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WO1992017775A1 - Etalonnage d'electrodes - Google Patents

Etalonnage d'electrodes Download PDF

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Publication number
WO1992017775A1
WO1992017775A1 PCT/EP1992/000769 EP9200769W WO9217775A1 WO 1992017775 A1 WO1992017775 A1 WO 1992017775A1 EP 9200769 W EP9200769 W EP 9200769W WO 9217775 A1 WO9217775 A1 WO 9217775A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
instrument
calibration
electrodes
measuring
Prior art date
Application number
PCT/EP1992/000769
Other languages
English (en)
Inventor
Stephen John Edwards
Graham Anthony Fuggle
Original Assignee
Eastman Kodak Company
Kodak Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company, Kodak Limited filed Critical Eastman Kodak Company
Priority to JP4506871A priority Critical patent/JPH06506060A/ja
Priority to BR9205841A priority patent/BR9205841A/pt
Publication of WO1992017775A1 publication Critical patent/WO1992017775A1/fr

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
    • G01N27/4165—Systems checking the operation of, or calibrating, the measuring apparatus for pH meters

Definitions

  • This invention relates to electro-analytical sensing instruments having sensor probe electrodes, and is particularly concerned with the calibration and use of the electrodes.
  • an active electrochemical species potentio etrically that is by measurement of the voltage between electrodes in an electrolyte (the analyte)
  • the measuring electrodes - either a separable indicator electrode and reference electrode, or a combined pair - cannot be disconnected from that instrument and connected to another, perhaps in a different area, without re-calibration.
  • the present invention is concerned therefore with the problem of allowing the calibration and measurement of such sensors to be carried out at one site or in one instrument and used in another instrument or at another site.
  • the invention is further concerned with the problem of providing a device which can be used for any type of sensor which requires re-calibration.
  • the reference half cell and junction potentials are not predictable to more than a few millivolts and may vary considerably between different reference electrodes. If it is necessary to obtain a direct instrument read-out in either concentration or In(concentration) it is necessary to first convert from the millivolts measured by calibrating the system on a number of standard solutions. The difference between theoretical millivolts and those measured is the offset voltage of that particular system. It is stored in the measuring instrument for later use, either by using a potentiometer to offset the millivolts measured back to the theoretical reading or digitally by using a micro-processor and memory.
  • the calibration data is stored in a calibration unit in close physical association with the electrode or electrode pair assembly rather than in the broader confines of the instrument itself. This means that the electrode assembly and calibration unit can be disconnected from the instrument and taken to a remote site. A new instrument can then read this information and be ready to measure without the need for re-calibration.
  • the invention provides an electrode assembly for connection to an electro-analytical sensing instrument which comprises at least one measuring electrode and, associated with said electrode, a calibration unit including a memory means, which is arranged to store calibration data to enable the assembly to be used with more than one sensing instrument.
  • This approach means that one indicator and reference electrode pair can be calibrated in a laboratory or clean area and can then be taken into a factory environment, where buffer or standard solution might be contaminated, for solution measurements.
  • the assembly in accordance with the invention comprises a small memory and communications integrated circuit sealed into either electrode or probe or holder assembly together with a micro ⁇ processor instrument.
  • the electrode pair can be calibrated in the normal process with buffers or standard solutions and the calibration data such as the slope and the offset voltage, can then be stored in the memory means in the electrode pair via a serial communications link. This information may then be stored in non-volatile memory, for example in battery- backed RAM, EPROM or EEPROM for future use.
  • the electrodes may then be disconnected, taken into a new area and connected to a different instrument. The new instrument will then retrieve this calibration data and be ready to carry out measurements.
  • the memory means is conveniently incorporated in the lead assembly of an existing electrode system.
  • the memory means may also include line drivers or impedance converters if the electrodes are of high impedance or the measuring instrument is likely to be located at a large distance from the electrodes.
  • the electrode assembly according to the invention may also be made intrinsically safe for areas where inflammable solvents are used. Calibration can then take place in a normal area where water baths and associated equipment can be safely used. Connection of the assembly to the measurement instrument is then preferably made via a shunt-diode safety barrier.
  • Figure 1 is a schematic diagram of an indicator electrode with the calibration unit installed
  • Figure 2 is a schematic diagram of an electrode combination pair with the calibration unit installed
  • Figure 3 is a schematic diagram of a sensor probe with the calibration unit installed in a corner unit separate from the sensors;
  • Figure 4 shows a schematic diagram of an electrode system with the calibration unit installed in a lead
  • FIG 5 is a block circuit diagram of the calibration unit; and Figures 6a to 6e show various known electrodes which can incorporate the invention.
  • FIG. 1 shows an indicator electrode incorporating a calibration unit.
  • a cylindrical glass container 1 carries at its lower end an electrode membrane 2 and encloses an electrolyte 3.
  • the membrane 2 is connected by an electrically conducting lead 4 to a screened multi strand output lead 5.
  • the lead 4 is screened by a metallic screening sheath 6. This is shown schematically but in practice can be located between inner and outer glass concentric walls rather than within the electrolyte 3.
  • the glass container 1 is carried by a carrier 7 at the top of the electrode assembly which as well as supporting the container 1 encloses wiring which feeds out into the multicore cable 5.
  • the carrier 7 also encloses a calibration unit 8 whose output leads are connected into the multi strand cable 5.
  • the electrode is used in conjunction with a reference electrode, which then forms a part of the calibrated pair.
  • the significant difference in the reference electrode is that instead of an electrode membrane 2 across which a voltage will be developed, a porous wall is employed at its lower end so that the reference electrode is retained at a potential derived from the solution within the electrode and is therefore constant. While the calibration data is retained in the unit associated with the indicator electrode, the calibration also takes account of variations within the reference electrode. Therefore a particular reference electrode always has to be identified and used together with the same calibrated indicator electrode.
  • Figure 2 shows a combined electrode consisting essentially of a measuring electrode of the kind shown in Figure 1 combined with a reference electrode surrounding it.
  • FIG. 3 shows a further arrangement.
  • a measuring electrode 20 and a reference electrode 21 substantially of the form shown in
  • Figure 1 are carried out in a connecting carrier 22 which connects to the main carrier 7.
  • the two electrodes 20 and 21 and an earthing terminal 22 are connected by conductors 23 via plugs and sockets 24 to an output amplifier 25 and thence to the multi strand cable 5 for feeding to the instrument (not shown) .
  • Figure 4 shows a further form of the invention where a combined electrode 31 is fed by conductors 32 via the calibration unit 8 to the instrument (not shown), i.e the calibration unit is incorporated in the electrode connecting lead.
  • the calibration unit 8 is always associated with one or both electrodes whereby when the or each electrode is unplugged from the instrument and taken to another location, it will always have its correct calibration.
  • Figure 5 shows a schematic of a particular form of calibration unit. This comprises a pair of high impedance operational amplifiers 41 and 42 which are fed from the sensors via input leads at the right hand side of the Figure and thence are fed to a pair of output leads on the left hand side of Figure 5.
  • the unit also incorporates a microprocessor with encapsulated battery and memory unit 43 fed from multi- strand cable 5 via serial line drives 44 and 45.
  • a pair of electrodes can be calibrated and the calibration stored in the memory unit 43 and the electrodes will then be available for use when plugged into other instruments at other sites.
  • the invention can be applied to various forms of known measuring electrode.
  • a unit of the kind shown in Figure 5 for example can readily be incorporated in the output lead or in the carrier head for the electrode.
  • Figure 6a to Figure 6e show various electrodes to which the invention may be applied. These electrodes are as follows:-
  • Figure 6a shows a metal electrode
  • Figure 6b shows a coated metal electrode
  • Figure 6c shows a solid state ion selective electrode.
  • Figure 6d shows a liquid iron exchange ion selective electrode.
  • Figure 6e is a pH electrode.
  • the liquid ion exchange ion selective electrode 57 is an internal reference solution 58 is an internal reference element and 56 is a sensing membrane across which a voltage can be developed.
  • Figure 6e denotes a conventional pH electrode incorporating a glass membrane 59 and extending from a glass body 60 which encloses an internal reference element 61 within an internal reference solution 62.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Oscillators With Electromechanical Resonators (AREA)
  • Drying Of Semiconductors (AREA)

Abstract

Instrument détecteur à analyse électrolytique tel qu'un pH-mètre. Il possède une électrode détectrice placée dans un électrolyte, et on lit les tensions de sortie afin de mesurer les caractéristiques, telles que le pH de l'électrolyte. On peut étalonner un ensemble d'électrodes dans un premier endroit et l'utiliser ailleurs sans procéder à un nouvel étalonnage, au moyen d'une unité d'étalonnage comprenant une mémoire et intégrée à l'ensemble d'électrodes pour l'utilisation dans d'autres endroits. On a prévu divers ensembles d'électrodes auxquels peut s'appliquer cette invention.
PCT/EP1992/000769 1991-04-04 1992-04-02 Etalonnage d'electrodes WO1992017775A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP4506871A JPH06506060A (ja) 1991-04-04 1992-04-02 電極の調整
BR9205841A BR9205841A (pt) 1991-04-04 1992-04-02 Instrumento de medição, e, conjunto de elétrodo

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919107036A GB9107036D0 (en) 1991-04-04 1991-04-04 Electrode calibration
GB9107036.7 1991-04-04

Publications (1)

Publication Number Publication Date
WO1992017775A1 true WO1992017775A1 (fr) 1992-10-15

Family

ID=10692613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/000769 WO1992017775A1 (fr) 1991-04-04 1992-04-02 Etalonnage d'electrodes

Country Status (7)

Country Link
EP (1) EP0579632A1 (fr)
JP (1) JPH06506060A (fr)
AU (1) AU1430692A (fr)
BR (1) BR9205841A (fr)
CA (1) CA2106666A1 (fr)
GB (1) GB9107036D0 (fr)
WO (1) WO1992017775A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545242A1 (fr) * 1991-11-28 1993-06-09 Paul-Gerhard Fenzlein Dispositif pour déterminer les mesurages électrochimiques médicaux d'un organe ou fonction métabolique
US5502388A (en) * 1993-02-04 1996-03-26 Hoechst Aktiengesellschaft Method of measuring the pH value of a test solution with glass-electrode measuring cells and of simultaneously calibrating the measuring cells
EP1143239A1 (fr) * 2000-04-04 2001-10-10 Metrohm Ag Procédé de surveillance de la qualité de capteurs de mesures électrochimiques et dispositif de mesure avec un capteur électrochimique
WO2004102175A1 (fr) * 2003-05-15 2004-11-25 Endress + Hauser Conducta Gmbh+Co. Kg Capteur potentiometrique
WO2007067881A3 (fr) * 2005-12-05 2007-07-26 Sencal Llc Detecteurs jetables, pre-calibres et pre-valides a utiliser dans des applications de traitement biologique
US8025779B2 (en) 2003-11-14 2011-09-27 Tanita Corporation Water quality analyzer
US8419912B2 (en) 2003-11-14 2013-04-16 Tanita Corporation Water quality analyzer
US9575087B2 (en) 2012-09-06 2017-02-21 Parker-Hannifin Corporation Risk-managed, single-use, pre-calibrated, pre-sterilized sensors for use in bio-processing applications
USRE49221E1 (en) 2002-06-14 2022-09-27 Parker Intangibles, Llc Single-use manifolds for automated, aseptic handling of solutions in bioprocessing applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6311903B2 (ja) * 2017-02-08 2018-04-18 横河電機株式会社 液分析用スマートセンサにおけるインテリジェンス部の再利用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2354558A1 (fr) * 1976-06-10 1978-01-06 Boeke Jan Electrode combinee, destinee a la mesure de la concentration des ions et du ph dans un liquide, ainsi que son procede de realisation
DE2845805A1 (de) * 1977-10-20 1979-04-26 Olympus Optical Co Verfahren und vorrichtung zum messen von ionenkonzentrationen
EP0074498A1 (fr) * 1981-09-04 1983-03-23 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé et dispositif d'étalonnage de capteurs
DE3323040A1 (de) * 1983-06-27 1985-01-17 Walter 2000 Hamburg Nicolai Redoxpotential-messgeraet
EP0142226A2 (fr) * 1983-08-29 1985-05-22 Instrument Technology Incorporated Appareil pour la mesure des ions comportant un moyen de stockage d'une solution étalon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2354558A1 (fr) * 1976-06-10 1978-01-06 Boeke Jan Electrode combinee, destinee a la mesure de la concentration des ions et du ph dans un liquide, ainsi que son procede de realisation
DE2845805A1 (de) * 1977-10-20 1979-04-26 Olympus Optical Co Verfahren und vorrichtung zum messen von ionenkonzentrationen
EP0074498A1 (fr) * 1981-09-04 1983-03-23 F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft Procédé et dispositif d'étalonnage de capteurs
DE3323040A1 (de) * 1983-06-27 1985-01-17 Walter 2000 Hamburg Nicolai Redoxpotential-messgeraet
EP0142226A2 (fr) * 1983-08-29 1985-05-22 Instrument Technology Incorporated Appareil pour la mesure des ions comportant un moyen de stockage d'une solution étalon

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545242A1 (fr) * 1991-11-28 1993-06-09 Paul-Gerhard Fenzlein Dispositif pour déterminer les mesurages électrochimiques médicaux d'un organe ou fonction métabolique
US5502388A (en) * 1993-02-04 1996-03-26 Hoechst Aktiengesellschaft Method of measuring the pH value of a test solution with glass-electrode measuring cells and of simultaneously calibrating the measuring cells
EP1143239A1 (fr) * 2000-04-04 2001-10-10 Metrohm Ag Procédé de surveillance de la qualité de capteurs de mesures électrochimiques et dispositif de mesure avec un capteur électrochimique
USRE49221E1 (en) 2002-06-14 2022-09-27 Parker Intangibles, Llc Single-use manifolds for automated, aseptic handling of solutions in bioprocessing applications
WO2004102175A1 (fr) * 2003-05-15 2004-11-25 Endress + Hauser Conducta Gmbh+Co. Kg Capteur potentiometrique
US7704357B2 (en) 2003-05-15 2010-04-27 Endress + Hauser Conducta Gesellschaft Fur Mess- Und Regeltechnik Mbh + Co. Kg Potentiometric sensor
EP2204647A3 (fr) * 2003-05-15 2010-12-01 Endress+Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH+Co. KG Capteur potentiométrique pour la mesure de pH
US8025779B2 (en) 2003-11-14 2011-09-27 Tanita Corporation Water quality analyzer
US8419912B2 (en) 2003-11-14 2013-04-16 Tanita Corporation Water quality analyzer
US7788047B2 (en) * 2005-12-05 2010-08-31 Sencal Llc Disposable, pre-calibrated, pre-validated sensors for use in bio-processing applications
US7927010B2 (en) 2005-12-05 2011-04-19 SenCal, LLC Disposable, pre-calibrated, pre-validated sensors for use in bio-processing applications
US7857506B2 (en) 2005-12-05 2010-12-28 Sencal Llc Disposable, pre-calibrated, pre-validated sensors for use in bio-processing applications
US8506162B2 (en) 2005-12-05 2013-08-13 Parker-Hannifin Corporation Disposable, pre-calibrated, pre-validated sensors for use in bio-processing applications
WO2007067881A3 (fr) * 2005-12-05 2007-07-26 Sencal Llc Detecteurs jetables, pre-calibres et pre-valides a utiliser dans des applications de traitement biologique
US9575087B2 (en) 2012-09-06 2017-02-21 Parker-Hannifin Corporation Risk-managed, single-use, pre-calibrated, pre-sterilized sensors for use in bio-processing applications

Also Published As

Publication number Publication date
JPH06506060A (ja) 1994-07-07
EP0579632A1 (fr) 1994-01-26
AU1430692A (en) 1992-11-02
CA2106666A1 (fr) 1992-10-05
BR9205841A (pt) 1994-10-11
GB9107036D0 (en) 1991-05-22

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