EP3036536A1 - Cellule de titrage coulométrique - Google Patents

Cellule de titrage coulométrique

Info

Publication number
EP3036536A1
EP3036536A1 EP14747947.1A EP14747947A EP3036536A1 EP 3036536 A1 EP3036536 A1 EP 3036536A1 EP 14747947 A EP14747947 A EP 14747947A EP 3036536 A1 EP3036536 A1 EP 3036536A1
Authority
EP
European Patent Office
Prior art keywords
electrode
housing
coulometric titration
coulometric
diaphragm
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP14747947.1A
Other languages
German (de)
English (en)
Inventor
Thomas Blank
Günter Pfuhl
Félix Bécheiraz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mettler Toledo Schweiz GmbH
Original Assignee
Mettler Toledo Schweiz GmbH
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 Mettler Toledo Schweiz GmbH filed Critical Mettler Toledo Schweiz GmbH
Priority to EP14747947.1A priority Critical patent/EP3036536A1/fr
Publication of EP3036536A1 publication Critical patent/EP3036536A1/fr
Withdrawn legal-status Critical Current

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
    • G01N27/447—Systems using electrophoresis
    • G01N27/44704—Details; Accessories
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
    • G01N31/162—Determining the equivalent point by means of a discontinuity
    • G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
    • 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
    • G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
    • G01N27/44—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte using electrolysis to generate a reagent, e.g. for titration
    • 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
    • G01N27/447—Systems using electrophoresis
    • G01N27/44756—Apparatus specially adapted therefor

Definitions

  • the invention relates to a coulometric titration cell for carrying out
  • volumetric titration is in many industrial laboratories one of
  • Routine methods for the quantitative determination of the substance amount of a substance or an analyte in a fluid sample are Traditionally, for this purpose, a titrant is added from a burette of a sample, which is stirred, and follows the change, for example, in the pH or conductivity of the sample with corresponding sensors. Based on the titrant volume consumed up to the end point or equivalence point of the titration and the titer of the titrant, it is then possible to use the
  • the unknown concentration or amount of analyte in the sample can be calculated.
  • the "titer” is the quotient of the actual concentration of a titration or mass solution and the desired concentration of the same solution, and the titer is therefore a factor for labeling normal solutions.
  • Titration machines used which are also referred to as titrators.
  • Titrators comprise at least one automatic dosing element with which the titrant is added in predetermined increments or dynamically to a sample, at least one suitable sensor, a control unit and a display unit.
  • the titrant is also usually liquid in a titrator, and it is necessary that the titre of the titrant is periodically checked and / or the titrant is newly prepared to detect a change due to aging and / or deterioration
  • volumetric titration is also the coulometric titration or
  • Titration cell comprises two electrochemical half-cells, wherein one electrochemical half cell acts as a working electrode and the other electrochemical half cell acts as a counter electrode arranged in an electrolyte.
  • titrant is generated electrochemically at the working electrode and the electric charge which is converted at the working electrode is determined.
  • the reverse electrochemical process takes place, wherein the Electrolyte is consumed within the electrochemical half cell of the counter electrode during the titration due to the reduction or oxidation of the substances contained at the counter electrode.
  • the two electrochemical half-cells of the coulometric titration cell can be separated from each other by a diaphragm which, depending on the type and polarity of the working electrode, allows charge and mass transfer between the two electrochemical half-cells, the transport through the diaphragm being unidirectional or bidirectional.
  • Titration cell be designed as a base or acid generator, wherein a
  • WO 2009/076144 A1 discloses a coulometric titration cell with a platinum working electrode, a platinum counter-electrode and a multi-layered ion-exchange membrane as a diaphragm.
  • the coulometric titration cell can be used either for acid titration or for base titration, depending on the polarization of the electrodes.
  • an aqueous sodium hydroxide solution NaOH
  • a cation exchange membrane a cation exchange membrane
  • sample contains iodide, it can be reduced to iodine at the working electrode and, for example, sulfur dioxide (SO 2 ) in the sample can be determined.
  • SO 2 sulfur dioxide
  • the known coulometric titration cells have the disadvantage that, when carrying out the titration, gases are produced at the working and / or counterelectrode, which have to be removed from the coulometric titration cell; moreover, they are also due to the frequently used noble-metal electrodes expensive in production. In particular, the provision of small and compact coulometric titration cells is therefore not yet possible.
  • the object of this invention is to provide a coulometric
  • Titration cell which is designed to be small and compact and during which essentially no gas evolution occurs during operation.
  • This object is achieved by a coulometric titration cell for performing a coulometric titration on a sample with a first electrochemical half-cell having a first electrode, and with a second housing comprising a second electrochemical half cell with a second electrode and an electrolyte. The second electrode is immersed in the electrolyte.
  • the coulometric titration cell comprises a redox system with a first and second
  • Redox partner a diaphragm, which between the first and second
  • electrochemical half-cell is arranged, and a circuit in which the first and second electrochemical half-cell are integrated.
  • the diaphragm and the first electrode are in contact with the sample.
  • the second housing is closed, so that a charge and mass transport is only possible via the diaphragm.
  • the electrolyte which is solid or solidified, contains the first redox partner.
  • the first and second redox partners of the redox system are selected so that gas evolution at the second electrode is substantially suppressed.
  • the coulometric titration cell according to the invention is very advantageous since, owing to the choice of the first and second redox partners of the redox system, of which the first redox partner is arranged in the solid or solidified electrolyte, during operation gas evolution at the second electrode, which into the electrolyte dips, can essentially be prevented. This makes it possible to design the second housing, which surrounds the second electrochemical half cell, particularly small and compact.
  • the diaphragm separates the second electrochemical half cell from the first electrochemical half cell and, in use, from the sample or the
  • electrochemical half-cell can therefore only be done via the diaphragm.
  • the second housing is interchangeably disposed in a first housing, so that the second electrochemical half cell can be easily replaced together with the second housing when the electrolyte contained therein is consumed.
  • the first housing may also include the first electrochemical half cell.
  • Gas evolution within the coulometric titration cell can also be greatly reduced or even completely eliminated by choosing a suitable redox system be suppressed.
  • the redox system can be one of the following
  • Substance combinations and / or compounds of these substances as first and second redox partners include: iodine / iodide, iron (II / III) cyanide compounds
  • a zinc / zinc (II) redox system can in the inventive coulometric
  • Titration cell as the first redox partner include a zinc complex compound, such as Zn [(NH 3 ) 2 (H 2 0) 2 ] 2+ as a chloride, nitrate or sulfate compound.
  • a zinc complex compound such as Zn [(NH 3 ) 2 (H 2 0) 2 ] 2+ as a chloride, nitrate or sulfate compound.
  • a zinc sacrificial electrode can be used as the second electrode.
  • the second redox partner may be present in the form of zinc powder, which is added to the solid electrolyte.
  • the electrolyte may also contain as an additive an electrically conductive compound, such as graphite or conductive salts (eg K 2 SO 4,
  • the electrolyte or the second electrode comprises the second
  • Redox partner Both redox partners can thus be present in the electrolyte.
  • the first redox partner is present in the electrolyte and the second redox partner is contained in the second electrode, which can be realized, for example, by using a sacrificial electrode as a second electrode.
  • the coulometric titration cell comprises a reversible redox system, so that depending on the circuit, the first electrode can be connected and used as the anode or cathode.
  • a reversible redox system is designed such that the chemical equilibrium between the two redox partners is shifted in one direction or the other by the circuit of the first electrode as anode or cathode.
  • Redox partners allows at least partial regeneration of the coulometric titration cell and / or the flexible use of the same coulometric titration cell as an acid or base generator.
  • the first electrode and the second electrode are, in contrast to the known prior art, preferably free of noble metals.
  • the first electrode may comprise a metal, a metal compound or mixtures thereof, preferably the metal is selected from the group comprising iron, chromium, molybdenum, nickel and / or titanium.
  • the second electrode may also be a metal, a metal compound or
  • the metal is preferably selected from the group comprising iron, chromium, molybdenum, titanium, nickel and / or zinc.
  • a zinc-containing second electrode can, for example, as
  • Victim electrode can be used.
  • the first and / or second electrode may consist wholly or partly of a glass carbon material or an electrically conductive polymer.
  • the first or second housing may contain an electrically conductive polymer or consist of an electrically conductive polymer, which can be integrated by virtue of its properties even in the circuit of the coulometric titration cell, so that the first or second housing as the first Electrode can act.
  • an electrically conductive polymer or consist of an electrically conductive polymer which can be integrated by virtue of its properties even in the circuit of the coulometric titration cell, so that the first or second housing as the first Electrode can act.
  • Titration cell are in particular polymers which contain one or more additives to increase the electrical conductivity. Suitable additives are
  • the additive is preferably added to the polymer in an admixture of about 20 to about 35%.
  • a solid electrolyte may for example be an aqueous solution of the first
  • Redoxpartners or the first and second Redoxpartners include, for example, about 10% to about 40% silica gel was added to bind the water contained.
  • Hydroxyethylene cellulose used for water binding.
  • the result during the titration in the electrolyte Zn 2+ which may be bound with a suitable chelating agents or ion exchangers.
  • the complexing agent is also the Electrolytes added.
  • complexing agents or ion exchangers for example, zeolites or similarly acting clay minerals or silicates can be used.
  • an I 2 / I 3 _ or Fe (CN) g - 4- used -Redoxsystem it can be dispensed with the use of further complexing agents or ion exchangers, since in this case the first and second redox partners themselves are complexing agents , Again, these redox systems can work together with a solid or solidified
  • Electrolytes are used.
  • Solid electrolytes such as hydrogels, which contain at least the first redox partner, can also be used instead of solid electrolytes.
  • a hydrogel electrolyte for a coulometric titration cell can be generated, for example, by converting an aqueous n.sup. + Solution into a hydrogel, wherein X in particular comprises one of the following anions: CT, SOI ⁇ , CH 3 S0 3 , triflate: - CF 3 S0 3 (triflate), p - Tol S0 3 (tosylate).
  • linear polymer chains such as poly-N-vinylformamide
  • crosslinked polymer chains such as a copolymer of glycerol methacrylate and N, N'-bis-acrylamide
  • a suitable viscosity can be achieved by using about 10% to about 30% monomer by weight.
  • hydrogels have a technical production advantage, since they are introduced in liquid form into the second housing and there directly, so in situ, polymerized and so can be solidified.
  • the diaphragm which is between the first and second electrochemical
  • the diaphragm consists essentially of a porous ceramic, a porous glass and / or an ion-selective membrane.
  • the diaphragm can be configured as an anion-exchange membrane or cation-exchange membrane, wherein the type and design of the diaphragm depends on the use of the coulometric titration cell as the acid or base generator as well as the redox system used.
  • an inert salt may be added to the sample which does not chemically alter the sample and thus is chemically inert to the sample. Examples of such inert salts are, for example, potassium sulfate ⁇ K 2 S0 4 ) or potassium nitrate (KN0 3 ).
  • an inert salt By adding an inert salt, the conductivity of the sample can be increased, which is usually present as a fluid, for example as a solution or suspension. Increasing the conductivity of the sample enables a coulometric titration to be carried out with a lower voltage applied between the first and second electrodes, since the increased ion mobility due to the addition of the inert salt increases the ion mobility
  • Titration cell have a chemical or physical diffusion trap, which serves to prevent mass transfer from the second electrochemical half-cell into the sample or the measuring medium.
  • diffusion or ion traps to maintain the functionality of coulometric
  • Titration cells is known in principle.
  • a further aspect of the invention relates to the provision of a measuring arrangement for carrying out a coulometric titration on a sample with a coulometric titration cell having the features described above.
  • the measuring arrangement also comprises a container which receives the sample during operation, a sensor for detecting the endpoint or equivalence point of the titration and a control and / or display unit.
  • the coulometric titration cell is in operation at least via the diaphragm and the first electrode in contact with the sample.
  • the second housing of the coulometric titration cell is closed, so that charge and mass transfer is only possible via the diaphragm.
  • the electrolyte is solid or solidified and contains a first redox partner.
  • the first and second redox partners of the redox system are chosen so that during operation gas evolution at the second electrode is largely suppressed.
  • an ion-selective, potentiometric or conductivity sensor can be used in an inventive measuring arrangement, with which during the titration at least one parameter of the sample is detected until reaching the end or equivalence point.
  • FIG. 1 Schematic representation of a coulometric titration cell, in which a second housing is arranged interchangeably in a first housing;
  • FIG. 2 Schematic representation of another coulometric titration cell, wherein the first housing is formed as a first electrode;
  • FIG. 3 Schematic representation of a measuring arrangement with a coulometric titration cell according to FIG. 2 and a sensor;
  • FIG. 4 Schematic representation of another measuring arrangement with a
  • FIG. 5 Schematic representation of a flow measuring device with a
  • FIG. 7 partial view of the coulometric titration cell of Figure 6 in section.
  • FIG. 9 partial representation of another coulometric titration cell with two laterally arranged diaphragms and a replaceable second housing.
  • Figure 1 shows a schematic representation of an inventive
  • coulometric titration cell with a second housing 1, which is filled with a solid or solidified electrolyte 2, in which a second electrode 3 dips.
  • the second housing 1 is designed to be closed. A charge and mass transport is only possible by a diaphragm 4, which is arranged in the first housing so that it is in operation in contact with a sample to be titrated. An electrical connection 8 of the second electrode 3 is led out of the second housing 1.
  • the coulometric titration cell shown in FIG. 1 comprises a first
  • Housing 5 which has an opening 6 for contacting the sample.
  • a first electrode 7 and the second housing 1 are arranged.
  • the first housing 5 is closed with a cover 10 such that an exchange of the second housing 1 and the components contained therein is possible.
  • electrical contacts 8, 9 are guided over which the first and second electrodes 3, 7 are integrated in a regulated circuit 1 1, as it is indicated here greatly simplified.
  • FIG. 2 shows a further embodiment of an inventive device
  • Embodiment in the first housing 205 is not arranged a separate first electrode, but the first housing 205 itself represents the first electrode.
  • the first housing 205 may act as a first electrode, it consists at least partially of an electrically conductive polymer and is connected via an electrical connection involved in the circuit 1 1, as indicated in Figure 2.
  • FIG. 3 shows a schematic representation of a measuring arrangement with a
  • coulometric titration cell 312 corresponds to that shown in FIG.
  • Titration cell 312 immerse in a sample 14 at which a titrimetric determination or a coulometric titration is to be carried out.
  • the sample 14 or the measuring medium is arranged in a suitable container 15 during the titration.
  • the sample 14 is usually a fluid, for example a solution or a
  • the sample 14 may be added to increase its conductivity an inert salt.
  • an inert salt here salt compounds are referred to, which behave chemically inert to the sample and these do not change chemically.
  • examples of such inert salts include potassium sulfate (K 2 S0 4 ) or potassium nitrate ⁇ KN0 3 ).
  • K 2 S0 4 potassium sulfate
  • KN0 3 potassium nitrate ⁇ KN0 3
  • FIG. 4 schematically shows a further measuring arrangement with a sensor 13 and a coulometric titration cell in a further embodiment.
  • Coulometric titration cell comprises a second housing 401, in which a second electrode 403 is arranged.
  • the second electrode 403 is incorporated in a circuit 41 1 and the second housing 401 has an overpass 416, which contains a diaphragm or is formed as a diaphragm.
  • the transfer 416 is in operation in contact with a sample 14, which is located in a container 15.
  • a first electrode 407 which is likewise integrated in the circuit 41 1, and a sensor 13, which is connected to a suitable control and / or display unit 17, dip into the sample 14.
  • the transfer 416 establishes contact between the second electrochemical half-cell with the second electrode 403 and the first electrochemical half-cell with the first electrode 407, so that charge and mass transfer can take place between the two electrochemical half-cells.
  • FIG. 5 shows schematically a flow measuring arrangement with a sensor 13 and a coulometric titration cell.
  • a sample 14 flows through a flow cell
  • the sensor 13 in which the sensor 13 and a first electrode 507 are arranged.
  • the sensor 13 is in turn connected to a control and / or display unit 17.
  • the first electrode 507 and a second electrode 503 are integrated in a circuit 51 1.
  • the second electrode 503 is disposed in a closed case 501 and immersed in an electrolyte 502 therein.
  • the second electrochemical half cell with the second electrode 503 is via a transfer
  • the transfer 516 which comprises a diaphragm, as already described in connection with FIG. 4, connected to the first electrochemical half-cell.
  • the transfer 516 is designed in such a way that both charge and mass transport are possible during operation of the coulometric titration cell between the second and first electrochemical half cells.
  • Figures 6 to 8 show two further embodiments of an inventive coulometric titration cell in section, wherein Figure 7 is a partial view of Figure 6.
  • the coulometric titration cell shown in Figures 6 and 7 comprises an elongate tubular second housing 601 filled with a solid or solidified electrolyte 602.
  • a second electrode 603 is immersed in the electrolyte 602.
  • the second electrode 603 in this embodiment is a thin plate or a thin plate made of a suitable electrode material, which is arranged on the inner wall of the housing 601.
  • Housing 601 is closed with a lid 624, which also the
  • Closing element of a handle member 618 is.
  • the lid 624 may be removed, for example, to replenish or replace the electrolyte 602.
  • the lid 602 is detachably connected to the handle member 618 and the second housing 601.
  • the second housing 601 On the front side, on the immersed in operation in a measuring medium or a sample end, the second housing 601 is closed by a diaphragm 604, which is fixed by a holding member 621 on the second housing 601. In order that the sample can not penetrate into the second housing 601, is between the
  • Diaphragm 607 and the second housing 601 arranged a sealant 626, here an O-ring.
  • a first electrode 607 is arranged, which in this embodiment is annular, so that the sample, in operation, can come into contact with the diaphragm 604 via the recess in the annular first electrode 607.
  • the front end of the second housing 601 is enclosed by a first housing 620 omitting an opening 625.
  • the opening 625 ensures contact between the diaphragm 604 and the sample into which the coulometric titration cell is dipped end face.
  • the first electrode 607 is also arranged in the first housing 620.
  • Both the first and second electrodes 603, 607 are electrical
  • control and / or display unit 17 can also be used to regulate the voltage or the current between the first and second electrodes, to analyze the determined parameter values, to determine the result of the coulometric titration and to display it.
  • the control and / or display unit 17 can be configured as separate components or as a combined component.
  • an adapter 619 is shown in FIG. 6, which serves to use the coulometric titration cell, for example, in a holder of a titrator.
  • FIG. 8 shows a further exemplary embodiment of a coulometric titration cell with an end-face diaphragm 804, which terminates an elongated tubular second housing 801. Between the diaphragm 804 and the second housing 801, as already shown in Figures 6 and 7, a sealing means is arranged. The diaphragm 804 is held or fixed to the second housing 801 with a holding member 821.
  • the second housing 801 is filled with a solid or solidified electrolyte 802 into which a rod-shaped second electrode 803 is inserted.
  • the end of the second housing 801 facing away from the sample during operation is partially of one
  • electrical connections 808, 809 are led to the connection of the second electrode 803 and a first electrode.
  • the first electrode is formed in this embodiment of the second housing 801, which comprises an electrically conductive polymer or an electrically conductive layer.
  • the second housing 801 is connected to the electrical connection 809.
  • FIG. 9 shows a partial representation of a further coulometric titration cell with at least two laterally arranged diaphragms 922, 923 in section.
  • the coulometric titration cell again comprises an elongate and in the
  • Substantially tubular second housing 901 which is arranged exchangeably in a first housing 905.
  • the second housing 901 is filled with a solid or solidified electrolyte 902 and is laterally separated by at least two
  • diaphragms 922, 923 completed in operation against a sample.
  • the diaphragms 922, 923 are sealed by two sealants 926 so that the sample in use contacts only the diaphragms 922, 923 with the second electrochemical half cell.
  • a rod-shaped second electrode 903, as has already been described in connection with FIG. 8, is immersed in the electrolyte 902.
  • a first electrode 907 is mounted, which is embedded here as a flat disc in the first housing 905.
  • the first housing 905 has at least two lateral openings 906 arranged so that in operation the diaphragms 922, 923 and the first electrode 907 may be in contact with the sample.
  • the first and second electrodes 903, 907 are in turn via suitable electrical
  • Embodiments with knowledge of the present invention can be provided, for example, by combining the features of the individual embodiments with each other and / or individual functional units of the embodiments are exchanged.
  • the embodiments shown in FIGS. 6 to 9 can be configured with or without an exchangeable second housing, and furthermore the first electrode can be designed as a rod, sheet or plate.
  • a coulometric titration cell according to the described exemplary embodiments can be used in one of the measuring arrangements shown for carrying out a
  • coulometric titration the coulometric titration cells according to FIGS. 6 to 8 can be designed with or without adapters.
  • the adapter can be designed in various forms, which are suitable for use in a desired automatic titration or on a suitable stand.

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  • Life Sciences & Earth Sciences (AREA)
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  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Electrochemistry (AREA)
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Abstract

L'invention concerne une cellule de titrage coulométrique et un système de mesure comportant une cellule de titrage coulométrique qui comprend une première demi-cellule électrochimique munie d'une première électrode (205, 801, 7, 407, 507, 607, 907), un deuxième boîtier (1, 401, 501, 601, 801, 901) qui comprend une deuxième demi-cellule électrochimique munie d'une deuxième électrode (3, 403, 503, 603, 803, 903) et d'un électrolyte (2, 302, 402, 502, 602, 802, 902) dans lequel la deuxième électrode (3, 403, 503, 603, 803, 903) est immergée, un système redox muni d'au moins un premier et un deuxième élément redox, au moins un diaphragme (4, 604, 804) qui est agencé entre la première et la deuxième demi-cellule électrochimique, et un circuit électrique (11, 411, 511) dans lequel la première et la deuxième demi-cellule électrochimique sont incorporées, au moins le diaphragme (4, 604, 804) et la première électrode (7, 407, 507, 607, 907) étant en contact avec l'échantillon pendant le fonctionnement. Selon l'invention, le deuxième boîtier (1, 401, 501, 601, 801, 901) est fermé, de sorte qu'un échange de charge et de matière n'est possible que par l'intermédiaire du diaphragme (4, 604, 804), l'électrolyte (2, 302, 402, 502, 602, 802, 902) est solide ou solidifié et contient un premier élément redox, et le premier et le deuxième élément redox du système redox sont sélectionnés de telle manière que la production de gaz à l'intérieur de la cellule de titrage coulométrique est largement réduite pendant le fonctionnement.
EP14747947.1A 2013-08-19 2014-08-07 Cellule de titrage coulométrique Withdrawn EP3036536A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14747947.1A EP3036536A1 (fr) 2013-08-19 2014-08-07 Cellule de titrage coulométrique

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13180899.0A EP2840390A1 (fr) 2013-08-19 2013-08-19 Cellule de titration coulométrique
EP14747947.1A EP3036536A1 (fr) 2013-08-19 2014-08-07 Cellule de titrage coulométrique
PCT/EP2014/066953 WO2015024787A1 (fr) 2013-08-19 2014-08-07 Cellule de titrage coulométrique

Publications (1)

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EP3036536A1 true EP3036536A1 (fr) 2016-06-29

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EP14747947.1A Withdrawn EP3036536A1 (fr) 2013-08-19 2014-08-07 Cellule de titrage coulométrique

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Country Status (5)

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US (1) US10352896B2 (fr)
EP (2) EP2840390A1 (fr)
JP (1) JP6420343B2 (fr)
CN (1) CN105474009B (fr)
WO (1) WO2015024787A1 (fr)

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CN106383163B (zh) * 2016-10-19 2023-10-17 中国人民解放军国防科学技术大学 一种基于单电子晶体管的电离式气敏传感器及其制备方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
US20040231984A1 (en) * 2002-12-02 2004-11-25 Imants Lauks Heterogeneous membrane electrodes

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JP6420343B2 (ja) 2018-11-07
JP2016528507A (ja) 2016-09-15
US10352896B2 (en) 2019-07-16
EP2840390A1 (fr) 2015-02-25
CN105474009A (zh) 2016-04-06
WO2015024787A1 (fr) 2015-02-26
US20160161447A1 (en) 2016-06-09
CN105474009B (zh) 2019-03-29

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