US3840438A - Method of direct potentiometric analysis of a liquid sample - Google Patents

Method of direct potentiometric analysis of a liquid sample Download PDF

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Publication number
US3840438A
US3840438A US00242556A US24255672A US3840438A US 3840438 A US3840438 A US 3840438A US 00242556 A US00242556 A US 00242556A US 24255672 A US24255672 A US 24255672A US 3840438 A US3840438 A US 3840438A
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United States
Prior art keywords
sample
electrode
ion
stream
conduit
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Expired - Lifetime
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US00242556A
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English (en)
Inventor
K Rao
T Ast
M Pelavin
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Bayer Corp
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Technicon Instruments Corp
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Application filed by Technicon Instruments Corp filed Critical Technicon Instruments Corp
Priority to US00242556A priority Critical patent/US3840438A/en
Priority to CA164,106A priority patent/CA974304A/en
Priority to AU52529/73A priority patent/AU466148B2/en
Priority to NLAANVRAGE7302616,A priority patent/NL174875C/xx
Priority to JP2912173A priority patent/JPS5630499B2/ja
Priority to IT67830/73A priority patent/IT980675B/it
Priority to BE129305A priority patent/BE797384A/xx
Priority to SE7304841A priority patent/SE393680B/xx
Priority to DE2365386A priority patent/DE2365386C3/de
Priority to CH636574A priority patent/CH556537A/de
Priority to CH496973A priority patent/CH555540A/de
Priority to DE2317273A priority patent/DE2317273C3/de
Priority to GB1700873A priority patent/GB1395673A/en
Priority to FR7312613A priority patent/FR2180323A5/fr
Application granted granted Critical
Publication of US3840438A publication Critical patent/US3840438A/en
Assigned to TECHNICON INSTRUMENTS CORPORATION reassignment TECHNICON INSTRUMENTS CORPORATION MERGER (SEE DOCUMENT FOR DETAILS). Assignors: REVGROUP PANTRY MIRROR CORP.
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/08—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a stream of discrete samples flowing along a tube system, e.g. flow injection analysis

Definitions

  • the method includes the step in the analysis of blood samples of conditioning such a sodium ion electrode, immediately before running a first series of such samples, by exposure over a period of time to blood protein and the blood ion constituents which will affect the sodium ion electrode on exposure of the later to the samples, as well as buffer of the type used in analysis.
  • Human blood serum or plasma is useful for such conditioning.
  • Such conditioning effectively tends to avoid drift and speeds the response of the sodium ion electrode.
  • the samples are heated so as to have a temperature above 40 C. on exposure of the samples to the last-named electrode.
  • Such fast electrode response reduces to an insignicant factor potassium transient effects in sodium analyses of blood samples.
  • Field of Invention This invention relates to a method of measuring ionic parameters, especially those of sodium, potentiometrically or electrochemically in monitoring a stream or analyzing up to a very fast rate a series of samples.
  • the sodium ion electrode was associated with a conventional reference electrode providing what is known as a leak junction in communication with the sample stream to complete an electrical circuit.
  • the sodium ion electrode used was also of the bulb type having a portion of the bulb, which was exposed to the sample, constructed of sodium-sensitive glass. The analysis rate of samples was relatively very slow.
  • One object of the invention is to provide an improved method of potentiometric analysis of various liquid samples, which offers the advantages of simplicity, ease of operation and precision which is as good as, if not better than, flame photometric methods.
  • Another object is to provide such a method, susceptible of automation, of monitoring a stream or analyzing up to a very fast rate a series of samples by direct potentiometric measurements, particularly useful for sodium determinations, which samples are separated from one another by immiscible fluid segments in a conduit, which segments cleanse the conduit and maintain sample integrity, utilizing both an ion-selective electrode and a reference electrode associated with the segmented stream, and wherein both the reference and the indicator electrodes are exposed to the segmented stream.
  • Such analysis of discrete samples makes possible a much faster rate of analysis. Contrary to prior thinking, polarization of the electrodes is avoided.
  • the method includes the step in the analysis of blood samples of conditioning such a sodium ion electrode, immediately before running a first series of such samples, by exposure over a period of time to blood protein and the blood ion constituents which will affect the sodium ion electrode on exposure of the latter to the samples, as well as the type of buffer solution used in analysis.
  • Human blood serum or plasma is useful for such conditioning.
  • Such conditioning contrary to prior thinking, effectively tends to avoid drift and speeds the response of the sodium ion-selective electrode.
  • the response of the sodium ion-selective electrode is further speeded for faster analysis of each sample by heating the samples so that they have a temperature above 40 C. on exposure of the samples to the last-named electrode.
  • FIG. 1 is a diagrammatic view illustrating a system useful for carrying out a method of analysis embodying the invention.
  • FIG. 2 is a somewhat diagrammatic view illustrating in elevation a useful form of ion-selective electrode and reference electrode for analysis in accordance with FIG. 1.
  • immiscible fluid segments separating the samples from one another.
  • immiscible fluid segments may be formed of a gas and the stream may be further segmented by segments of a wash solution separated from the samples by segments of the immiscible fluid such as i1- lustrated and described by de Jong, ⁇ U.S. Pat. 3,134,263 issued May 26, 1964.
  • sample may flow at a volumetric rate of between approximately 200 microliters per minute.
  • the -ow from an outlet of conduit 10 enters an adjoining inlet of conduit 14.
  • conduit 14 there is added through an outlet of a conduit 16 an appropriate buffer solution to dilute each sample and provide both pH and ionic strength adjustment.
  • the buffer solution is caused to flow into the inlet 18 of the conduit 16 from a source, not shown, by a pressure differential, and a flow controller, as indicated, is interposed in the conduit 16 to control the ow of the buffer solution into the conduit 14, such controlled flow of the last-mentioned solution being approximately SOO-1000 microliters per minute.
  • the buffer solution flowing to the conduit 14 from the conduit 16 is segmented at a controlled rate by air under pressure owing in a conduit 20 through inlet 22 from a conventional source not shown.
  • the thusly combined segmented sample and buffer streams received in the conduit 14 flow through a mixing coil interposed in conduit 14, wherein the sample segments and the buffer solution are intermixed.
  • the thusly treated sample stream is heated to a temperature above body temperature and approximately between 40-50" C. prior to exposure to an ion-selective electrode which in this case is a sodium ion-selective electrode.
  • a conventional heating bath may be employed as shown in FIG. 1.
  • a three-way valve 24 is interposed intermediate the outlet of the mixing coil and the inlet of the heating bath.
  • the valve 24 has an outlet connected to a waste bypass as shown so that when it is desired to flush out the aforementioned liquid conduits extending toward and through the mixing coil with a flushing solution, such flushing solution is diverted so that it does not reach and does not affect the sodium ion-selective electrode shown in FIG. 1 as being associated with the outlet of theA treated sample stream from the heating bath.
  • conduit 26 Downstream from the heating bath in conduit 26 in communication through valve 24 in one position of the latter with the outlet of conduit 14, there is provided a conductor pin, not shown, extending into the conduit 26 for exposure to the stream therein and connected to a ground wire 28, which pin and wire 28 are located upstream of the sodium ion electrode indicated in FIG. 1.
  • a sodium ion-selective electrode and a reference electrode structure is not critical to the invention, provided that the ion-selective electrode is of the continuous-flow type and the electrical connection of the reference electrode to the sample stream is close to the ion-sensitive surface of the ion-selective electrode.
  • a very satisfactory combination electrode structure is illustrated diagrammatically in FIG. 2. This electrode structure is illustrated and described in the co-pending Brand and Rao U.S. Patent application assigned to the same assignee, Ser. No. 242,507 filed on Apr. 10, 1972. Hence the electrode structure, indicated generally at 30, does not require a detailed description here.
  • the electrode structure 30 comprises a body member 32 of a block-like form structured of an insulating material and having a bore 34 therethrough enlarged as at 36.
  • a cannula 38 structured of sodium-selective glass of any known suitable type and fixed in the bore 34 by any suitable means.
  • the cannula 38 has an outer diameter considerably less than the enlargement 36 of the bore and extends to the right beyond the block 32.
  • the inner diameter of the cannula 38 is flush with the portion of the bore 34 of smaller diameter.
  • the cannula 38 extends through a suitable seal 40, which seal forms with the body member 32 and the cannula 38 in the area of the bore enlargement 36 a chamber 41 for the electrolyte filling solution for the internal reference electrode.
  • the chamber 41 is preferably provided with a filling port 42 in the body member 32 which may be closed by a suitable plug not shown.
  • the cannula 38 in the area where it passes through the chamber 41 is completely surrounded by the electrolyte solution in the chamber.
  • the ion-selective half cell is completed by an internal reference electrode 44 of conventional silversilver chloride wire which is shown extending into the body member 32 and into the electrolyte in the chamber 41.
  • the inlet end 46 of the cannula 38 is suitably connected to the outlet of the conduit 26 of FIG. l.
  • the reference electrode portion of the combined electrode structure 30 includes a conduit 48 in the member 32 (FIG. 2) the inlet of which is connected to the outlet of a conduit 50 (FIG. l) having an inlet end connected to an electrolyte reservoir which electrolyte is here shown as potassium chloride (KCl).
  • the reservoir is sealed and is pressurized through a conduit 52 having an outlet connected to the reservoir and having an inlet end 54 connected to a source of air under pressure, not shown.
  • the KCl reservoir of FIG. 1 may be supplied with KCl solution by any suitable means not shown.
  • the conduit 50 conveys KCl under pressure to conduit 48 into which conduit electrode 56 extends formed of siliver-silver chloride wire, for example, forming with the KCl solution the reference half cell.
  • the reference electrode portion of the combined electrode structure 30 is shown as being of the leak-junction type for electrical connection to the segmented, treated sample stream. As previously indicated, this stream enters the sample passageway 34 through the cannula 38 inserted in the inlet portion of the passageway-forming bore 34. The sample stream exits from the cannula 38 into the last-mentioned passageway which is continued through the axis of a boss 60 of the block member 32 which boss is formed as a truncated cone.
  • the aforementioned conduit 48 for pressurized KCl extends through a face of the block member 32 so as to have an outlet in a location above and closely adjacent the base of the cone-like boss in a planar annular surface of the block member 32.
  • a block-like body member 62 coacts with the body member 32.
  • the block-like member 62 structured of an insulating material, has a sample passageway 64 extending therethrough into the outlet end of which a nipple 66 is inserted for connection to the inlet end of a waste conduit 68 (FIG. 1) which has an outlet end connected to a suitable waste receptacle or drain not shown.
  • the inlet end of the sample passageway 64 is through the bottom of a recess 70 having a shape complemental to the cone-like boss 60 of the member 32.
  • a yieldable annular gasket 72 carried by one of the block members 32, 62 to provide a seal between the block members as shown in FIG. 2.
  • the block members 32 and 62 provide a liquid passageway therebetween in communication with the outlet of the KCl conduit 48 and defined at least in part by the boss 60 and the recess 70.
  • This construction provides a leak junction between the KCl electrolyte of the reference electrode and the segmented sample stream flowing from the block 32 through the outlet thereof in the cone 60 to the inlet of the passageway 64 for the sample stream provided in the block 62.
  • the leak junction of the reference electrode may -be spaced only 2 mm. from the sodiumsensitive glass cannula 38 of the ion-selective electrode.
  • the block-like members 32 and 62 may be supported for relative adjustment toward and away from each other for restriction or enlargement of the leak junction therebetween.
  • the cross-sectional size of the passageway for the leak junction between the block-like members 32, 62 is relatively small. Furthermore, only a very small volume of the KCl solution is permitted to enter the sample stream. It will be understood from the foregoing that the leak junction is formed entirely around the periphery of the sample stream.
  • the sodium-selective electrode is interconnected to an input terminal of a differential amplifier by a conducter 76.
  • the conductor 76 is connected to the silver-silver chloride wire 44 of this electrode.
  • the reference electrode is interconnected to a second input terminal of the differential amplifier by a conductor 78.
  • the conductor 78 is connected to the silver-silver chloride wire 56 of the reference electrode.
  • the aforementioned ground wire or conductor 28 connected to the aforementioned conductor pin (not shown) exposed to the stream in the conduit 26, interconnects this pin to a third input terminal of the differential amplilier which amplifier has an output terminal as shown which may be connected to any suitable display and/or recording device commonly in use for potentiometric measurements.
  • the function of the differential amplifier is to subtract the common mode signal from each of the reference electrode and sodium electrode signals and to produce a potentiometric signal corresponding to the difference between the sodium-selective electrode and the reference electrode.
  • the output of the amplifier is proportional to sodium activity which is proportional to sodium ion concentration.
  • the ion-sensitive cannula 38 of the sodium electrode may be conditioned for the next use by leaving the cannula 38 exposed to a buffered solution of the type used in analysis.
  • a buffered solution may include a blood serum or plasma standard.
  • Such buffered solution would provide human blood protein in contact with the sodium glass cannula 38 to speed the response of the ion-selective electrode when the system is again put in use and which exposure to a protein also avoids drift when the system is next put in use.
  • such conditioning with blood protein is contrary to known prior teachings.
  • the sodium ion-selective glass of the cannula 38 may be left exposed to the buffered serum or plasma by avoiding, in any well known manner, drainage of such buffered solution from the cannual 38 and from the system when the system is at rest.
  • the sodium ion-selective glass may be conditioned by operating the system with a few specimens of plasma or sera standards. Conditioning by this alternative technique may be faster and more satisfactory than conditioning by the technique rst mentioned. In either event, the ion-selective sodium electrode is conditioned by exposure to blood protein and the ions which will affect the electrode in analysis, as well as the buffer solution.
  • the ion-selective electrode As previously indicated, response of the ion-selective electrode is speeded by exposure of this electrode to heat above body temperature but not to a degree high enough to damage the sodium ion-selective electrode. While the heating of the sample has been illustrated and described with reference to a heating bath separate and apart from the combined electrode structure 30, it will be obvious to those versed in the art that a heated coil for the sample may be built into the electrode structure if desired. It will also be evident that instead of using a liquid filling solution in the chamber 41 of the ion-selective electrode, the electrolyte may be a solid, if desired, which encircles the cannual 38 in closecontacttherewith, which has an electrical Contact with the silver-silver chloride wire 44.
  • the volume of the sample may be reduced and the time required for exposure of the sample to such electrode may be reduced to 18 seconds or less enabling a much faster sample rate of analysis than heretofore, provided that the immiscible fluid segments such as gas bubbles are also maintained in a small size range but naturally of a size sufficient to occlude the sample passageway.
  • Polarizing of the ion-selective electrode is also effectively inhibited by maintaining such gas bubbles in the aforementioned small size range and reducing as far as is practical the time over which such a gas bubble is exposed t the ion-selective electrode. It is theorized that the thin liquid boundary of bubbles of such small size is sufficiently conductive to avoid polarization of the electrodes.
  • the method of the invention efliectively avoids confusing initial transient responses of the Sodium-selective electrode to changes in concentrations between samples of potassium present in the samples.
  • recorder pen tracings of peak values of sodium in samples containing both sodium and potassium in different concentrations of potassium as well as different concentrations of sodium no transient potassium effect has been evident.
  • the initial response of the sodium ion electrode to potassium is countered by the effect of the wash between samples of the aforementioned wash solution interposed in the segmented sample stream intermediate samples.
  • the wash solution is interposed in the segmented sample stream in segments of such solution, each of which Wash solution segments being interposed between a pair of gas segments.
  • a method of potentiometric analysis of a series of liquid samples for a constituent of interest utilizing a reference electrode and a sensing electrode having an ion-selective surface portion, said reference electrode and said ion-selection surface portion of said sensing electrode dening, in part, a ow-thru conduit, comprising the steps of:
  • each sample liquid segment in said stream bridges said reference electrode and said ion-selective surface portion of said sensing electrode; and measuring the electrical potential across said electrodes for analysis of said liquid sample segments.
  • said samples contain both sodium and potassium and said sensing electrode is a sodium-selective electrode, further including heating said stream in transit toward said electrodes so that the sample segments on exposure to the electrodes 'are at a tcmperement of substantially 40-50 C., substantially eliminating a potassium transient effect on said sensing electrode.
  • said samples are blood samples, and further including:
  • sensing electrode conditioning of said sensing electrode prior to analysis by exposure of the latter over a period of time to a solution containing blood proteins and ions present in human blood to which the sensing electrode will respond, in amounts substantially the same as in human blood, and
  • said conditioning includes flowing said solution past said electrodes for exposure of the latter thereto.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
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US00242556A 1972-04-10 1972-04-10 Method of direct potentiometric analysis of a liquid sample Expired - Lifetime US3840438A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US00242556A US3840438A (en) 1972-04-10 1972-04-10 Method of direct potentiometric analysis of a liquid sample
CA164,106A CA974304A (en) 1972-04-10 1973-02-20 Method of direct potentiometric analysis of a liquid sample
AU52529/73A AU466148B2 (en) 1972-04-10 1973-02-23 Method of direct potentiometric analysis of a liquid sample
NLAANVRAGE7302616,A NL174875C (nl) 1972-04-10 1973-02-26 Werkwijze voor het uitvoeren van een potentiometrische analyse.
JP2912173A JPS5630499B2 (de) 1972-04-10 1973-03-14
IT67830/73A IT980675B (it) 1972-04-10 1973-03-22 Procedimento e dispositivo per aumentare la velocita e l accura tezza dell analisi potenziometri ca di campioni liquidi in serie
BE129305A BE797384A (fr) 1972-04-10 1973-03-27 Analyse potentiometrique directe d'un echantillon liquide
SE7304841A SE393680B (sv) 1972-04-10 1973-04-05 Forfarande for potentiometrisk analys av en serie vetskeprov pa en viss bestandsdel med hjelp av en referenselektrod och en med ett jonselektivt ytparti utford metelektrod, vilka delvis begrensar en ...
DE2365386A DE2365386C3 (de) 1972-04-10 1973-04-06 Verfahren zur potentiometrischen Analyse einer Reihe von Flüssigkeitsproben auf eine interessierende Substanz
CH636574A CH556537A (de) 1972-04-10 1973-04-06 Verfahren zur potentiometrischen analyse einer reihe von fluessigkeitsproben auf eine interessierende substanz.
CH496973A CH555540A (de) 1972-04-10 1973-04-06 Verfahren zur direkten potentiometrischen analyse einer reihe von fluessigkeitsproben auf eine interessierende substanz.
DE2317273A DE2317273C3 (de) 1972-04-10 1973-04-06 Verfahren zur direkten potentiometrischen Analyse einer Reihe von Flüssigkeitsproben auf eine interessierende Substanz
GB1700873A GB1395673A (en) 1972-04-10 1973-04-09 Method of direct potentiometric analysis of a liquid sample
FR7312613A FR2180323A5 (de) 1972-04-10 1973-04-09

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US00242556A US3840438A (en) 1972-04-10 1972-04-10 Method of direct potentiometric analysis of a liquid sample

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US00242556A Expired - Lifetime US3840438A (en) 1972-04-10 1972-04-10 Method of direct potentiometric analysis of a liquid sample

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US (1) US3840438A (de)
JP (1) JPS5630499B2 (de)
BE (1) BE797384A (de)
CA (1) CA974304A (de)
CH (2) CH555540A (de)
DE (2) DE2365386C3 (de)
FR (1) FR2180323A5 (de)
GB (1) GB1395673A (de)
IT (1) IT980675B (de)
NL (1) NL174875C (de)
SE (1) SE393680B (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007733A1 (de) * 1978-07-13 1980-02-06 Brown Boveri Kent Limited Vorrichtung und Verfahren für die Messung mit ionenselektiven Elektroden
DE2931774A1 (de) * 1978-08-07 1980-02-14 Technicon Instr Durchfluss-pruefzelle zum messen der ionenaktivitaet einer loesung
US4227973A (en) * 1976-09-15 1980-10-14 Bifok Ab Automatic analysis of alkali metals halides etc. by means of the use of ion-selective electrodes
US4519890A (en) * 1983-06-07 1985-05-28 Horiba, Ltd. Flow system glass electrode
US4531088A (en) * 1982-08-06 1985-07-23 Allied Corporation Blood analysis
US4556473A (en) * 1984-06-02 1985-12-03 Horiba, Ltd. Flow through type glass electrode
US4604166A (en) * 1984-08-28 1986-08-05 Amdev, Inc. Apparatus and process for reducing peristaltic pump noise in a high impedance electrochemical measuring system
US4627893A (en) * 1984-03-28 1986-12-09 Amdev, Inc. Means and methods for quantitative determination of analyte in liquids
WO1988008532A1 (en) * 1987-04-30 1988-11-03 Pennwalt Corporation Residual analyzer assembly
US4786372A (en) * 1985-07-22 1988-11-22 Amdev, Inc. Electrochemical measuring
US4981572A (en) * 1988-06-16 1991-01-01 Glastron, Inc. Electrode unit and package for a blood analyzer
US5019238A (en) * 1984-03-28 1991-05-28 Baxter Diagnostics Inc. Means for quantitative determination of analyte in liquids
US5297431A (en) * 1992-06-01 1994-03-29 Thermo Separation Products (California) Inc. Automated sample dilution
US9389200B2 (en) 2012-11-09 2016-07-12 Infineon Technologies Ag Sensor device, a method and a sensor to determine a relative concentration of a first kind of ions with respect to a second kind of ions solute in a drop of liquid

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5522649U (de) * 1978-07-31 1980-02-14
JPS58129366A (ja) * 1982-01-29 1983-08-02 Olympus Optical Co Ltd 分配分注方法
GB8709514D0 (en) * 1987-04-22 1987-05-28 Manchester Inst Science Tech Measuring amount of selected component
US9605916B2 (en) * 2014-09-19 2017-03-28 Johannes Stickling Cleaning apparatus for cooling tube array

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE623890A (de) * 1961-10-20
US3804593A (en) * 1964-05-25 1974-04-16 Technicon Instr Automatic analysis apparatus and method
US3357910A (en) * 1964-12-08 1967-12-12 Corning Glass Works Electrode structure including temperature control means
DE1548912B1 (de) * 1965-03-26 1971-11-25 Ceskoslovenska Akademie Ved Vorrichtung zum aufteilen stroemender medien auf einzelne aufeinanderfolgende abschnitte
US3556950A (en) * 1966-07-15 1971-01-19 Ibm Method and apparatus for automatic electrochemical analysis

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4227973A (en) * 1976-09-15 1980-10-14 Bifok Ab Automatic analysis of alkali metals halides etc. by means of the use of ion-selective electrodes
EP0007733A1 (de) * 1978-07-13 1980-02-06 Brown Boveri Kent Limited Vorrichtung und Verfahren für die Messung mit ionenselektiven Elektroden
DE2931774A1 (de) * 1978-08-07 1980-02-14 Technicon Instr Durchfluss-pruefzelle zum messen der ionenaktivitaet einer loesung
FR2433180A1 (fr) * 1978-08-07 1980-03-07 Technicon Instr Cellule a ecoulement continu pour determiner l'activite ionique
US4531088A (en) * 1982-08-06 1985-07-23 Allied Corporation Blood analysis
US4519890A (en) * 1983-06-07 1985-05-28 Horiba, Ltd. Flow system glass electrode
US4627893A (en) * 1984-03-28 1986-12-09 Amdev, Inc. Means and methods for quantitative determination of analyte in liquids
US5019238A (en) * 1984-03-28 1991-05-28 Baxter Diagnostics Inc. Means for quantitative determination of analyte in liquids
US4556473A (en) * 1984-06-02 1985-12-03 Horiba, Ltd. Flow through type glass electrode
US4604166A (en) * 1984-08-28 1986-08-05 Amdev, Inc. Apparatus and process for reducing peristaltic pump noise in a high impedance electrochemical measuring system
US4786372A (en) * 1985-07-22 1988-11-22 Amdev, Inc. Electrochemical measuring
WO1988008532A1 (en) * 1987-04-30 1988-11-03 Pennwalt Corporation Residual analyzer assembly
US4822474A (en) * 1987-04-30 1989-04-18 Pennwalt Corporation Residual analyzer assembly
GB2211304A (en) * 1987-04-30 1989-06-28 Pennwalt Corp Residual analyzer assembly
GB2211304B (en) * 1987-04-30 1991-12-18 Pennwalt Corp Amperometric probe for residual analyser apparatus
US4981572A (en) * 1988-06-16 1991-01-01 Glastron, Inc. Electrode unit and package for a blood analyzer
US5297431A (en) * 1992-06-01 1994-03-29 Thermo Separation Products (California) Inc. Automated sample dilution
US9389200B2 (en) 2012-11-09 2016-07-12 Infineon Technologies Ag Sensor device, a method and a sensor to determine a relative concentration of a first kind of ions with respect to a second kind of ions solute in a drop of liquid

Also Published As

Publication number Publication date
CH556537A (de) 1974-11-29
GB1395673A (en) 1975-05-29
AU5252973A (en) 1974-08-29
CA974304A (en) 1975-09-09
JPS4910793A (de) 1974-01-30
NL174875C (nl) 1984-08-16
CH555540A (de) 1974-10-31
DE2317273A1 (de) 1973-10-18
DE2365386C3 (de) 1982-01-07
IT980675B (it) 1974-10-10
DE2317273C3 (de) 1978-06-01
DE2317273B2 (de) 1977-10-13
DE2365386B2 (de) 1976-12-23
FR2180323A5 (de) 1973-11-23
SE393680B (sv) 1977-05-16
JPS5630499B2 (de) 1981-07-15
BE797384A (fr) 1973-09-27
NL174875B (nl) 1984-03-16
DE2365386A1 (de) 1974-10-03
NL7302616A (de) 1973-10-12

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