13 and the surface of the positive electrode 12 is arranged at the tip of the holding portion 15 .
  • the surface of the positive electrode 12 is in contact with the permeable film 11 in order to efficiently cause the electrochemical reaction at the positive electrode 12 .
  • the surface of the positive electrode 12 is in contact with the permeable membrane 11 includes, for example, a state in which a small amount of the electrolytic solution 9 exists in the gap between the surface of the positive electrode 12 and the permeable membrane 11 due to capillary action.
  • a configuration in which the surface of the positive electrode 12 is pressed against the permeable membrane 11 so as to apply tension to the elastic permeable membrane 11 is more preferable.
  • the positive electrode 12 and the negative electrode 13 close to each other. Therefore, it is preferable that the minimum distance W1 between the surface of the positive electrode 12 and the surface of the negative electrode 13 is 4.5 mm or less, as in the present embodiment. Thereby, it is possible to suppress the occurrence of a difference between the temperature of the positive electrode 12 and the temperature of the negative electrode 13 through the electrolyte solution 9 . Note that the electrolytic solution 9 is not shown in FIG.
  • the minimum distance W2 between the surface of the negative electrode 13 and the permeable film 11 is 4.0 mm or less, as in the present embodiment.
  • the temperature of the positive electrode 12 and the temperature of the negative electrode 13 become closer to the temperature of the target liquid, respectively, so that the occurrence of a difference between the temperature of the positive electrode 12 and the temperature of the negative electrode 13 can be suppressed. .
  • the target liquid is not particularly limited. It can be human waste, cooling water for air conditioning, etc., and it can be a treatment liquid in a treatment facility (liquid during treatment, liquid after treatment), or a test solution put in a container.
  • the temperature of the target liquid is not particularly limited, it may be 0° C. or lower or 40° C. or higher, for example.
  • the electrolytic solution 9 contains a water-soluble and non-volatile polyol.
  • the electrolytic solution 9 preferably contains at least one of glycerol, erythritol, sorbitol, ethylene glycol, and propanediol among polyols.
  • the solidification point of the electrolytic solution 9 is preferably -30°C to -5°C, for example.
  • the freezing point of the electrolyte solution 9 it is possible to set the freezing point of the electrolyte solution 9 to 0° C. or lower by adjusting the concentration of the salt contained in the electrolyte solution 9 due to the freezing point effect. Only the concentration of the salt equal to or less than the concentration can be dissolved in the electrolytic solution 9 . That is, the freezing point of the electrolytic solution 9 is equal to or higher than the freezing point of the target liquid.
  • the electrolyte solution 9 contains a polyol, even if the concentration of the salt is the same as that of the target solution, the solidification point of the electrolyte solution 9 is lower than that of the target solution due to the presence of the polyol. Therefore, the dissolved oxygen in the target liquid can be properly measured even near the temperature at which the target liquid starts to solidify.
  • the polarity of the polyol contained in the electrolyte 9 is preferably close to that of water.
  • polarity can be represented by a solubility parameter (SP value).
  • SP value solubility parameter
  • the solubility parameter of water is not particularly limited to 23.4 [(MPa) 1/2 ], but the solubility parameter of polyol is, for example, 11 [(MPa) 1/2 ] or more.
  • it is more preferably 14 [(MPa) 1/2 ] or more, and for example, it is very preferably 16 [(MPa) 1/2 ] or more.
  • the solubility parameter of glycerol is 16.5 [(MPa) 1/2 ], that of ethylene glycol is 14.2 [(MPa) 1/2 ], and that of 1,3-propanediol.
  • the solubility parameter is 11.5 [(MPa) 1/2 ]. Therefore, it is preferable that the electrolytic solution 9 contains glycerol among the polyol substances, and it is more preferable that the polyol contained in the electrolytic solution 9 is only glycerol.
  • glycerol is water-soluble, moisturizing, non-volatile, and non-toxic.
  • the volume ratio of the polyol in the electrolytic solution 9 is preferably set appropriately.
  • the electrolytic solution 9 contains salts (eg, NaOH, KOH, etc.), and the volume ratio of polyol in the electrolytic solution 9 is the ratio of "volume of polyol" to "volume of electrolytic solution 9".
  • the volume ratio of the polyol in the electrolytic solution 9 is preferably, for example, 10% or more, and for example, 20% or more. It is even more preferable to have As a result, freezing of the electrolytic solution 9 can be suppressed when a target liquid with a low temperature is measured.
  • the volume ratio of the polyol in the electrolyte solution 9 is preferably 70% or less, for example, 50% More preferably: As a result, the volume ratio of the salt can be ensured, so that the electrochemical reaction can be reliably generated via the electrolytic solution 9 .
  • FIG. 4 shows a potential-pH diagram (temperature: 25° C.) of the Sn—H 2 O system.
  • the horizontal axis is the pH of the aqueous solution
  • the vertical axis is the NHE-based potential. 4
  • SnH 4 (g) Sn (s), Sn(OH) 2 (s), Sn(OH) 4 (s), Sn 2+ (aq), Sn 4+ (aq), SnO 3 2
  • the regions marked with - (aq) indicate that each exists stably.
  • the negative electrode 13 is formed of tin, based on the potential (vertical axis) generated on the negative electrode 13 and the pH (horizontal axis) of the electrolytic solution 9, You can see the substances that do, that is, the substances that are produced in large quantities.
  • (g) indicates a gas
  • (s) indicates an insoluble solid
  • (aq) indicates a water-soluble ion.
  • the one-dot chain line is the boundary line corresponding to the oxidation-reduction equilibrium between water and oxygen
  • the two-dot chain line is the boundary line corresponding to the oxidation-reduction equilibrium between water and hydrogen.
  • the positive electrode 12 preferably contains at least one of gold, silver, platinum, and carbon.
  • the positive electrode 12 is made of gold, silver, platinum, or carbon and the negative electrode 13 is made of tin, the following electrochemical reactions occur.
  • ⁇ Positive electrode reaction> O 2 +2H 2 O+4e ⁇ 4OH ⁇ +0.401 V (standard redox potential of positive electrode)
  • ⁇ Negative electrode reaction> Sn Sn 2+ +2e ⁇ +0.138 V (standard redox potential of negative electrode)
  • the dashed line indicates the generated potential of -0.539V.
  • the pH value that is the boundary B1 between the region where tin hydroxide [Sn(OH) 2 ] is stably present and the region where stannate ion [SnO 3 2 ⁇ ] is stably present is estimated to be 12.2.
  • tin hydroxide [Sn(OH) 2 ], which is an insoluble solid, stably exists in the oxygen sensor 5 when the pH of the electrolytic solution 9 is lower than 12.2. Therefore, tin hydroxide is generated and covers the surfaces of the electrodes 12 and 13 (especially the negative electrode 13), which may hinder the above electrochemical reaction.
  • the pH of the electrolytic solution 9 is 12.2 or higher.
  • water-soluble stannate ions [SnO 3 2 ⁇ ] exist stably. Therefore, since it is possible to suppress the generation of tin hydroxide, it is possible to suppress the tin hydroxide from covering the surfaces of the electrodes 12 and 13 .
  • the pH value which is the boundary B1 between the region where tin hydroxide [Sn(OH) 2 ] is stably present and the region where stannate ion [SnO 3 2 ⁇ ] is stably present, varies depending on the temperature of the aqueous solution. do not.
  • the pH of the electrolyte solution 9 is, for example, 12.3 or higher, and more preferably, for example, 12.4 or higher, or for example, 12.5 or higher.
  • the configuration is very preferable.
  • the presence of tin hydroxide [Sn(OH) 2 ] which is an insoluble solid, can be suppressed.
  • the pH of the electrolyte solution 9 may be 12.8 or higher as in the present embodiment.
  • the pH of the electrolytic solution 9 may be 14.0 or less as in the present embodiment.
  • the surface of the positive electrode 12 is in contact with the permeable membrane 11 .
  • tin hydroxide which is an insoluble solid
  • the electrolytic solution 9 may contain a buffer substance. Thereby, it is possible to suppress the pH of the electrolytic solution 9 from fluctuating due to the influence of the acid gas.
  • buffers containing buffer substances include phosphate buffers, KCl-NaOH buffers, and the like.
  • the product generated by the electrode reaction may eventually become zinc oxide (ZnO) (Zn ⁇ Zn 2+ ⁇ Zn(OH) 2 and , ZnO).
  • ZnO zinc oxide
  • the zinc oxide may act as a photocatalyst and generate hydrogen.
  • the permeable membrane 11 swells, so that a gap is generated between the positive electrode 12 and the permeable membrane 11 .
  • the oxygen sensor 5 cannot properly measure the dissolved oxygen in the target liquid.
  • the negative electrode 13 contains tin, it does not have a catalytic function to generate hydrogen in the electrolytic solution 9. It is possible to suppress the occurrence of gaps between them.
  • the water quality measuring device 1 includes the oxygen sensor 5 .
  • the oxygen sensor 5 has the electrolyte 9 and the opening 10a, the liquid containing portion 10 for containing the electrolyte 9, the oxygen permeability, and the opening 10a. and a positive electrode 12 and a negative electrode 13 arranged so as to be in contact with the electrolytic solution 9, wherein the negative electrode 13 contains tin and the electrolytic solution 9 contains a polyol. preferable.
  • the solidification point of the electrolyte 9 is lower than 0°C. Therefore, when the temperature of the target liquid is higher than the freezing point of the electrolytic solution 9, freezing of the electrolytic solution 9 can be suppressed. Therefore, it is possible to properly measure the dissolved oxygen in the target liquid with a low temperature.
  • the polyol preferably contains at least one of glycerol, erythritol, sorbitol, ethylene glycol, and propanediol.
  • the positive electrode 12 contains at least one of gold, silver, platinum, and carbon, and the electrolyte 9 has a pH of 12.2 or higher. is preferable.
  • the negative electrode 13 contains tin
  • the positive electrode 12 contains at least one of gold, silver, platinum, and carbon
  • the pH of the electrolytic solution 9 is 12.2 or higher.
  • the potential generated above can suppress the generation of insoluble solid tin hydroxide. This can prevent tin hydroxide from covering the surfaces of the electrodes 12 and 13 .
  • the oxygen sensor 5 further includes a holding portion 15 that holds the positive electrode 12 and the negative electrode 13, the negative electrode 13 is formed in a cylindrical shape, and the holding portion 15 is a distal end portion. is arranged inside the negative electrode 13 so as to protrude from the negative electrode 13 , and the surface of the positive electrode 12 is arranged at the tip of the holding portion 15 .
  • the negative electrode 13 is formed in a cylindrical shape, the surface area of the negative electrode 13 can be increased with respect to the surface area of the positive electrode 12, so that the electrochemical reaction can occur efficiently. can. Moreover, since it is possible to suppress the volume of the negative electrode 13 from increasing, it is possible to suppress the oxygen sensor 5 from increasing in size.
  • the minimum distance W1 between the surface of the positive electrode 12 and the surface of the negative electrode 13 is preferably 4.5 mm or less.
  • the minimum distance W1 between the surface of the positive electrode 12 and the surface of the negative electrode 13 is 4.5 mm or less. It is possible to suppress the occurrence of a difference. As a result, it is possible to suppress the occurrence of measurement errors in the dissolved oxygen content.
  • the minimum distance W2 between the surface of the negative electrode 13 and the permeable film 11 is 4.0 mm or less.
  • the minimum distance W2 between the surface of the negative electrode 13 and the permeable membrane 11 is 4.0 mm or less, the temperature of the positive electrode 12 and the temperature of the negative electrode 13 approach the temperature of the target liquid. Become. As a result, it is possible to suppress the occurrence of a difference between the temperature of the positive electrode 12 and the temperature of the negative electrode 13, and thus it is possible to suppress the occurrence of an error in measuring the amount of dissolved oxygen.
  • the water quality measuring device 1, the oxygen sensor 5, and the oxygen measuring method are not limited to the configurations of the above-described embodiments, nor are they limited to the above-described effects. Further, the water quality measuring device 1, the oxygen sensor 5, and the oxygen measuring method can of course be modified in various ways without departing from the gist of the present invention. For example, it is of course possible to arbitrarily select one or a plurality of configurations, methods, etc., according to various modified examples described below and employ them in the configurations, methods, etc., according to the above-described embodiment.
  • the negative electrode 13 is configured to be cylindrical.
  • the oxygen sensor 5 is not limited to such a configuration.
  • the negative electrode 13 may be formed in a plate shape.

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PCT/JP2022/031052 2021-08-27 2022-08-17 酸素センサ、水質測定装置及び酸素測定方法 Ceased WO2023026918A1 (ja)

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CN202280057116.1A CN117836619A (zh) 2021-08-27 2022-08-17 氧传感器、水质测定装置和氧测定方法
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP7440691B1 (ja) 2023-06-29 2024-02-28 理研計器株式会社 電気化学式ガスセンサ、電気化学式ガス測定方法
JP7446509B1 (ja) 2023-06-29 2024-03-08 理研計器株式会社 電気化学式ガスセンサ、電気化学式ガス測定方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268370A (en) * 1980-01-11 1981-05-19 Beckman Instruments, Inc. High temperature, CO2 interference free, electrochemical O2 sensor
JPH0666761A (ja) * 1992-08-18 1994-03-11 Mitsubishi Electric Corp ガルバニ電池式ガスセンサ
JP2004132915A (ja) * 2002-10-15 2004-04-30 Oji Keisoku Kiki Kk 微生物電極、微生物電極用酸素電極及びそれを用いる測定装置
JP2006300530A (ja) * 2005-04-15 2006-11-02 Fuji Electric Systems Co Ltd 溶存酸素センサ
WO2009069749A1 (ja) * 2007-11-28 2009-06-04 Gs Yuasa Corporation 電気化学式酸素センサ
JP2016161395A (ja) * 2015-03-02 2016-09-05 ハネウェル・インターナショナル・インコーポレーテッド 無鉛ガルバニ式酸素センサー
JP2016534360A (ja) * 2013-09-09 2016-11-04 ドレーガー セイフティー アクチエンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト アウフ アクチエン 電気化学式ガスセンサ、液体電解質及び液体電解質の使用
JP2018059719A (ja) * 2016-09-30 2018-04-12 株式会社Ｇｓユアサ 電気化学式酸素センサ
JP2018173375A (ja) * 2017-03-31 2018-11-08 マクセル株式会社 酸素センサ

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0546291A1 (de) * 1991-12-11 1993-06-16 Drägerwerk Aktiengesellschaft Elektrochemische Messzelle zur Bestimmung von Ammoniak oder Hydrazin in einer Messprobe
US20150219583A1 (en) * 2014-02-06 2015-08-06 Honeywell International Inc. Lead-free galvanic oxygen sensor
JP6537491B2 (ja) * 2016-12-28 2019-07-03 マクセル株式会社 電気化学式酸素センサ

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268370A (en) * 1980-01-11 1981-05-19 Beckman Instruments, Inc. High temperature, CO2 interference free, electrochemical O2 sensor
JPH0666761A (ja) * 1992-08-18 1994-03-11 Mitsubishi Electric Corp ガルバニ電池式ガスセンサ
JP2004132915A (ja) * 2002-10-15 2004-04-30 Oji Keisoku Kiki Kk 微生物電極、微生物電極用酸素電極及びそれを用いる測定装置
JP2006300530A (ja) * 2005-04-15 2006-11-02 Fuji Electric Systems Co Ltd 溶存酸素センサ
WO2009069749A1 (ja) * 2007-11-28 2009-06-04 Gs Yuasa Corporation 電気化学式酸素センサ
JP2016534360A (ja) * 2013-09-09 2016-11-04 ドレーガー セイフティー アクチエンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト アウフ アクチエン 電気化学式ガスセンサ、液体電解質及び液体電解質の使用
JP2016161395A (ja) * 2015-03-02 2016-09-05 ハネウェル・インターナショナル・インコーポレーテッド 無鉛ガルバニ式酸素センサー
JP2018059719A (ja) * 2016-09-30 2018-04-12 株式会社Ｇｓユアサ 電気化学式酸素センサ
JP2018173375A (ja) * 2017-03-31 2018-11-08 マクセル株式会社 酸素センサ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7440691B1 (ja) 2023-06-29 2024-02-28 理研計器株式会社 電気化学式ガスセンサ、電気化学式ガス測定方法
JP7446509B1 (ja) 2023-06-29 2024-03-08 理研計器株式会社 電気化学式ガスセンサ、電気化学式ガス測定方法

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