CN1098502A - Phosphoric acid radical ion-selective electrode and uses thereof - Google Patents
Phosphoric acid radical ion-selective electrode and uses thereof Download PDFInfo
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- CN1098502A CN1098502A CN 93111643 CN93111643A CN1098502A CN 1098502 A CN1098502 A CN 1098502A CN 93111643 CN93111643 CN 93111643 CN 93111643 A CN93111643 A CN 93111643A CN 1098502 A CN1098502 A CN 1098502A
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Abstract
Phosphoric acid radical ion-selective electrode belongs to the electrode of measuring phosphate anion.The design with metallic cobalt, cobalt-base alloy, contain the cobalt mineral compound and be that to form above-mentioned top layer or the film that contains the cobalt metal be that sensitive material is made sensitive membrane to matrix at metal or other materials with physics or chemical method, in the sensitive membrane intercalation electrode head, compress with the copper post, be packaged in the electrode body of electrode cap, electrode stem and electrode tip composition, the activated processing of electrode promptly can be used for the mensuration and the analysis of phosphorus acid ion concentration, also can make the living matter sensor of phosphorous acid group.The design's electrode has good stable, reappearance and selectivity, and electrode life is long.
Description
The invention belongs to a kind of electrode of measuring phosphate anion.
Phosphate anion adopts molybdenum blue spectrophotometric method to measure usually, promptly in containing the liquid to be measured of phosphate anion, add the ammonium molybdate developer, make it to form color-developing compounds, use spectrophotometric determination solution absorbency to be measured then, determine the content of phosphate anion again by absorbance with phosphate radical.The method of this mensuration phosphate anion, it is loaded down with trivial details to handle formality, and can not realize that continuous interior lines analyze automatically.Someone adopts the PVC film, methods such as liquid film and modified membrane electrode are measured phosphate anion, the PVC film, it is that active substance such as organic tin ion exchanger are mixed in nitrobenzene or the PVC plastifier that the liquid film phosphate radical is selected electrode, prepare the phosphate radical sensitive membrane by Kynoar barrier film or PVC, be fixed on electrode tip, by internal electrolyte solution and in lead the Ag/AgCl electrode and constitute the internal reference electrode system and measure, this method is based on the principle of film-water ion-exchange, but phosphate radical is low in the mobility that the sensitive membrane with the preparation of organotin ion exchanger active substance goes up mutually, and ion exchanger easily runs off mutually from film, so stability of electrode, reappearance is relatively poor, and the life-span is shorter.The modified membrane phosphoric acid radical ion-selective electrode utilizes inorganic difficulty soluble salt to prepare electrode, though the stability of electrode and serviceable life certain improvement has been arranged, is subjected to common anionic serious interference, especially Cl
-The interference of ion, thereby make electrode lose response function to phosphate anion, do not develop a kind of problem that solves above-mentioned existence so far as yet, can be for practical phosphoric acid radical ion-selective electrode.
The present invention is intended to develop a kind of phosphoric acid radical ion-selective electrode with good stability, reappearance, selectivity and long service life, and is widely used in the analysis and the mensuration of phosphorus acid ion concentration.
The technical scheme that realizes the object of the invention is: a kind of phosphoric acid radical ion-selective electrode comprises by electrode cap (1), the packing washer (4) of liner between the electrode body that electrode stem (2) and electrode tip (8) constitute and extension line (3) and electrode stem and the electrode tip, the present invention's metallic cobalt, cobalt-base alloy, contain the cobalt mineral compound and be the metallic cobalt that the surface of matrix forms at metal or other materials with physics or chemical method, cobalt-base alloy or contain cobalt mineral compound top layer or film is made sensitive membrane (7) as sensitive material, closely press a bronze medal post (6) on the sensitive membrane (7) of intercalation electrode head (8), be screwed on the copper post (6) and be welded with extension line (3), be fixed on the copper post (5) on the electrode stem (2).A kind of plain type phosphoric acid radical ion-selective electrode is at metallic cobalt, cobalt-base alloy, contains the cobalt mineral compound and be the surface of the matrix metallic cobalt, the cobalt-base alloy that form or contain cobalt mineral compound top layer or sensitive membrane (7) that film is made as sensitive material goes up welding extension line (3) at metal or other materials with physics or chemical method, wringing fit is embedded in the plastics (9) or directly after sensitive membrane (7) goes up coated with resins or glue (9) electrode obtain stable potential in deionized water, the phthalic acid of putting into PH=4.0 is that end liquid, concentration are 10
-4Obtain after the activation processing of equilibrium potential sensor in the phosphorous acid group living matter solution of mol/L as phosphorous acid group living matter.
Be described in further detail the present invention below in conjunction with accompanying drawing.
Fig. 1 phosphoric acid radical ion-selective electrode structural drawing;
Fig. 2 plain type phosphoric acid radical ion-selective electrode structural drawing.
Sensitive membrane in the design's the phosphoric acid radical ion-selective electrode (7) is to make with metallic cobalt class solid sensitive material, such as metal Co, and cobalt-nickel alloy (Co
I), phosphatization cobalt (CoPx) and be top layer or the film that the surface of matrix forms the metallic cobalt class at metal (such as copper) or other materials with physics or chemical method such as the methods such as electrochemistry. Sensitive membrane (7) has certain taper, is coated with at the conical surface Put into electrode tip behind a small amount of silicon rubber, compress with copper post (6) (5), be encapsulated in by electrode cap (1), in the plastic electrode that electrode stem (2) and electrode tip (8) consist of, lead-out wire (3) directly is welded on the copper post (5), copper post (5) is coated epoxy resin on every side, be pressed in the hole of electrode stem (2), be fixed on the electrode stem (2), copper post (5) be pressed on sensitive membrane (7) on copper post (6) for spiral is connected, the joint liner seal washer (4) of electrode stem (2) and electrode tip (8). The design's phosphoric acid radical ion-selective electrode should carry out activation process before use or before the product export, namely use abrasive paper for metallograph sensitive membrane (7) surface finish, lead-out wire (3) is received the input of ionometer, and connects the external biliquid of saturated potassium nitrate agar bridge and connect calomel electrode. Under agitation, in deionized water, obtain stable potential, be placed on then in the Potassium Hydrogen Phthalate solution of PH=4, obtain equilibrium potential. Phosphoric acid radical ion-selective electrode through processing like this can use half a year, when performance changes such as linear response range narrow down and carry out again can continuing again to use after the above-mentioned processing.
The design's electrode also can adopt as shown in Figure 2 plain type structure, upward directly weld lead-out wire (3) in the sensitive membrane (7) that containing metal cobalt class sensitive material is made, tight fit embeds in the plastics (9) or directly coated resin or glue (9) on sensitive membrane, and the activation process of plain type phosphoric acid radical ion-selective electrode is also identical with preceding method.
The sensitive membrane of the phosphoric acid radical ion-selective electrode of the present invention development is optionally combination to phosphate radical, therefore can be used as the sensor of the living matters such as the ATP of phosphorous acid group and AOP, measures the content of phosphate anion in the living matter. When using as ATP, AOP sensor, electrode obtains stable potential earlier in deionized water after, put into take the phthalic acid of PH=4.0 to end liquid, phosphorus acid ion concentration to 10-4Obtain in the phosphorous acid group living matter solution of mol/L can make the living matter sensors such as ATP, AOP after the equilibrium potential, measure phosphoric acid in the living matter The content of radical ion.
The design makes electrode with metallic cobalt or containing metal cobalt solid sensitive material as sensitive membrane, after metallic cobalt and cobalt-base alloy process activation processing, form non-stoichiometric compound on the surface, there is the cobalt hole in this compound, thereby dihydrogen phosphate and phosphorous acid group living matter there are combination, and follow
The ernst equation
E＝E
0+ (RT)/(F) ln[H
2PO
4]
Therefore phosphoric acid radical ion-selective electrode has following characteristics:
(1) in liquid at the bottom of the Potassium Hydrogen Phthalate of PH=4.0, electrode pair H
2PO
- 410
-5～10
-2Be linear response in the mol/L concentration range, response slope is 56～59mv/dec, is limited to 8 * 10 under detecting
-6Mol/L;
(2) adopt solid material to make sensitive membrane, obtained lower impedance, thereby obtained good stable, reappearance, electrode is 10
-4Mol/L H
2PO
- 4METHOD FOR CONTINUOUS DETERMINATION is 2 hours in the solution, and potential drifting is less than 2mv, and electrode life is long;
(3) the common negative ion of electrode pair has good selectivity, Cl
-, SO
2- 4, NO
- 3, AcO
-And Br
-Plasma is to determination of electrode H
2PO
- 4All do not have obviously and disturb.
This shows, the design has overcome the defective that PVC film, liquid film and modified membrane two class phosphoric acid radical ion-selective electrodes exist, obtained comprehensive premium properties such as good stable, reappearance and selectivity, and have permanent electrode life, go for the actual analysis and the mensuration of phosphorus acid ion concentration in the fields such as chemical, environment, life science and clinical medicine fully.
Example 1
Be processed into the sensitive membrane of certain taper with metallic cobalt (Co) as sensitive material, the electrode tip of Pei Heing (8) also is processed into certain taper with it, coats minor amount of silicon rubber at the sensitive membrane conical surface, presses copper post (6) above in the intercalation electrode head; Lead (3) is welded on the copper post (5) in advance, electrode stem (2) bottom has and the suitable hole of copper post (5) diameter, after coating epoxy resin on every side, copper post (5) is pressed in the hole of electrode stem (2), pad is gone up O-ring seal (4) between electrode stem (2) and the electrode tip (8), screw, load onto electrode cap (1) and promptly obtain phosphoric acid radical ion-selective electrode.
Example 2
Directly at Co
Lead (3) is drawn in welding on the i alloy sensitive blocks, on sensitive blocks, apply epoxy resin the plain type phosphoric acid radical ion-selective electrode.
Example 3
Copper wire or copper post are cleaned, and an end immerses CoSO
4In the solution, and receive the negative pole of battery, the positive pole of battery is received on the Pt silk with copper wire, and Pt silk skewer is gone into CoSO
4Solution is electroplated into the sensitive membrane that the metal Co film is arranged on copper wire or the copper post top layer, and sensitive membrane is made phosphoric acid radical ion-selective electrode by embodiment 1 or 2 methods.
Claims (3)
1, a kind of phosphoric acid radical ion-selective electrode comprises the invention is characterized in the packing washer (4) of liner between the electrode body that is made of electrode cap (1), electrode stem (2) and electrode tip (8) and extension line (3) and electrode stem and the electrode tip:
(1) with metallic cobalt, cobalt-base alloy, contain the cobalt mineral compound and be the metallic cobalt that the surface of matrix forms at metal or other materials, cobalt-base alloy or contain cobalt mineral compound top layer or film is made sensitive membrane (7) as sensitive material with physics or chemical method;
(2) closely press a bronze medal post (6) on the sensitive membrane (7) of intercalation electrode head (8), be screwed into and be welded with extension line (3), be fixed on the copper post (5) on the electrode stem (2) on the copper post (6).
2, a kind of plain type phosphoric acid radical ion-selective electrode, it is characterized in that with metallic cobalt, cobalt-base alloy, contain the cobalt mineral compound and be the surface of the matrix metallic cobalt, the cobalt-base alloy that form or contain cobalt mineral compound top layer or sensitive membrane (7) that film is made as sensitive material goes up welding extension line (3) that at metal or other materials wringing fit is embedded in the plastics (9) or directly goes up coated with resins or glue (9) in sensitive membrane (7) with physics or chemical method.
3, a kind of purposes of phosphoric acid radical ion-selective electrode as claimed in claim 1 or 2, it is characterized in that this electrode obtains stable potential in deionized water after, the phthalic acid of putting into PH=4.0 is that end liquid, concentration are 10
-4Obtain after the activation processing of equilibrium potential sensor in the phosphorous acid group living matter solution of mol/L as phosphorous acid group living matter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111643A CN1038159C (en) | 1993-08-06 | 1993-08-06 | Phosphoric acid radical ion-selective electrode and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111643A CN1038159C (en) | 1993-08-06 | 1993-08-06 | Phosphoric acid radical ion-selective electrode and its use |
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| Publication Number | Publication Date |
|---|---|
| CN1098502A true CN1098502A (en) | 1995-02-08 |
| CN1038159C CN1038159C (en) | 1998-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93111643A Expired - Fee Related CN1038159C (en) | 1993-08-06 | 1993-08-06 | Phosphoric acid radical ion-selective electrode and its use |
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| Country | Link |
|---|---|
| CN (1) | CN1038159C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915798A (en) * | 2010-08-04 | 2010-12-15 | 三峡大学 | Ion selective electrode |
| WO2012154028A1 (en) * | 2011-05-12 | 2012-11-15 | Mimos Berhad | A phosphate sensor and method of formation thereof |
| GB2503689A (en) * | 2012-07-04 | 2014-01-08 | Compact Instr Ltd | Phosphate Detection |
| CN103868968A (en) * | 2014-03-12 | 2014-06-18 | 西安建筑科技大学 | Discrete PO4<3-> ion selective micro electrode and preparation method thereof |
| CN104428673A (en) * | 2012-07-06 | 2015-03-18 | 罗伯特·博世有限公司 | Methods for generating ph/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| CN104730120A (en) * | 2013-12-19 | 2015-06-24 | 恩德莱斯和豪瑟尔测量及调节技术分析仪表两合公司 | Sensor arrangement and method for determining orthophosphate content of a liquid |
| US9766197B2 (en) | 2014-02-13 | 2017-09-19 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions, and bubble detection using electrodes |
| US9874538B2 (en) | 2012-07-06 | 2018-01-23 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| US9910008B2 (en) | 2012-07-06 | 2018-03-06 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| CN107831200A (en) * | 2017-10-25 | 2018-03-23 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on nickel wire, preparation method and application |
| CN107860803A (en) * | 2017-10-25 | 2018-03-30 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on chromium silk, preparation method and application |
| CN107860806A (en) * | 2017-10-25 | 2018-03-30 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on titanium silk, preparation method and application |
| US10011549B2 (en) | 2015-07-06 | 2018-07-03 | Robert Bosch Gmbh | Electrochemically active agents for pH modulation in biological buffers |
| US10379080B2 (en) | 2015-07-06 | 2019-08-13 | Robert Bosch Gmbh | Electronic control of the pH of a solution close to an electrode surfaces |
| CN114258487A (en) * | 2019-08-21 | 2022-03-29 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Sensor element of an electrical potential sensor and production method |
| CN114942262A (en) * | 2022-02-25 | 2022-08-26 | 南京农业大学 | Laser-induced graphene electrode for detecting phosphate ions and preparation method |
| US11867660B2 (en) | 2015-07-06 | 2024-01-09 | Robert Bosch Gmbh | Electronic control of the pH of a solution close to an electrode surface |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287042A (en) * | 1979-03-09 | 1981-09-01 | National Research Development, Corp. | Ion-selective electrode and method of making said electrode |
| US4900404A (en) * | 1988-08-15 | 1990-02-13 | University Of Iowa Research Foundation | Phosphate selective membrane electrode |
-
1993
- 1993-08-06 CN CN93111643A patent/CN1038159C/en not_active Expired - Fee Related
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915798B (en) * | 2010-08-04 | 2014-04-09 | 三峡大学 | Ion selective electrode |
| CN101915798A (en) * | 2010-08-04 | 2010-12-15 | 三峡大学 | Ion selective electrode |
| WO2012154028A1 (en) * | 2011-05-12 | 2012-11-15 | Mimos Berhad | A phosphate sensor and method of formation thereof |
| GB2503689A (en) * | 2012-07-04 | 2014-01-08 | Compact Instr Ltd | Phosphate Detection |
| GB2503689B (en) * | 2012-07-04 | 2016-12-07 | Compact Instr Ltd | Phosphate detection |
| US9910008B2 (en) | 2012-07-06 | 2018-03-06 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| CN104428673B (en) * | 2012-07-06 | 2019-05-21 | 罗伯特·博世有限公司 | Method of the pH/ ion concentration gradient to adjust bio-molecular interaction is generated near electrode surface |
| CN104428673A (en) * | 2012-07-06 | 2015-03-18 | 罗伯特·博世有限公司 | Methods for generating ph/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| US9874538B2 (en) | 2012-07-06 | 2018-01-23 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions |
| CN104730120A (en) * | 2013-12-19 | 2015-06-24 | 恩德莱斯和豪瑟尔测量及调节技术分析仪表两合公司 | Sensor arrangement and method for determining orthophosphate content of a liquid |
| US10267760B2 (en) | 2013-12-19 | 2019-04-23 | Endress+Hauser Conducta Gmbh+Co. Kg | Sensor arrangement and method for determining orthophosphate content of a liquid |
| CN104730120B (en) * | 2013-12-19 | 2017-09-12 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Sensor device and method for the orthophosphoric acid radical content that determines liquid |
| US9766197B2 (en) | 2014-02-13 | 2017-09-19 | Robert Bosch Gmbh | Methods for generating pH/ionic concentration gradient near electrode surfaces for modulating biomolecular interactions, and bubble detection using electrodes |
| CN103868968B (en) * | 2014-03-12 | 2016-05-04 | 西安建筑科技大学 | A kind of separate type PO43-Ion-selective microelectrode and preparation method thereof |
| CN103868968A (en) * | 2014-03-12 | 2014-06-18 | 西安建筑科技大学 | Discrete PO4<3-> ion selective micro electrode and preparation method thereof |
| US11867660B2 (en) | 2015-07-06 | 2024-01-09 | Robert Bosch Gmbh | Electronic control of the pH of a solution close to an electrode surface |
| US10942146B2 (en) | 2015-07-06 | 2021-03-09 | Robert Bosch Gmbh | Electrochemically active agents for pH modulation in biological buffers |
| US11561198B2 (en) | 2015-07-06 | 2023-01-24 | Robert Bosch Gmbh | Electronic control of the pH of a solution close to an electrode surface |
| US10011549B2 (en) | 2015-07-06 | 2018-07-03 | Robert Bosch Gmbh | Electrochemically active agents for pH modulation in biological buffers |
| US10041905B2 (en) | 2015-07-06 | 2018-08-07 | Robert Bosch Gmbh | Electrochemically active agents for pH modulation in biological buffers |
| US10379080B2 (en) | 2015-07-06 | 2019-08-13 | Robert Bosch Gmbh | Electronic control of the pH of a solution close to an electrode surfaces |
| CN107860803A (en) * | 2017-10-25 | 2018-03-30 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on chromium silk, preparation method and application |
| CN107860806B (en) * | 2017-10-25 | 2019-12-03 | 三峡大学 | A kind of solid-state phosphate anion selection electrode, preparation method and application based on titanium silk |
| CN107860803B (en) * | 2017-10-25 | 2019-12-13 | 三峡大学 | Solid phosphate ion selective electrode based on chromium wire, preparation method and application |
| CN107831200B (en) * | 2017-10-25 | 2019-09-24 | 三峡大学 | A kind of solid-state phosphate anion selection electrode, preparation method and application based on nickel wire |
| CN107860806A (en) * | 2017-10-25 | 2018-03-30 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on titanium silk, preparation method and application |
| CN107831200A (en) * | 2017-10-25 | 2018-03-23 | 三峡大学 | A kind of solid-state phosphate anion selection electrode based on nickel wire, preparation method and application |
| CN114258487A (en) * | 2019-08-21 | 2022-03-29 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Sensor element of an electrical potential sensor and production method |
| CN114942262A (en) * | 2022-02-25 | 2022-08-26 | 南京农业大学 | Laser-induced graphene electrode for detecting phosphate ions and preparation method |
| CN114942262B (en) * | 2022-02-25 | 2024-03-08 | 南京农业大学 | Laser-induced graphene electrode for phosphate ion detection and preparation method thereof |
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|---|---|
| CN1038159C (en) | 1998-04-22 |
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