USRE31299E - Ion-selective electrode device for polarographic measurement of oxygen - Google Patents

Ion-selective electrode device for polarographic measurement of oxygen Download PDF

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Publication number
USRE31299E
USRE31299E US06/357,563 US35756382A USRE31299E US RE31299 E USRE31299 E US RE31299E US 35756382 A US35756382 A US 35756382A US RE31299 E USRE31299 E US RE31299E
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United States
Prior art keywords
ligand
membrane
ion
selective
electrode
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Expired - Lifetime
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US06/357,563
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English (en)
Inventor
Manfred Kessler
Jens Hoper
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KESSLER MANFRED DORTMUND GERMANY
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Max Planck Gesellschaft zur Foerderung der Wissenschaften
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Assigned to KESSLER, MANFRED, DORTMUND, GERMANY reassignment KESSLER, MANFRED, DORTMUND, GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MAX PLANCK GESELLSCHAFT ZUR FOERDERUNG DER WISSENSCHAFTEN
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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

Definitions

  • the invention relates to a device for the polarographic measurement of oxygen.
  • a device comprising a source of potential voltage; a reduction electrode for the oxygen composed of a noble metal and connected to said voltage source; a reference electrode connected to said reduction electrode; a ligand membrane provided in front of the reduction electrode, the ligand membrane containing a cation-selective carrier and being permeable to hydrogen ions; a closure membrane to seal the electrodes against the outside space, the closure membrane being permeable to oxygen and impermeable to water, and an aqueous electrolyte containing the ligand cation of the ligand membrane, the said electrolyte being disposed between said ligand membrane and said closure membrane.
  • the selective action of the ligand membrane causes only the reaction material to come in contact with the reduction electrode while no such contact takes place with the materials of which the electrolyte or the opposite electrode are composed. Chemical changes in the reduction electrode are thus avoided and the time of constant operation of the device is substantially extended. Furthermore, the particle flow of the oxygen is drastically reduced. An interference of the concentration field of the oxygen through the measurement activity is therefore extremely small.
  • the signal produced is measured by means of an amplifier which in order to preserve the above advantages should have an input value of about 10 12 ⁇ .
  • the device operates with particular success if the ligand is Na-selective. It has been found that in that case an easily indicated signal which is highly proportional to the actual oxygen concentration is produced.
  • the ligands or ion-sensitive molecule may be 3,6-dioxaoctanediacid-bis-diphenylamine, or preferably may consist of N,N,N,N,-tetrabenzyl-3,6-dioxaoctane diamide or N,N'-dibenzyl-N,N'-diphenyl-1,2-phenylenedioxydiacetamide.
  • the ion selective reference electrode is covered by a corresponding reference ligand membrane which contains an ion-sensitive molecule or ligand different from the cation ligand of the ligand membrane. This will protect the reference electrode from physical or chemical damage.
  • the electrolyte preferably consists of 0.1 M HCl and 0.01 M NaCl, NaCl and HCl are required for the function of the oxygen electrode 2 if the electrode consists of platinum covered with a Na + membrane.
  • 0.01 M KCl should be used for the electrode if the reference electrode consists of platinum covered with a K + membrane.
  • the voltage provided is 200 mV. In this manner at the boundary layer of the platinum a Po 2 dependent oxygen potential is generated.
  • the resistance of the electrode is: ##EQU1##
  • R Po2 resistance of polarization layer (Helmholtz layer)
  • R membrane resistance of Na + membrane
  • the total resistance is in the range of 10 10 Ohms and decreases by less than one order of magnitude with an increasing oxygen potential.
  • the membranes are preferably made of PVC impregnated with a solvent containing the ion-sensitive molecule.
  • the membrane is for instance made by setting up a solution of PVC in dibenzyl ether. The solution is then mixed with about 0.6% by weight of the Na-ligand or 2.7% weight of the K-ligand (such as valinomycin) and subjected to drying.
  • K-ligand such as valinomycin
  • membranes are then placed onto a body of PVC comprising the platium electrodes and are welded together with the main body chemically by using again a small amount of solvent.
  • the thus formed structure is then covered with a membrane of PVC or Teflon which does not contain a ligand.
  • the space between the two membranes in the device is thereafter filled with an electrolyte.
  • the electrolyte does not contain the ligand itself, but only the ions.
  • oxygen concentrations can be measured in a range of pressure from 1/100 mm mercury up to several psi.
  • the measurement can be carried out amperometrically, that is with a measuring resistance of about 10 6 ⁇ which will cause a stationary particle flow in the measuring system.
  • FIGURE of the drawing shows in a diagrammatic form the device of the invention.
  • a source of polarization voltage 1 of 200 mV is connected with the reduction electrode 2 which preferably consists of platinum.
  • Another electrode, the reference electrode 3, is arranged in annular manner around the reduction electrode.
  • a PVC membrane (20) In front of the reduction electrode a PVC membrane (20) is arranged which contains an ion selective cation molecular or ligand and is permeable to hydrogen ions and oxygen.
  • the reference electrode 3 In front of the other electrode, the reference electrode 3, a similar membrane, the reference ligand membrane 30, is provided which, however, contains an ion-sensitive molecule or ligand which is different from the ligand of the ligand membrane 20.
  • the device can be operated also without the reference ligand membrane.
  • the ion-sensitive molecule provided in the ligand membrane may consist of any of the products listed above and in the example was formed of 3,6-dioxaoctanediacid-bis-diphenylamine.
  • An electrolyte 5 is disposed so as to cover the entire device.
  • the device is furthermore sealed against the exterior space by a closure membrane 6 which may be of polymerized tetrafluoroethylene synthetic plastic, commercially available under the trade name "Teflon".
  • a closure membrane 6 which may be of polymerized tetrafluoroethylene synthetic plastic, commercially available under the trade name "Teflon". If no reference ligand membrane 30 is provided the electrolyte may consist only of 0.1 M HCl and 0.01 M NaCl. If a reference ligand membrane such as the membrane 30 is provided the electrolyte must additionally also contain the ion of the ligand used in the latter membrane, e.g. KCl.
  • the operation of the device is as follows: In the exterior space there is a specific concentration of the oxygen 7. The oxygen then will diffuse through the closure membrane 6 which may be made of Teflon and furthermore will penetrate together with the hydrogen ions from the electrolyte 5 into the ligand membrane 20. After reduction of the oxygen water is formed with the hydrogen ions according to the equation
  • This reaction results in a change of potential of the electrode 2-20 in the chain of potential formed by the electrodes 2-20, 3-30, the electrolyte 5 and the voltage source 1. This change of potential is then indicated by means of the amplifier 4. As already noted the amplifier 4 has an input resistance of about 10 12 ⁇ .
  • the electrolyte in case of the use of a reduction membrane and a reference membrane must contain the ions of both ligands.
  • the ions are Na + and K + in the case of an Na-ligand membrane used on the electrode 2 and in case of a K + ligand membrane on the reference electrode 3 the electrolyte must contain both Na + and K + ions.
  • the polarization voltage is generated by a battery-driven, stabilized, and highly insulated power supply which is connected in series to the oxygen electrode.
  • the slope of the calibration curve increases with higher polarization voltage.
  • a polarization voltage of -200 mV there was obtained a linear calibration curve with a slope of approximately 40 mV per decade of oxygen tension.
  • the cathode is protected against deposition of metals and other reducible species in an almost ideal way.
  • the platinum interface is not in contact with an aqueous phase.
  • the ions which are supposed to be involved in the electrochemical reaction can be selected.
  • the oxygen sensor described is very suitable for tissue measurements because of its small convection sensitivity, is high sensitivity in the low PO 2 range and its relatively small drift.
  • the device can be used for PO 2 measurements in:
  • tissues brain, heart, liver, kidney, skeletal muscle

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
US06/357,563 1977-07-04 1982-03-12 Ion-selective electrode device for polarographic measurement of oxygen Expired - Lifetime USRE31299E (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2730143 1977-07-04
DE2730143A DE2730143C3 (de) 1977-07-04 1977-07-04 Elektrode zur Sauerstoffmessung

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US05/921,259 Reissue US4263115A (en) 1978-07-03 1978-07-03 Ion-selective electrode device for polarographic measurement of oxygen

Publications (1)

Publication Number Publication Date
USRE31299E true USRE31299E (en) 1983-07-05

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US06/357,563 Expired - Lifetime USRE31299E (en) 1977-07-04 1982-03-12 Ion-selective electrode device for polarographic measurement of oxygen

Country Status (8)

Country Link
US (1) USRE31299E (enrdf_load_stackoverflow)
JP (1) JPS5440693A (enrdf_load_stackoverflow)
AT (1) AT381594B (enrdf_load_stackoverflow)
CH (1) CH629305A5 (enrdf_load_stackoverflow)
DE (1) DE2730143C3 (enrdf_load_stackoverflow)
DK (1) DK150997C (enrdf_load_stackoverflow)
FR (1) FR2396972A1 (enrdf_load_stackoverflow)
GB (1) GB2000595B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968340A (en) 1997-04-07 1999-10-19 Marine Biological Laboratory Polarographic self-referencing probe and method for using

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5752918A (en) * 1980-09-09 1982-03-29 Toyota Motor Corp Constant-speed running device
DE3120559A1 (de) * 1981-05-23 1982-12-09 Robert Bosch Gmbh, 7000 Stuttgart Reaktionsschneller servoantrieb
JPS5896142A (ja) * 1981-12-01 1983-06-08 Nippon Denso Co Ltd 自動車用オ−トドライブ走行装置
DE3332745A1 (de) * 1983-09-10 1985-03-28 Jens 8520 Erlangen Höper Anordnung zum messen der konzentration eines stoffes
DE3689131T2 (de) * 1985-06-10 1994-03-03 Orbisphere Corp Amperometrische Zelle und Verwendungsverfahren.
DE3537919A1 (de) * 1985-10-24 1987-04-30 Kessler Manfred Anordnung zur stabilisierung einer gas-bezugselektrode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857777A (en) * 1973-08-10 1974-12-31 Environmental Protection Agenc Ion exchange membrane for measuring orthophosphate
US3957607A (en) * 1972-04-24 1976-05-18 W. Moller Glasblaserei Process for the preparation of lipide soluble complexes of cations, application of the process and use of the complexes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985633A (en) * 1972-11-11 1976-10-12 Eschweiler & Co. Device for the polarographic measurement of oxygen pressure
CH585907A5 (enrdf_load_stackoverflow) * 1973-08-06 1977-03-15 Hoffmann La Roche
GB1506048A (en) * 1974-06-28 1978-04-05 Siemens Ag Electrode assembly for polarographic investigation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957607A (en) * 1972-04-24 1976-05-18 W. Moller Glasblaserei Process for the preparation of lipide soluble complexes of cations, application of the process and use of the complexes
US3857777A (en) * 1973-08-10 1974-12-31 Environmental Protection Agenc Ion exchange membrane for measuring orthophosphate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
The Condensed Chemical Dictionary, 7th Ed., Reinhold Book Corp., pp. V & 920. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5968340A (en) 1997-04-07 1999-10-19 Marine Biological Laboratory Polarographic self-referencing probe and method for using

Also Published As

Publication number Publication date
JPS6129458B2 (enrdf_load_stackoverflow) 1986-07-07
DK300678A (da) 1979-01-05
DE2730143B2 (de) 1979-10-04
DK150997C (da) 1988-02-15
FR2396972B1 (enrdf_load_stackoverflow) 1983-11-18
CH629305A5 (de) 1982-04-15
FR2396972A1 (fr) 1979-02-02
GB2000595B (en) 1982-01-13
DK150997B (da) 1987-10-05
GB2000595A (en) 1979-01-10
JPS5440693A (en) 1979-03-30
DE2730143C3 (de) 1980-06-26
ATA484378A (de) 1986-03-15
AT381594B (de) 1986-11-10
DE2730143A1 (de) 1979-01-18

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Owner name: KESSLER, MANFRED, DORTMUND, GERMANY

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Effective date: 19840424