WO1985002465A1 - Electrochemical sensing of carbon monoxide - Google Patents

Electrochemical sensing of carbon monoxide Download PDF

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Publication number
WO1985002465A1
WO1985002465A1 PCT/US1984/001954 US8401954W WO8502465A1 WO 1985002465 A1 WO1985002465 A1 WO 1985002465A1 US 8401954 W US8401954 W US 8401954W WO 8502465 A1 WO8502465 A1 WO 8502465A1
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solution
electrolyte
cell means
solvent
electrode
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PCT/US1984/001954
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French (fr)
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Hanumanthaiya V. Venkatasetty
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Honeywell Inc.
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Application filed by Honeywell Inc. filed Critical Honeywell Inc.
Priority to JP60500129A priority Critical patent/JPS61500566A/en
Priority to DE8585900346T priority patent/DE3478954D1/en
Publication of WO1985002465A1 publication Critical patent/WO1985002465A1/en
Priority to DK350085A priority patent/DK350085D0/en

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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
    • G01N27/403—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
    • G01N27/4045—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 for gases other than oxygen

Definitions

  • Aprotic Organic Electrolyte Solution involves an el ectrochemical cell utilizing nonaqueous electrolyte solutions with aprotic solvents. An electrochemical oxidation process at the platinum electrode is imployed for the detection of small amounts of chemical agent simulants such as dimethyl methyl phosphonate (DMMP) and diethyl malonate (DEM) in the electrolyte solution.
  • Electrolyte solutions include propylene carbonate or ⁇ -butyrolactone containing lithium perchlorate or tetraethylammonium perchlorate.
  • the present invention involves the detection of carbon monoxide (CO) electrochemically using a gelled electrolyte containing an amount of polyethylene oxide.
  • An electrolyte solution of approximately 1.0M lithium perchlorate (LiClO 4 ) in y-butyrolactone or approximately 0.75M LiClO 4 in propylene carbonate when gelled with polyethylene oxide has been found to be especially suited to the detection of CO by oxidation at the platinum electrode.
  • BACKGROUND OF THE INVENTION Electrochemical reactions based on oxidation or reduction (redox) of metals and compounds at an electrode are highly selective because of the characteristic redox potential at which oxidation or reduction of the electroactive species occurs. With electrochemical sensing, selection of the electrode material and electrolyte solution has been very important in determining sensitivity and selectivity. A detailed description of the theoretical considerations is contained in the above cross-referenced application and is incorporated by reference in this application to the extent required.
  • an electrochemical detection system has been developedwhich is extremely sensitive to the presence of CO and can also be used to detect other toxic gases such as nitrogen oxides (N 2 O 4 , NO x ) SO 2 , H 2 S and the like.
  • the system includes a nonaqueous, aprotic electrolyte system of approximately 1.0M LiClO4 in ⁇ -butyrolactone or approximately 0.75M LiClO 4 in propylene carbonate gelled with a small amount of polyethylene oxide (about 1% by weight based on the other constituents).
  • a platinum electrode is used on the oxidation site for the gas detection.
  • the polymer containing electrolyte solutions have high electrolytic conductivity, low vapor pressure, high solubility for carbon monoxide and high chemical and electrochemical stability.
  • the electrolyte solution and electrodes can be packaged into a low-cost electrochemical cell for detecting carbon monoxide or other gases using a semipermeable membrane coated on one side with platinum metal film as the sensing electrode.
  • the polymer based electrolyte solution can be easily contained in the cell assuring long shelf life.
  • FIGURES 1 and la are schematic diagrams of an electrochemical cell for demonstrating the invention.
  • FIGURE 2 is a graphical presentation of specific conductance vs. concentraction (25°C) of several electrolytes in nonaqueous solvents.
  • FIGURE 3 is a graphical presentation of potential ranges available in nonaqueous vs. aqueous electrolyte solutions.
  • FIGURES 4 and 5 show graphical plots of the sensor response to CO.
  • FIGURE 1 generally illustrates an electrochemical cell 10 consisting of a chamber 11 having a semipermeable membrane 12 across an opening.
  • the chamber 11 contains a film of platinum working or sensing electrode 14, a counter electrode 15 of platinum film and a Ag/Ag+ reference electrode 16.
  • An adjustable potential source 20 is connected across the sensing and counter electrode and the current is measured. A voltage exists but no current flows from the reference electrode to the sensing electrode.
  • a preferred form of this energizing circuit may include an operational amplifier as shown in Figure 1a wherein no current flows in the feedback loop from the reference electrode to the negative input of the operational amplifier.
  • the three electrodes are internally separated by a material which also acts as a wicking material for the electrolyte.
  • a gelled nonaqueous electrolyte solution 17 permeates and fills the chamber.
  • This solution utilizes an aprotic organic solvent such as propylene carbonate or y-butyrolactone and an active electrolyte such as LiClO 4 which has a wide potential window so that gases sought to be detected can be oxidized or reduced without decomposing the electrolyte solution.
  • the electrolyte solvent should be aprotic (no replaceable hydrogen atoms) and it should have a high boiling point, low freezing point to provide a wide operating temperature range between boiling point and freezing point, and low vapor pressure so that it is stable.
  • the solvent should have a fairly high dielectric constant and low viscosity so that the solutes are easily soluble, giving solutions with fairly high conductivity.
  • the solvent and electrolyte solutions from such solvents should be electrochemically stable to oxidation and reduction, giving a wide voltage window to carry out electrochemical redox reactions at an electrode surface.
  • the solvent should be low cost, should be easily purified, and should be nontoxic.
  • the following solvents have been chosen for the electrolyte system of the invention. Propylene
  • the electrochemical method for the quantitative determination of materials is based on the principle of limiting current density measured at the electrode surface.
  • Limiting current density is defined as the current density resulting from the oxidation or reduction of every molecule of the electroactive material or chemical agent reaching the electrode surface.
  • a linear relationship between the limiting current density (i L ) and the bulk concentration (C b ) of the electroactive material or chemical agent can beobtained using Fick's law of diffusion
  • D is the diffusion coefficient of the electroactive molecules in the electrolyte
  • n is the number of electrons involved
  • F is the Faraday constant
  • ⁇ is the diffusion layer thickness.
  • FIGURE 3 shows graphically a sample comparison of potential ranges available in nonaqueous vs. aqueous electrolyte solutions.
  • Aqueous electrolytes are limited to a voltage range of about 1.5 volts of redox potential as shown in the figure. The presence of protons in aqueous based electrolytes interferes with redox processes of organic molecules, even within this range.
  • Aprotic electrolytes (nonaqueous) contain no protons and can achieve three times the voltage range of aqueous electrolytes, or about 4.5 volts as shown.
  • Nonaqueous organic electrolytes are preferable for the analysis of CO and organic compounds such as chemical agents which are more soluble in organic electrolyte solutions compared to aqueous electrolyte solutions.
  • Electrochemical experiments have been conducted to demonstrate the feasibility of nonaqueous electrochemical redox techniques for the detection and identification of simulants for chemical agents.
  • Concentrated solutions of supporting electrolytes such as 0.5M lithium perchlorate (LiClO 4 ) and 0.1M tetraethylammonium perchlorate (TEAP) in propylene carbonate (PC) or ⁇ -butyrolactone were prepared and used in a conventional electrochemical setup.
  • the sensing and counter electrodes were platinum and the reference electrode was Ag/Ag+.
  • the preferred solvent was y-butyrolactone.
  • the preferred electrolyte/solvent system is 1M LiClO 4 in ⁇ -butyrolactone.
  • the electrochemical instrumentation consisted of a Princeton Applied Research Model 173 potentiostat/galvanostat with a Model 175 Universal Programmer, Model 179 digital Coulometer, and Hewlett-Packard Model 7040A x-y recorder.
  • the gelled nonaqueous electrolyte solution is prepared by dissolving 1% (by wt.) of the polymer, polyethylene oxide (Molecular weight approximately 100,000) in 1.0M LiClO 4 in ⁇ -butyrolactone or 0.75M LiClO 4 in propylene carbonate.
  • the solution in ⁇ -butyrolactone has specific conductivity of 9 ⁇ 89x10 -3 ohm -1 cm -1 whereas the solution in propylene carbonate has specific conductivity of 5.389x10 -3 ohm -1 cm -1 at 25°C.
  • These solutions can be used as media for the dissolution of carbon monoxide gas and the carbon monoxide gas can be oxidized at the platinum electrode surface at a known potential.
  • electrolyte solutions are stable to electrochemical oxidation and reduction within the potential range of interest to carbon monoxide detection.
  • the gelled electrolyte solutions do not flow through, semipermeable membranes like PTFE (polytetrafluoroethylene) that are used in low cost carbon monoxide sensors and, therefore, the cells can be made to last longer.
  • PTFE polytetrafluoroethylene
  • the polymer containing electrolyte solutions can be packaged easily for sensing CO.
  • H 2 S should produce distinct results also.
  • the three electrode configuration cell structure shown in Figure 1 is set up with a small amount of the electrolyte solution ( ⁇ 1cc) with arrangement to apply a known potential and measuring the current generated.
  • the carbon monoxide gas is allowed to enter the cell through the semipermeable membrane and establish equilibrium state.
  • the electroactive species namely CO around the sensing anode is completely oxidized and the current-concentration relationship can be established according to the relationship.

Abstract

Apparatus and method for an electrochemical sensor for carbon monoxide detection in a gelled aprotic organic nonaqueous electrolyte solution.

Description

ELECTROCHEMICAL SEN SING OF CARBON MONOXIDE
CROSS REFERENCE TO RELATED APPLICATION
Cross reference is made to application Serial Number 557,037, filed of even date, entitled "An Electrochemical Sensor for Multiagent Detection in
Aprotic Organic Electrolyte Solution". That application also is by H. V. Venkatasetty, the inventor in this application and is assigned to the same assignee as the present application. That invention involves an el ectrochemical cell utilizing nonaqueous electrolyte solutions with aprotic solvents. An electrochemical oxidation process at the platinum electrode is imployed for the detection of small amounts of chemical agent simulants such as dimethyl methyl phosphonate (DMMP) and diethyl malonate (DEM) in the electrolyte solution. Electrolyte solutions include propylene carbonate or γ-butyrolactone containing lithium perchlorate or tetraethylammonium perchlorate. The present invention, on the other hand, involves the detection of carbon monoxide (CO) electrochemically using a gelled electrolyte containing an amount of polyethylene oxide. An electrolyte solution of approximately 1.0M lithium perchlorate (LiClO4) in y-butyrolactone or approximately 0.75M LiClO4 in propylene carbonate when gelled with polyethylene oxide has been found to be especially suited to the detection of CO by oxidation at the platinum electrode. BACKGROUND OF THE INVENTION Electrochemical reactions based on oxidation or reduction (redox) of metals and compounds at an electrode are highly selective because of the characteristic redox potential at which oxidation or reduction of the electroactive species occurs. With electrochemical sensing, selection of the electrode material and electrolyte solution has been very important in determining sensitivity and selectivity. A detailed description of the theoretical considerations is contained in the above cross-referenced application and is incorporated by reference in this application to the extent required.
One limitation of the prior art is that the presence of hydrogen ions, either in the solvent or in the additive (electrolyte), will interfere with the oxidation and reduction of chemical agents sought to be detected. This has lead to the necessity for developing aprotic (free of replaceable hydrogen ions) electrolyte systems.
SUMMARY OF THE INVENTION By means of the present invention, an electrochemical detection system has been developedwhich is extremely sensitive to the presence of CO and can also be used to detect other toxic gases such as nitrogen oxides (N2O4, NOx) SO2, H2S and the like. The system includes a nonaqueous, aprotic electrolyte system of approximately 1.0M LiClO4 in γ-butyrolactone or approximately 0.75M LiClO4 in propylene carbonate gelled with a small amount of polyethylene oxide (about 1% by weight based on the other constituents). A platinum electrode is used on the oxidation site for the gas detection. The polymer containing electrolyte solutions have high electrolytic conductivity, low vapor pressure, high solubility for carbon monoxide and high chemical and electrochemical stability. The electrolyte solution and electrodes can be packaged into a low-cost electrochemical cell for detecting carbon monoxide or other gases using a semipermeable membrane coated on one side with platinum metal film as the sensing electrode. The polymer based electrolyte solution can be easily contained in the cell assuring long shelf life.
BRIEF DESCRIPTION OF THE DRAWINGS FIGURES 1 and la are schematic diagrams of an electrochemical cell for demonstrating the invention.
FIGURE 2 is a graphical presentation of specific conductance vs. concentraction (25°C) of several electrolytes in nonaqueous solvents. FIGURE 3 is a graphical presentation of potential ranges available in nonaqueous vs. aqueous electrolyte solutions.
FIGURES 4 and 5 show graphical plots of the sensor response to CO.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGURE 1 generally illustrates an electrochemical cell 10 consisting of a chamber 11 having a semipermeable membrane 12 across an opening. The chamber 11 contains a film of platinum working or sensing electrode 14, a counter electrode 15 of platinum film and a Ag/Ag+ reference electrode 16. An adjustable potential source 20 is connected across the sensing and counter electrode and the current is measured. A voltage exists but no current flows from the reference electrode to the sensing electrode. A preferred form of this energizing circuit may include an operational amplifier as shown in Figure 1a wherein no current flows in the feedback loop from the reference electrode to the negative input of the operational amplifier. The three electrodes are internally separated by a material which also acts as a wicking material for the electrolyte. A gelled nonaqueous electrolyte solution 17 permeates and fills the chamber. This solution utilizes an aprotic organic solvent such as propylene carbonate or y-butyrolactone and an active electrolyte such as LiClO4 which has a wide potential window so that gases sought to be detected can be oxidized or reduced without decomposing the electrolyte solution.
A previously stated, the electrolyte solvent should be aprotic (no replaceable hydrogen atoms) and it should have a high boiling point, low freezing point to provide a wide operating temperature range between boiling point and freezing point, and low vapor pressure so that it is stable. The solvent should have a fairly high dielectric constant and low viscosity so that the solutes are easily soluble, giving solutions with fairly high conductivity. The solvent and electrolyte solutions from such solvents should be electrochemically stable to oxidation and reduction, giving a wide voltage window to carry out electrochemical redox reactions at an electrode surface. The solvent should be low cost, should be easily purified, and should be nontoxic. The following solvents have been chosen for the electrolyte system of the invention. Propylene
Properties Carbonate y-Butyrolactons
Boiling point (°C) 241 202
Freezing point (ºC) -49 -43
Dielectric constant 64.4(25ºC) 39(20°C)
Viscosity mP (25ºC) 25.3 17.5
Density (25°C) g/ml 1.19 1.13
The conductivity concentration studies carried out using lithium perchlorate solute as the supporting electrolyte in propylene carbonate show a maximum conductivity at about 0.75M (Figure 2, curve A) whereas similar studies in the preferred y-butyrolactone show a much higher maximum conductivity at about 1M (Figure 2, curve B). As seen from the above, solvents such as propylene carbonate or y-butyrolactone have a high boiling point, low melting point, and very low vapor pressure. They are also non-corrosive so that the electrochemical cell can operate over a wide temperature range for an extended period. Gases such as CO are highly soluble in these nonaqueous organic solvents making for high sensitivity of detection.
With the wide range of potential window available for oxidation and reduction, many gases can be oxidized or reduced in the same cell so that the electrochemical cell can be used for different gases of interest.
The electrochemical method for the quantitative determination of materials is based on the principle of limiting current density measured at the electrode surface. Limiting current density is defined as the current density resulting from the oxidation or reduction of every molecule of the electroactive material or chemical agent reaching the electrode surface. A linear relationship between the limiting current density (iL) and the bulk concentration (Cb) of the electroactive material or chemical agent can beobtained using Fick's law of diffusion
Figure imgf000008_0001
where D is the diffusion coefficient of the electroactive molecules in the electrolyte, n is the number of electrons involved, F is the Faraday constant, andδis the diffusion layer thickness. Thus, the limiting current density provides the quantitative measure of the concentration, while the characteristic redox potential identifies the molecules.
FIGURE 3 shows graphically a sample comparison of potential ranges available in nonaqueous vs. aqueous electrolyte solutions. Aqueous electrolytes are limited to a voltage range of about 1.5 volts of redox potential as shown in the figure. The presence of protons in aqueous based electrolytes interferes with redox processes of organic molecules, even within this range. Aprotic electrolytes (nonaqueous) contain no protons and can achieve three times the voltage range of aqueous electrolytes, or about 4.5 volts as shown. Nonaqueous organic electrolytes are preferable for the analysis of CO and organic compounds such as chemical agents which are more soluble in organic electrolyte solutions compared to aqueous electrolyte solutions. Electrochemical experiments have been conducted to demonstrate the feasibility of nonaqueous electrochemical redox techniques for the detection and identification of simulants for chemical agents. Concentrated solutions of supporting electrolytes such as 0.5M lithium perchlorate (LiClO4) and 0.1M tetraethylammonium perchlorate (TEAP) in propylene carbonate (PC) or γ-butyrolactone were prepared and used in a conventional electrochemical setup. The sensing and counter electrodes were platinum and the reference electrode was Ag/Ag+. The preferred solvent was y-butyrolactone. The preferred electrolyte/solvent system is 1M LiClO4 in γ-butyrolactone. The electrochemical instrumentation consisted of a Princeton Applied Research Model 173 potentiostat/galvanostat with a Model 175 Universal Programmer, Model 179 digital Coulometer, and Hewlett-Packard Model 7040A x-y recorder.
The gelled nonaqueous electrolyte solution is prepared by dissolving 1% (by wt.) of the polymer, polyethylene oxide (Molecular weight approximately 100,000) in 1.0M LiClO4 in γ-butyrolactone or 0.75M LiClO4 in propylene carbonate. The solution in γ-butyrolactone has specific conductivity of 9·89x10-3ohm-1cm-1 whereas the solution in propylene carbonate has specific conductivity of 5.389x10-3ohm-1cm-1 at 25°C. These solutions can be used as media for the dissolution of carbon monoxide gas and the carbon monoxide gas can be oxidized at the platinum electrode surface at a known potential. In the caes of propylene carbonate solution, carbon monoxide can be oxidized at +1.25 to +1.30V VsAg/Ag+ whereas in γ-butyrolactone solution, carbon monoxide can be oxidized at +1.20V VsAg/Ag+. This is illustrated in Figures 4 and 5, respectively. The oxidation shown beyond 1.3V (curve f of Figure 4) and 1.2V (curve g of Figure 5) are due to oxidation of other components at higher potentials. The very sharp, distinct change in current is very accurate and repeatable. The current generated at these oxidation potential (s) is proportional to the concentration of carbon monoxide in the electrolyte solution. These electrolyte solutions are stable to electrochemical oxidation and reduction within the potential range of interest to carbon monoxide detection. The gelled electrolyte solutions do not flow through, semipermeable membranes like PTFE (polytetrafluoroethylene) that are used in low cost carbon monoxide sensors and, therefore, the cells can be made to last longer. The polymer containing electrolyte solutions can be packaged easily for sensing CO.
While the invention has been particularly described with reference to CO, other gases such as oxide of nitrogen (N2O4, NOx) and gases such as SO2 and
H2S should produce distinct results also. The three electrode configuration cell structure shown in Figure 1 is set up with a small amount of the electrolyte solution (~1cc) with arrangement to apply a known potential and measuring the current generated. The carbon monoxide gas is allowed to enter the cell through the semipermeable membrane and establish equilibrium state. By applying a potential slightly higher than the oxidation value, the electroactive species, namely CO around the sensing anode is completely oxidized and the current-concentration relationship can be established according to the relationship.

Claims

CLAIMSThe embodiments of the invention in which an exclusive property or right is claimed are defined as follows:
1. An electrochemical sensor for toxic gas detection comprising: electrochemical cell means having therein an electrode configuration comprising a plurality of noble metal electrodes including sensing electrode and a platinum counter electrode and an Ag/Ag+ reference electrode; a nonaqueous gelled electrolyte solution in said cell means, said solution comprising an aprotic organic solvent based solution wherein said solvent is selected from the group consisting of γ-butyrolactone and propylene carbonate the solution also containing an amount of lithium perchlorate electrolyte, the gelled solution also containing an amount of polyethylene oxide as the gelling agent; and adjustable potential electrical source means, to energize said electroch emical cell means at desired potentials, connected across said working and counter electrodes.
2. The apparatus according to claim 1 wherein the nonaqueous electrolyte solvent is y-butyrolactone and said electrolyte is lithium perchlorate (LiClO4) having a concentrate of about 1.0M based on the solvent.
3. The apparatus according to claim 1 wherein the nonaqueous electrolyte solvent is propylene carbonate and said electrolyte is LiClO4 having a concentration of about 0.75M.
4. The apparatus according to claim 2 wherein the amount of said polyethylene oxide is about 1% by weight based on the weight of the solution.
5. The apparatus according to claim 3 wherein the amount of said polyethylene oxide is about 1% by weight based on the weight of the solution.
6. A method for detecting the presence of a plurality of toxic agents comprising the steps of: providing electrochemical cell means having an electrode configuration comprising a plurality of electrodes; providing a nonaqueous gelled electrolyte solution in the electrochemical cell means, said solution comprising an aprotic organic solvent selected from the group consisting of γ-butyrolactone and propylene carbonate, the solution also containing an amount of lithium perchlorate electrolyte and polyethylene oxide gelling agent; exposing the electrochemical cell means to an atmosphere suspected of containing the gas sought to be detected; providing electrical source means and connecting the source means to the electrode configuration to energize the cell means.
PCT/US1984/001954 1983-12-01 1984-11-28 Electrochemical sensing of carbon monoxide WO1985002465A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP60500129A JPS61500566A (en) 1983-12-01 1984-11-28 Electrochemical detection of carbon monoxide
DE8585900346T DE3478954D1 (en) 1983-12-01 1984-11-28 Electrochemical sensing of carbon monoxide
DK350085A DK350085D0 (en) 1983-12-01 1985-08-01 ELECTROCHEMICAL DETECTION OF CARBON MONOXIDE

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US06/557,072 US4522690A (en) 1983-12-01 1983-12-01 Electrochemical sensing of carbon monoxide
US557,072 1983-12-01

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0237914A2 (en) * 1986-03-20 1987-09-23 Bayer Diagnostic GmbH Method of producing electrochemical gas sensors
GB2277378A (en) * 1993-03-05 1994-10-26 Mine Safety Appliances Co Electrochemical membrane gas sensor
EP0740149A1 (en) * 1995-04-26 1996-10-30 ProMinent Dosiertechnik GmbH Electrochemical sensor
GB2303710A (en) * 1993-03-05 1997-02-26 Mine Safety Appliances Co Electrochemical toxic gas sensor with gas permeable membrane

Families Citing this family (107)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4591414A (en) * 1984-08-27 1986-05-27 The United States Of America As Represented By The United States Department Of Energy Method of determining methane and electrochemical sensor therefor
EP0218694A1 (en) * 1985-04-19 1987-04-22 The Regents Of The University Of California Transparent multi-oxygen sensor array
US4781798A (en) * 1985-04-19 1988-11-01 The Regents Of The University Of California Transparent multi-oxygen sensor array and method of using same
US4662996A (en) * 1985-12-20 1987-05-05 Honeywell Inc. Method and electrochemical sensor for sensing chemical agents using a sensing elctrode coated with electrically conductive polymers
US4744954A (en) * 1986-07-11 1988-05-17 Allied-Signal Inc. Amperometric gas sensor containing a solid electrolyte
US4851088A (en) * 1987-03-05 1989-07-25 Honeywell Inc. Electrochemical detection of carbon dioxide
US4948490A (en) * 1988-02-19 1990-08-14 Honeywell Inc. Tetraalkylammonium ion solid electrolytes
US5173166A (en) * 1990-04-16 1992-12-22 Minitech Co. Electrochemical gas sensor cells
US5302274A (en) * 1990-04-16 1994-04-12 Minitech Co. Electrochemical gas sensor cells using three dimensional sensing electrodes
CA2050057A1 (en) 1991-03-04 1992-09-05 Adam Heller Interferant eliminating biosensors
US5593852A (en) 1993-12-02 1997-01-14 Heller; Adam Subcutaneous glucose electrode
US5497772A (en) * 1993-11-19 1996-03-12 Alfred E. Mann Foundation For Scientific Research Glucose monitoring system
US5791344A (en) * 1993-11-19 1998-08-11 Alfred E. Mann Foundation For Scientific Research Patient monitoring system
WO1995014226A1 (en) * 1993-11-19 1995-05-26 Ceramatec, Inc. Multi-functional sensor for combustion systems
US6051123A (en) * 1995-06-15 2000-04-18 Gas Research Institute Multi-functional and NOx sensor for combustion systems
US5591896A (en) * 1995-11-02 1997-01-07 Lin; Gang Solid-state gas sensors
US5746900A (en) * 1996-03-07 1998-05-05 H.V. Setty Enterprises, Inc. Non-aqueous amperometric multi-gas sensor
GB2323673B (en) * 1996-03-15 2000-01-12 Mine Safety Appliances Co Electrochemical sensor with a non-aqueous electrolyte system
US6488826B2 (en) * 1996-12-09 2002-12-03 Patrick Altmeier Fluid electrode system for resistive slope sensors
JP3394262B2 (en) * 1997-02-06 2003-04-07 セラセンス、インク． Small volume in vitro analyte sensor
US6001240A (en) * 1997-07-02 1999-12-14 Mine Safety Appliances Company Electrochemical detection of hydrogen cyanide
US6098523A (en) * 1997-07-10 2000-08-08 Draeger Safety, Inc. Testing apparatus for gas sensors
CA2215108C (en) * 1997-09-11 1999-10-26 Senco Sensors Inc. Electrochemical gas sensor
CA2245050C (en) * 1997-09-11 2000-09-05 Kehoe Component Sales Inc. Dba Pace Electronic Products Inc. Three-electrode electrochemical gas sensor
US6103033A (en) 1998-03-04 2000-08-15 Therasense, Inc. Process for producing an electrochemical biosensor
US6134461A (en) * 1998-03-04 2000-10-17 E. Heller & Company Electrochemical analyte
US8480580B2 (en) 1998-04-30 2013-07-09 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8974386B2 (en) 1998-04-30 2015-03-10 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8688188B2 (en) 1998-04-30 2014-04-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8465425B2 (en) 1998-04-30 2013-06-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US6175752B1 (en) 1998-04-30 2001-01-16 Therasense, Inc. Analyte monitoring device and methods of use
US8346337B2 (en) 1998-04-30 2013-01-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9066695B2 (en) 1998-04-30 2015-06-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US6949816B2 (en) 2003-04-21 2005-09-27 Motorola, Inc. Semiconductor component having first surface area for electrically coupling to a semiconductor chip and second surface area for electrically coupling to a substrate, and method of manufacturing same
US6251260B1 (en) 1998-08-24 2001-06-26 Therasense, Inc. Potentiometric sensors for analytic determination
US6591125B1 (en) 2000-06-27 2003-07-08 Therasense, Inc. Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
US6338790B1 (en) 1998-10-08 2002-01-15 Therasense, Inc. Small volume in vitro analyte sensor with diffusible or non-leachable redox mediator
EP2322645A1 (en) 1999-06-18 2011-05-18 Abbott Diabetes Care Inc. Mass transport limited in vivo analyte sensor
US6616819B1 (en) 1999-11-04 2003-09-09 Therasense, Inc. Small volume in vitro analyte sensor and methods
US6560471B1 (en) 2001-01-02 2003-05-06 Therasense, Inc. Analyte monitoring device and methods of use
JP3718467B2 (en) * 2001-03-28 2005-11-24 株式会社東芝 Non-aqueous electrolyte and non-aqueous electrolyte secondary battery
WO2002078512A2 (en) 2001-04-02 2002-10-10 Therasense, Inc. Blood glucose tracking apparatus and methods
US7381184B2 (en) 2002-11-05 2008-06-03 Abbott Diabetes Care Inc. Sensor inserter assembly
EP2305813A3 (en) * 2002-11-14 2012-03-28 Dharmacon, Inc. Fuctional and hyperfunctional sirna
US7811231B2 (en) 2002-12-31 2010-10-12 Abbott Diabetes Care Inc. Continuous glucose monitoring system and methods of use
US8066639B2 (en) 2003-06-10 2011-11-29 Abbott Diabetes Care Inc. Glucose measuring device for use in personal area network
USD914881S1 (en) 2003-11-05 2021-03-30 Abbott Diabetes Care Inc. Analyte sensor electronic mount
WO2005089103A2 (en) 2004-02-17 2005-09-29 Therasense, Inc. Method and system for providing data communication in continuous glucose monitoring and management system
US9788771B2 (en) 2006-10-23 2017-10-17 Abbott Diabetes Care Inc. Variable speed sensor insertion devices and methods of use
US8512243B2 (en) 2005-09-30 2013-08-20 Abbott Diabetes Care Inc. Integrated introducer and transmitter assembly and methods of use
US9572534B2 (en) 2010-06-29 2017-02-21 Abbott Diabetes Care Inc. Devices, systems and methods for on-skin or on-body mounting of medical devices
US9743862B2 (en) 2011-03-31 2017-08-29 Abbott Diabetes Care Inc. Systems and methods for transcutaneously implanting medical devices
US8333714B2 (en) 2006-09-10 2012-12-18 Abbott Diabetes Care Inc. Method and system for providing an integrated analyte sensor insertion device and data processing unit
US7883464B2 (en) 2005-09-30 2011-02-08 Abbott Diabetes Care Inc. Integrated transmitter unit and sensor introducer mechanism and methods of use
US8613703B2 (en) 2007-05-31 2013-12-24 Abbott Diabetes Care Inc. Insertion devices and methods
US20090105569A1 (en) 2006-04-28 2009-04-23 Abbott Diabetes Care, Inc. Introducer Assembly and Methods of Use
US7697967B2 (en) 2005-12-28 2010-04-13 Abbott Diabetes Care Inc. Method and apparatus for providing analyte sensor insertion
US9351669B2 (en) 2009-09-30 2016-05-31 Abbott Diabetes Care Inc. Interconnect for on-body analyte monitoring device
US10226207B2 (en) 2004-12-29 2019-03-12 Abbott Diabetes Care Inc. Sensor inserter having introducer
US7731657B2 (en) 2005-08-30 2010-06-08 Abbott Diabetes Care Inc. Analyte sensor introducer and methods of use
US8571624B2 (en) 2004-12-29 2013-10-29 Abbott Diabetes Care Inc. Method and apparatus for mounting a data transmission device in a communication system
US9398882B2 (en) 2005-09-30 2016-07-26 Abbott Diabetes Care Inc. Method and apparatus for providing analyte sensor and data processing device
US9259175B2 (en) 2006-10-23 2016-02-16 Abbott Diabetes Care, Inc. Flexible patch for fluid delivery and monitoring body analytes
US8112240B2 (en) 2005-04-29 2012-02-07 Abbott Diabetes Care Inc. Method and apparatus for providing leak detection in data monitoring and management systems
US20060278536A1 (en) * 2005-06-10 2006-12-14 The Regents Of The University Of California Sensor comprising supported aprotic ionic liquid
WO2007020410A1 (en) * 2005-08-12 2007-02-22 Isis Innovation Limited Detection of ammonia by electrodes comprising glassy carbon or boron-doped diamond
US9521968B2 (en) 2005-09-30 2016-12-20 Abbott Diabetes Care Inc. Analyte sensor retention mechanism and methods of use
US7766829B2 (en) 2005-11-04 2010-08-03 Abbott Diabetes Care Inc. Method and system for providing basal profile modification in analyte monitoring and management systems
EP1968432A4 (en) 2005-12-28 2009-10-21 Abbott Diabetes Care Inc Medical device insertion
US11298058B2 (en) 2005-12-28 2022-04-12 Abbott Diabetes Care Inc. Method and apparatus for providing analyte sensor insertion
US7885698B2 (en) 2006-02-28 2011-02-08 Abbott Diabetes Care Inc. Method and system for providing continuous calibration of implantable analyte sensors
DE102006014714B3 (en) * 2006-03-30 2007-05-16 Draegerwerk Ag Electrochemical sensor for gas detection has aromatic or alphatic acid carbonic acids in alkali electrolyte solution
DE102006014715B3 (en) * 2006-03-30 2007-06-06 Drägerwerk AG Electrochemical gas sensor for detecting analyte, has mediator that is dissolved in saturated form in electrolytes and is available as precipitate in electrolyte space, and protection electrode arranged at rear of measuring electrode
US7620438B2 (en) 2006-03-31 2009-11-17 Abbott Diabetes Care Inc. Method and system for powering an electronic device
US8226891B2 (en) 2006-03-31 2012-07-24 Abbott Diabetes Care Inc. Analyte monitoring devices and methods therefor
US20080071158A1 (en) 2006-06-07 2008-03-20 Abbott Diabetes Care, Inc. Analyte monitoring system and method
US8732188B2 (en) 2007-02-18 2014-05-20 Abbott Diabetes Care Inc. Method and system for providing contextual based medication dosage determination
US8930203B2 (en) 2007-02-18 2015-01-06 Abbott Diabetes Care Inc. Multi-function analyte test device and methods therefor
US8123686B2 (en) 2007-03-01 2012-02-28 Abbott Diabetes Care Inc. Method and apparatus for providing rolling data in communication systems
US8665091B2 (en) 2007-05-08 2014-03-04 Abbott Diabetes Care Inc. Method and device for determining elapsed sensor life
US7928850B2 (en) 2007-05-08 2011-04-19 Abbott Diabetes Care Inc. Analyte monitoring system and methods
US8461985B2 (en) 2007-05-08 2013-06-11 Abbott Diabetes Care Inc. Analyte monitoring system and methods
US8456301B2 (en) 2007-05-08 2013-06-04 Abbott Diabetes Care Inc. Analyte monitoring system and methods
US8103456B2 (en) 2009-01-29 2012-01-24 Abbott Diabetes Care Inc. Method and device for early signal attenuation detection using blood glucose measurements
US9402544B2 (en) 2009-02-03 2016-08-02 Abbott Diabetes Care Inc. Analyte sensor and apparatus for insertion of the sensor
US20100213057A1 (en) 2009-02-26 2010-08-26 Benjamin Feldman Self-Powered Analyte Sensor
WO2010127050A1 (en) 2009-04-28 2010-11-04 Abbott Diabetes Care Inc. Error detection in critical repeating data in a wireless sensor system
WO2010138856A1 (en) 2009-05-29 2010-12-02 Abbott Diabetes Care Inc. Medical device antenna systems having external antenna configurations
US9314195B2 (en) 2009-08-31 2016-04-19 Abbott Diabetes Care Inc. Analyte signal processing device and methods
EP2473099A4 (en) 2009-08-31 2015-01-14 Abbott Diabetes Care Inc Analyte monitoring system and methods for managing power and noise
WO2011041469A1 (en) 2009-09-29 2011-04-07 Abbott Diabetes Care Inc. Method and apparatus for providing notification function in analyte monitoring systems
USD924406S1 (en) 2010-02-01 2021-07-06 Abbott Diabetes Care Inc. Analyte sensor inserter
JP5904500B2 (en) 2010-03-24 2016-04-13 アボット ダイアベティス ケア インコーポレイテッドＡｂｂｏｔｔ Ｄｉａｂｅｔｅｓ Ｃａｒｅ Ｉｎｃ． Apparatus and system for inserting sharp member under skin surface
US11064921B2 (en) 2010-06-29 2021-07-20 Abbott Diabetes Care Inc. Devices, systems and methods for on-skin or on-body mounting of medical devices
US20120193229A1 (en) * 2011-01-27 2012-08-02 Life Safety Distribution Ag Electrochemical Oxygen Sensor with Internal Barrier to Oxygen Diffusion
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US9402570B2 (en) 2011-12-11 2016-08-02 Abbott Diabetes Care Inc. Analyte sensor devices, connections, and methods
US9459233B2 (en) 2012-06-25 2016-10-04 Steris Corporation Amperometric gas sensor
US9968306B2 (en) 2012-09-17 2018-05-15 Abbott Diabetes Care Inc. Methods and apparatuses for providing adverse condition notification with enhanced wireless communication range in analyte monitoring systems
GB2516932B (en) 2013-08-07 2018-12-26 Nokia Technologies Oy An apparatus and associated methods for water detection
US9983164B1 (en) * 2015-03-18 2018-05-29 Maxim Integrated Products, Inc. Mobile electrochemical air quality meter
US10213139B2 (en) 2015-05-14 2019-02-26 Abbott Diabetes Care Inc. Systems, devices, and methods for assembling an applicator and sensor control device
US10674944B2 (en) 2015-05-14 2020-06-09 Abbott Diabetes Care Inc. Compact medical device inserters and related systems and methods
US11071478B2 (en) 2017-01-23 2021-07-27 Abbott Diabetes Care Inc. Systems, devices and methods for analyte sensor insertion
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260656A (en) * 1962-09-27 1966-07-12 Corning Glass Works Method and apparatus for electrolytically determining a species in a fluid
US3833495A (en) * 1970-09-28 1974-09-03 Gen Electric Reference electrode half cell
US4049503A (en) * 1974-07-27 1977-09-20 Bayer Aktiengesellschaft Electrochemical gas detection
US4141800A (en) * 1976-05-15 1979-02-27 Bayer Aktiengesellschaft Electrochemical gas detector and method of using same
US4149948A (en) * 1976-12-18 1979-04-17 Bayer Aktiengesellschaft Electrochemical cell for detecting hydrogen sulphide in a gaseous mixture
US4169779A (en) * 1978-12-26 1979-10-02 Catalyst Research Corporation Electrochemical cell for the detection of hydrogen sulfide
US4197176A (en) * 1976-12-27 1980-04-08 Minas Ensanian Apparatus for measuring surface characteristics of metals and metalloids
US4394239A (en) * 1980-09-09 1983-07-19 Bayer Aktiengesellschaft Electro-chemical sensor for the detection of reducing gases, in particular carbon monoxide, hydrazine and hydrogen in air

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4720939U (en) * 1971-04-05 1972-11-09
JPS4829631U (en) * 1971-08-13 1973-04-11
JPS52116652A (en) * 1976-03-26 1977-09-30 Japan Electronic Control Syst Dish washer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260656A (en) * 1962-09-27 1966-07-12 Corning Glass Works Method and apparatus for electrolytically determining a species in a fluid
US3833495A (en) * 1970-09-28 1974-09-03 Gen Electric Reference electrode half cell
US4049503A (en) * 1974-07-27 1977-09-20 Bayer Aktiengesellschaft Electrochemical gas detection
US4141800A (en) * 1976-05-15 1979-02-27 Bayer Aktiengesellschaft Electrochemical gas detector and method of using same
US4149948A (en) * 1976-12-18 1979-04-17 Bayer Aktiengesellschaft Electrochemical cell for detecting hydrogen sulphide in a gaseous mixture
US4197176A (en) * 1976-12-27 1980-04-08 Minas Ensanian Apparatus for measuring surface characteristics of metals and metalloids
US4169779A (en) * 1978-12-26 1979-10-02 Catalyst Research Corporation Electrochemical cell for the detection of hydrogen sulfide
US4394239A (en) * 1980-09-09 1983-07-19 Bayer Aktiengesellschaft Electro-chemical sensor for the detection of reducing gases, in particular carbon monoxide, hydrazine and hydrogen in air

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0237914A2 (en) * 1986-03-20 1987-09-23 Bayer Diagnostic GmbH Method of producing electrochemical gas sensors
EP0237914A3 (en) * 1986-03-20 1988-05-04 Bayer Diagnostic + Electronic Gmbh Method of producing electrochemical gas sensors
GB2277378A (en) * 1993-03-05 1994-10-26 Mine Safety Appliances Co Electrochemical membrane gas sensor
GB2303710A (en) * 1993-03-05 1997-02-26 Mine Safety Appliances Co Electrochemical toxic gas sensor with gas permeable membrane
GB2277378B (en) * 1993-03-05 1997-04-30 Mine Safety Appliances Co Electrochemical toxic gas sensor
DE4407328B4 (en) * 1993-03-05 2008-11-06 Mine Safety Appliances Co. Electrochemical sensor for toxic gases
DE4407328B8 (en) * 1993-03-05 2009-03-26 Mine Safety Appliances Co. Electrochemical sensor for toxic gases
EP0740149A1 (en) * 1995-04-26 1996-10-30 ProMinent Dosiertechnik GmbH Electrochemical sensor
US5725747A (en) * 1995-04-26 1998-03-10 Prominent Dosiertechnik Gmbh Electrochemical measurement cell

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DE3478954D1 (en) 1989-08-17
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