WO1992001219A1 - Dispositif detecteur electrochimique a selectivite ionique - Google Patents

Dispositif detecteur electrochimique a selectivite ionique Download PDF

Info

Publication number
WO1992001219A1
WO1992001219A1 PCT/NO1991/000099 NO9100099W WO9201219A1 WO 1992001219 A1 WO1992001219 A1 WO 1992001219A1 NO 9100099 W NO9100099 W NO 9100099W WO 9201219 A1 WO9201219 A1 WO 9201219A1
Authority
WO
WIPO (PCT)
Prior art keywords
sensor device
ion
accordance
water
ions
Prior art date
Application number
PCT/NO1991/000099
Other languages
English (en)
Inventor
Rolf ØDEGÅRD
Sven Morten Hesjevik
Georg Hagen
Original Assignee
Sinvent A/S
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 Sinvent A/S filed Critical Sinvent A/S
Publication of WO1992001219A1 publication Critical patent/WO1992001219A1/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
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes

Definitions

  • the present invention concerns an ion-selective electro ⁇ chemical sensor device for analytical laboratory purposes, for process monitoring and for monitoring polluting discharges into the environment of special ions, particularly nitrate ions from industry and agriculture.
  • Previously known commercial nitrate sensors are based on measurement of potentials over an ion-selective diaphragm with an internal reference solution and a reference electrode.
  • the response time of commercial sensors is relatively long, and the precision is strongly influenced by interference from other ion types.
  • the sensors must be calibrated at short intervals, and the service life is very limited.
  • the purpose of the present invention is primarily to be able to detect and measure the concentration of nitrate ions in a aqueous solution containing other ions, in a fast and efficient manner, by means of a new type of nitrate sensor which can be regenerated and calibrated while in use.
  • the main component of the present invention is an electro ⁇ active polymer material which is applied on an electronically conducting solid state substrate, e.g. of platinum metal.
  • an electronically conducting solid state substrate e.g. of platinum metal.
  • the electroactive polymer material is manufactured by a direct, electrochemical polymerization on the substrate.
  • the polymer may first be provided by a chemical method, and subsequently be applied to the substrate.
  • An example of an electroactive polymer which can be used as a coating on the substrate in order to provide a sensor device in accordance with the invention is poly-(3-methyl- thiophene) .
  • the polymer electrode is included as an active (sensor) part of an electrochemical cell system.
  • An adjustable voltage is applied to the cell, and the current through the electroactive polymer electrode is recorded.
  • the current response at a certain potential, or the integrated charge which has passed through the polymer electrode, can be put in relation to the concentration of the particular ion it is desirable to detect in the solution.
  • the sensitivity and specificity regarding one particular ion type can be adjusted by selecting the electroactive polymer material.
  • the sensitivity can also be adjusted by adapting potential range and potential scan rate.
  • fig. 1 shows a cyclic voltammogram for a polymer electrode in accordance with the invention
  • fig. 2 shows the current response of the polymer electrode for different ion types
  • fig. 3 shows the current response of a polymer electrode in accordance with the invention as a function of potential scan rate.
  • fig. 1 shows curves recorded for a sensor device in accordance with the invention, with a poly-(3-methylthiophene) polymer electrode in aqueous solution of respectively 0.1 M KN0 3 and 0.1 M KCL.
  • the current response of the electrode is substantially stronger than in the chloride solution in the potential range about 700 mV (versus an Ag/AgCl reference electrode) .
  • Further experiments with sulfate and phosphate solutions result in current responses which are correspondingly weak as the chloride response.
  • fig. 2 is shown (in a log-log diagram) the current response (current density) of the polymer electrode at 700 mV (versus an Ag/AgCl reference electrode) as a function of the concentration of some ion-types in an aqueous solution (respec ⁇ tively KCIO4, KNO 3 , KC1 and K2SO4) .
  • the current response in the nitrate and perchlorate solutions shows a strong dependence of the ion concentrations, while sulfate and chloride merely exhibit a weak current response.
  • Fig. 3 shows the influence of potential scan rate on the current response (current density) of the polymer electrode at 700 V potential (versus an Ag/AgCl reference electrode) , for pure 0.1 M solutions of KC10 4 , KN0 3 , KC1 and K 2 S0 . It appears that the response in chloride and sulfate solutions is little influenced by the scan rate, while the response in nitrate and perchlorate solutions on the contrary depends strongly on the scan rate. This implies that it is possible to increase the sensitivity to nitrate ions (and possibly perchlorate ions) in relation to chloride and sulfate ions by increasing the scan rate.
  • the sensor device in accordance with the present invention exhibits clear advantages as to a strong response to nitrate ions, and little interference from other ion types.
  • this electrode is also sensitive to perchlorate ions in water.
  • the response time is short, and the sensor device can be regenerated and calibrated while in use.
  • the measurement procedure can be automatized, and can operate in a completely automatic environment monitoring system.
  • the active sensor material can be manufactured in a relatively simple manner, which makes reconditioning of the sensor device easy.

Landscapes

  • 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)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)

Abstract

Un dispositif détecteur destiné à détecter un type spécial d'ions en solution aqueuse, notamment les ions de nitrate, comporte un revêtement de polymère organique électro-actif appliqué sur un substrat monolithique à conductivité électronique et de préférence métallique.
PCT/NO1991/000099 1990-07-05 1991-07-04 Dispositif detecteur electrochimique a selectivite ionique WO1992001219A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO90903011A NO903011L (no) 1990-07-05 1990-07-05 Elektrokjemisk ioneselektiv sensor.
NO903011 1990-07-05

Publications (1)

Publication Number Publication Date
WO1992001219A1 true WO1992001219A1 (fr) 1992-01-23

Family

ID=19893329

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NO1991/000099 WO1992001219A1 (fr) 1990-07-05 1991-07-04 Dispositif detecteur electrochimique a selectivite ionique

Country Status (3)

Country Link
AU (1) AU8008191A (fr)
NO (1) NO903011L (fr)
WO (1) WO1992001219A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0684466A2 (fr) * 1994-05-27 1995-11-29 Kone Oy Electrode sensible aux ions et procédé pour fabriquer une électrode sensible aux ions
US5700922A (en) * 1991-12-24 1997-12-23 Isis Pharmaceuticals, Inc. PNA-DNA-PNA chimeric macromolecules
WO1999045376A1 (fr) * 1998-03-03 1999-09-10 Unisense Aps Procede de regulation de la sensibilite d'un microcapteur et microcapteur associe
US9281219B2 (en) 2013-09-18 2016-03-08 Suprasensor Technologies, Llc Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2157503A1 (fr) * 1993-03-05 1994-09-15 John M. Riviello Detection electrochimique par impulsions utilisant des electrodes en polymere electroactif

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989007262A1 (fr) * 1988-01-29 1989-08-10 Terumo Kabushiki Kaisha Capteur recouvert d'un film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989007262A1 (fr) * 1988-01-29 1989-08-10 Terumo Kabushiki Kaisha Capteur recouvert d'un film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT'S ABSTRACT No. 633 38 E/30; & SU,A,868 527, publ. week 8230. *
ELECTROANALYSIS, Vol. 2, 1990, HANS ZIMMER et al., "Conductivity Monitoring by an Amperometric Detector with a Cu(II)-Containing Poly(3-methylthiophene) Electrode", see page 1 - page 2. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700922A (en) * 1991-12-24 1997-12-23 Isis Pharmaceuticals, Inc. PNA-DNA-PNA chimeric macromolecules
EP0684466A2 (fr) * 1994-05-27 1995-11-29 Kone Oy Electrode sensible aux ions et procédé pour fabriquer une électrode sensible aux ions
US5584979A (en) * 1994-05-27 1996-12-17 Kone Instruments Oy Ion-selective electrode and procedure for producing an ion-selective electrode
EP0684466A3 (fr) * 1994-05-27 1998-06-10 KONE Instruments Oy Electrode sensible aux ions et procédé pour fabriquer une électrode sensible aux ions
WO1999045376A1 (fr) * 1998-03-03 1999-09-10 Unisense Aps Procede de regulation de la sensibilite d'un microcapteur et microcapteur associe
US9281219B2 (en) 2013-09-18 2016-03-08 Suprasensor Technologies, Llc Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils
US9535031B2 (en) 2013-09-18 2017-01-03 Suprasensor Technologies, Llc Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils

Also Published As

Publication number Publication date
NO903011L (no) 1992-01-06
NO903011D0 (no) 1990-07-05
AU8008191A (en) 1992-02-04

Similar Documents

Publication Publication Date Title
Wang et al. Effect of surface‐active compounds on the stripping voltammetric response of bismuth film electrodes
Lubert et al. History of electroanalytical methods
US5397451A (en) Current-detecting type dry-operative ion-selective electrode
Ilangovan et al. Enzyme based biosensor for heavy metal ions determination
US11119067B2 (en) Glass electrode
Ross Jr Solid-state and liquid membrane ion-selective electrodes
DE3752278T2 (de) Verfahren für elektrochemische Messungen
Kim et al. Evaluation of phosphate ion-selective membranes and cobalt-based electrodes for soil nutrient sensing
US20050252790A1 (en) Electrochemical sensor system and sensing method
Llenado Potentiometric response of the calcium selective membrane electrode in the presence of surfactants
US3915831A (en) Hydrogen sulfide sensing cell
US4229264A (en) Method for measuring the relative etching or stripping rate of a solution
Alegret et al. Response characteristics of conductive polymer composite substrate all-solid-state poly (vinyl chloride) matrix membrane ion-selective electrodes in aerated and nitrogen-saturated solutions
US5076904A (en) Electrochemical measuring cell for determining ammonia or hydrazine in a measuring sample
Gupta et al. A new Zn2+‐selective sensor based on 5, 10, 15, 20‐tetraphenyl‐21H, 23H‐porphine in PVC Matrix
US3859191A (en) Hydrogen cyanide sensing cell
US5489371A (en) Sensor for electrochemical measurements
WO1992001219A1 (fr) Dispositif detecteur electrochimique a selectivite ionique
Lewenstam Design and pitfalls of ion selective electrodes
EP0833149A1 (fr) Procédé pour mesurer la concentration ionique
Lee et al. Comparison of tubular polymeric pH and ammonium ion electrodes as detectors in the automated determination of ammonia
Jagner et al. Coulometric stripping potentiometry
US3655526A (en) Potentiometric titration process
Pletcher et al. Studies of a microelectrode sensor for monitoring chlorine in water supplies
US3528778A (en) Method for the determination of acid concentrations

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA FI JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA