CS231026B1 - Method of voltmetric determination of oxygen and sensor to perform this method - Google Patents

Method of voltmetric determination of oxygen and sensor to perform this method Download PDF

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Publication number
CS231026B1
CS231026B1 CS688982A CS688982A CS231026B1 CS 231026 B1 CS231026 B1 CS 231026B1 CS 688982 A CS688982 A CS 688982A CS 688982 A CS688982 A CS 688982A CS 231026 B1 CS231026 B1 CS 231026B1
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Czechoslovakia
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working electrode
membrane
sensor
oxygen
electrolyte
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CS688982A
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Czech (cs)
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Lubomir Serak
Jaroslav Cap
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Lubomir Serak
Jaroslav Cap
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Priority to CS688982A priority Critical patent/CS231026B1/en
Priority to GB08324822A priority patent/GB2127977B/en
Publication of CS231026B1 publication Critical patent/CS231026B1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/404Cells 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

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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)

Abstract

The voltametric determination of oxygen dissolved in liquids or present in gaseous mixtures consists in polarization of a sensor by rectangular potential pulses, each pulse being applied after the concentration of oxygen is restored in a space between a separation membrane (3) and the surface of a working electrode (4). The sensor has a limited space (1) filled with electrolyte (6) formed between membrane (3) and working electrode (4), which has advantageously a cylindric shape, the surface area of the base of the space ranges from one third to ten times the surface area of working electrode (4), and the height ranges from 1 to 500 mu m. The limited space (1) may be formed by means of a hole in a foil (2) inserted between membrane (3) and working electrode (4) or it may be formed by a hole in the insulation body (7) of the working electrode (4) between the membrane (3) and the working electrode (4) (Fig. 2). <IMAGE>

Description

Vynniez se týká jednak způsobu stanoveni tyslíku elektrochemickou voltaoetrickou metodou a jednak čidla, umooňujicího tento, způsob stanoveni, *The present invention relates both to a method for the determination of a housing by an electrochemical voltaoetric method and to a sensor enabling this method to be determined.

Vootameerická, resp. polarografické stanoveni kolíku je známo téměř 50 let, První polarografické stanoveni popsal V. Vítek, Collection 7, (1935) 537 až 547, polarografické stanoveni se rtulovou kapkovou elektrodou, která je oddělena od měřeného roztoku peraeebblni membránou, popsal jeden z autorů tohoto - vynálezu L· šerák: Z, Ptys, Chem,, beipsig, Sonderheft, 19519, s, 84, Stanovení s pevnou pracovní elektrodou, oddělenou od vzorku vrstvou elektrolytu poppali P, W, Daview a F, Brink,- Rev, Sel, Instrum, £3, 524, stanovení s pevnou pracovní elektrodou, oddělenou od měřeného vzorku membránou, popsal L. C, Clark, Trans, Anor, Soc, Art, Int, torg. 2, (1956), 41 až 45,Vootameerická, respectively. The pin polarographic assay has been known for almost 50 years. The first polarographic assay was described by V. Vítek, Collection 7, (1935) 537-547, a polarographic assay with a mercury droplet electrode separated from the measured solution by the perebeleb membrane, described by one of the inventors. Lyser: Z, Ptys, Chem, beipsig, Sonderheft, 19519, p, 84, Determination with fixed working electrode, separated from the sample by electrolyte layer, P, W, Daview and F, Brink, - Rev, Sel, Instrum, £ 3,524, a fixed working electrode assay separated from the measured sample by a membrane was described by L. C., Clark, Trans, Anor, Soc, Art, Int, torg. 2, (1956), 41-45,

V těchto pracích bylo voltametrické . stanoveni kyslíku postupně zdokonalováno „a v podobíš, vyCház^ící z práce Clarkovy,- je prováděno dodnes, . např, Kioich, Η, P, Kreuzer, F, Spaan, J; G: Biocapt 75, 307 až 312, 1975, V Clarkově uspořádáni je ěidlo složeno z pracovní polarizovenépevné elektrody, referentni elektrody, elektrolytu a bembrěány propustné pro kyslík a nepropustné pro vodu, ionty a velké molekuly - tak, že mm z i membránou a po- .In these works it was voltammetric. the determination of oxygen has been progressively improved and in a form based on Clark's work, it has been carried out today. e.g., Kioich, Η, P, Kreuzer, F, Spaan, J; G: Biocapt 75, 307-312, 1975. In Clark's arrangement, the sensor consists of a working polarized solid electrode, a reference electrode, an electrolyte, and a oxygen-permeable and water-impermeable, ion-impermeable, bromine-impermeable cell, so that the mm .

vrchem pracovní elektrody je jen tenká vrstva elektrolytu, Pracovní elektroda' je katodicky polarizovaná na konstantní p^lteJ^c^dLá:! a ' proud, p^^^c^th^ázeí^í^zí Sídlem, je při konstantní teplotě přímo úměrný mnoostvi tyelíku dopraveného k povrchu pracovní elektrody, a tedy i koncentraci kyslíku ve vyšetřovaném prostředí v bezprostřední blízkosti membrAny. V^yni^ajjc^zi vlastnosti Sídla jsou ale provázeny vlastností nevýhodnou, totiž znaSnou závislostí proudového signálu na teplotě (zvýšení signálu až o 8 % při zvýšení teploty o 1 °C), Tato závislost je urSována převážně vellým teplotním koeficientem prop^t^^si membrány pro kyslík, Tato propuutnost se s rostoucí teplotou eχpononoiáloě zvyšuje, Při praktickém měřeni musí být teplotní signálu automoticky komppnzována, což piři větších teplotních rozdílech om^e^i^jje r·proS^Ucovijtlnost i správnost oOěení,the top of the working electrode is only a thin layer of electrolyte. The working electrode is cathodically polarized to a constant electrolyte. and the current through the seat is at a constant temperature proportional to the amount of tulle delivered to the working electrode surface and hence to the oxygen concentration in the test environment in the immediate vicinity of the membrane. However, the properties of the seat are accompanied by a disadvantageous property, namely a significant dependence of the current signal on temperature (signal increase by up to 8% at a temperature increase of 1 ° C). This dependence is determined mainly by a large temperature coefficient prop. The oxygen permeability of this membrane increases substantially with increasing temperature. In practical measurements, the temperature signal must be auto-filled, which, in the case of larger temperature differences, increases the accuracy and accuracy of the treatment.

Uvedená nevýhoda je odstraněna způsobem - pulsního voltametrického stanoveni a Sídlem podle vynálezu, jehož postata spočívá v periodické polarizaci Sidla pravoúhlými napětovými pulsy, přičemž každý puls následuje až po obnovení koncentrace kyslíku v ohraničeném, elektrolytem vyplněném prostoru, vytvořeném mozi'bemmránou a povrchem pracovní elektrody,This disadvantage is overcome by the pulse voltametric method and the seat of the present invention, which is based on periodic polarization of the sensor by rectangular voltage pulses, each pulse following recovery of the oxygen concentration in the enclosed electrolyte-filled space formed by the diaphragm and working electrode surface.

Volba velikosti intervalu mezi jednotlivými pulsy od 1 až do 10 s či více závisí na vlastnostech membrány a rozměrech ohraničeného prostoru,The choice of the interval between individual pulses from 1 to 10 s or more depends on the properties of the membrane and the dimensions of the enclosed space,

Dle je předmětem vynálezu čidlo k prováděni způsobu podle vynálezu, jehož podstata spočívá v tom, že je . mozi m^i^t^b^tá^ou a pracovní elektrodou vytvořen ohraničený prostor vyplněný elektrolytem, s výhodou válcový, jehož plocha základny je v rozmezí jedné třetiny až desetinásobku plochy pracovní elektrody a výška je v rozoozí 1 až 500 <uo.According to the present invention there is provided a sensor for carrying out the method according to the invention, the principle of which is. a limited electrolyte-filled, preferably cylindrical, electrolyte-filled space having a base area in the range of one-third to ten times the area of the working electrode and a height in the range of 1 to 500 < RTI ID = 0.0 &gt;

Tento ohraničený prostor lze s výhodou vytvořit prostřednictvím válcového otvoru ve fólii, . která je vložena oozí membránu ' a pracovní elektrodu,This limited space can be advantageously formed by means of a cylindrical opening in the foil. which is inserted with a goat membrane and a working electrode,

Informace o kyslíku se získá měřením okambžtého proudu v přesně nastavené_ době po začátku pulsu, kdy se již neuplatňuje nabbjecí proud - dvojvrstvy a nedochází'ještě k podstatnému snížení koncentrace ^yslí^u v ohraničeném prostoru mezi membránou a povrchem pracovní elektrody, xOxygen information is obtained by measuring the current current at a precisely set time after the start of the pulse, when the charge current of the bilayers is no longer applied and there is no significant decrease in the concentration of the sclerosis in the confined space between the membrane and the working electrode surface.

Na připojeném.výkrese je v podélném řezu znázorněno čidlo podle vynálezu,The attached drawing shows a longitudinal section of a sensor according to the invention.

Čidlo se skládá z pláště čidla 8 odděleného vrstvou tmelu 2 jednak od referentni elektrody 2 a dále Pak od izolačního těla pracovní elektrody I, v němž je v podélné ose čidla vedena pracovní elektroda —. Obě elektrody jsou jedním koncem napojeny na koaxiální kabel 10 a jejich druhý konec vystupuje do prostoru elektrolytu 6, Elektrolyt 6 je oddělen od vnějšího prostředí membránou J, jež je připevněna k plášti čidla 8 prostřednictvím fixač3 ního pretence 11. Mezi membránou Д a plášť čidla 8 je v proetoru elektrolytu 6 vložena fólie 2 e válcovým otvorem, který mezi pracovní elektrodou £ a membránou J dává vznik ohraničenému proetoru 1·The sensor consists of a housing of the sensor 8 separated by a layer of sealant 2 from the reference electrode 2 and then from the insulating body of the working electrode I, in which the working electrode - is guided in the longitudinal axis of the sensor. Both electrodes are connected at one end to the coaxial cable 10 and the other end extends into the electrolyte compartment 6. The electrolyte 6 is separated from the outside by a membrane J which is attached to the sensor housing 8 by means of fixation brace 11. Between the membrane D and the sensor housing 8 in the electrolyte 6, a film 2 e is inserted through a cylindrical opening which gives rise to a limited proethore 1 between the working electrode 6 and the membrane.

Měřením okamžitého proudu v přesně nastavené době po začátku pulsu, kdy se již neuplatňuje nabíjecí proud dvojvrstvy a nedochází ještě к podstatnému snížení koncentrace Kyslíku v ohraničeném prostoru 1 mezi membránou Д a povrchem pracovní elektrody se získají údaje sloužící к určení stanovované koncentrace kyslíku·Measuring the instantaneous current in exactly the set time after the beginning of the pulse, when the charging current no longer applied bilayer and does not substantially decrease even к oxygen concentration in the space delimited between the membrane 1 and Д working electrode surface to obtain data serving к determination of an oxygen concentration ·

Vynálezu lze využít v provozních podmínkách ke stanovení kyslíku jednak rozpuštěného v kapalinách, ale též obsaženého v plynných směsích.The invention can be used under operating conditions to determine oxygen dissolved both in liquids but also contained in gaseous mixtures.

Claims (3)

P Ě £ D M Ё T VYNÁLEZUTHE INVENTION 1. Způsob voltametrického stanovení kyslíku pomocí čidla, které obsahuje separační membránu a pracovní elektrodu, a dále pomocí vyhodnocovače signálu, vyznačený tím, Že čidlo se polarizuje pravoúhlými napěťovými pulsy, přičemž každý puls následuje až po obnovení koncentrace kyslíku v prostoru mezi separační membránou a povrchem pracovní elektrody.Method for the voltammetric determination of oxygen by means of a sensor comprising a separating membrane and a working electrode, and further by means of a signal evaluator, characterized in that the sensor is polarized by rectangular voltage pulses, each pulse following the oxygen concentration in the space between the separating membrane and the surface working electrodes. 2. Čidlo к provádění způsobem podle bodu 1, složené z pracovní elektrody,* nepolarizované referentňí elektrody, elektrolytu a separační membrány, vyznačené tím, že mezi membránou (3) a pracovní elektrodou (4) je vytvořen ohraničený prostor (1) vyplněný elektrolytem, například válcový, jehož plocha základny je v rozmezí jedné třetiny až desetinásobku plochy pracovní elektrody a výška je v rozmezí 1 až 500 (om.2. A sensor according to claim 1, comprising a working electrode, an unpolarized reference electrode, an electrolyte and a separation membrane, characterized in that a boundary (1) filled with an electrolyte is formed between the membrane (3) and the working electrode (4). for example, cylindrical with a base area in the range of one third to ten times the area of the working electrode and a height in the range of 1 to 500 (om. 3. čidlo podle bodu 2, vyznačené tím, že ohraničený prostor (1) je vytvořen válcovým otvorem ve fólii (2), která je vložena mezi membránu (3) a pracovní elektrodu (4).The sensor according to claim 2, characterized in that the confined space (1) is formed by a cylindrical opening in the foil (2) which is interposed between the membrane (3) and the working electrode (4).
CS688982A 1982-09-27 1982-09-27 Method of voltmetric determination of oxygen and sensor to perform this method CS231026B1 (en)

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CS688982A CS231026B1 (en) 1982-09-27 1982-09-27 Method of voltmetric determination of oxygen and sensor to perform this method
GB08324822A GB2127977B (en) 1982-09-27 1983-09-16 Method and sensor for the voltametric determination of oxygen

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CS688982A CS231026B1 (en) 1982-09-27 1982-09-27 Method of voltmetric determination of oxygen and sensor to perform this method

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SE518437C2 (en) * 1997-09-07 2002-10-08 Appliedsensor Sweden Ab Electronic tongue
SE514042C2 (en) 1998-05-08 2000-12-18 Nordic Sensor Technologies Ab Sensor device
SE523918C2 (en) 1999-01-25 2004-06-01 Appliedsensor Sweden Ab Process for producing integrated sensor groups on a common substrate and a mask for use in the process

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US3575836A (en) * 1969-02-14 1971-04-20 Beckman Instruments Inc Polarographic sensor
US3830718A (en) * 1973-03-22 1974-08-20 Orion Research Ammonia sensor
DE2418397B2 (en) * 1974-04-16 1979-09-13 Siemens Ag, 1000 Berlin Und 8000 Muenchen Process for producing an electrode for polarographic measurements in physiological media
DE2701020B2 (en) * 1977-01-12 1979-06-07 Draegerwerk Ag, 2400 Luebeck Method for measuring the partial pressure of gases in body fluids with an incorporated measuring electrode and device for this purpose
DK133280A (en) * 1980-03-27 1981-09-28 Radiometer As Electrode arrangement

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GB2127977A (en) 1984-04-18
GB2127977B (en) 1986-10-29

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