CN104515794A - PH/ORP (Potential of Hydrogen/Oxidation-Reduction Potential) sensor - Google Patents
PH/ORP (Potential of Hydrogen/Oxidation-Reduction Potential) sensor Download PDFInfo
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Abstract
The invention provides a PH/ORP (Potential of Hydrogen/Oxidation-Reduction Potential) sensor which comprises a housing, a standard electrode, a measuring electrode, a grounding salt bridge and a voltage comparator, wherein an accommodation space is formed in the housing; a solution junction is arranged on the housing; the standard electrode comprises a terminal and a sensing end; the sensing end of the standard electrode is arranged in a first reference solution; the measuring electrode comprises a terminal and a sensing end; the sensing end of the measuring electrode extends out of the housing to be arranged in a solution to be measured; one end of the grounding salt bridge is connected with the solution junction; the voltage comparator comprises a first input end, a second input end, a grounding voltage input end and an output end; the first input end is connected with the terminal of the standard electrode; the second input end is connected with the terminal of the measuring electrode; and the grounding voltage input end is connected with the other end of the grounding salt bridge. The PH/ORP sensor measures an electric potential of the solution to be measured by a difference method, is not influenced by electric potential change of the solution junction and can measure a PH/ORP value of the solution to be measured more accurately and stably.
Description
Technical field
The present invention relates to a kind of electrochemical sensor, particularly a kind of PH/ORP sensor.
Background technology
ORP (Oxidation-Reduction Potential, oxidation-reduction potential) value and pH value are the important indicators of reflection solution situation.Traditional PH/ORP sensor is made up of a potential electrode and a contrast electrode, measures detected solution electrode potential, and reflect the H+ number of ions in detected solution according to oxidation-reduction method, thus obtain the pH value of detected solution.
This traditional PH/ORP sensor, its potential electrode and contrast electrode are be coated in Ag silk surface with solid-state Ag and AgCl to form redox system, i.e. AgCl+e=Ag with KCI solution respectively
++ Cl
-.But this traditional PH/ORP sensor also exists some problems:
1, when temperature variation, the molecular balance between contrast electrode and reference solution can change, and cause solid-liquid equilibria slow, therefore the response of sensor to the temperature variation of detected solution is slower.
2, when heating, be coated in solid-state AgCI on Ag silk soluble, come off, thus have impact on the accuracy of measured value.
3, when the detected solution high to some organic components is measured, on sensor as Ye Jie circle of reference solution and detected solution link easily contaminated, fouling even block, cause liquid junction electrical resistance to increase, during measurement, current potential is unstable, affects measurement accuracy.And, because the container of detected solution (retort or pipeline) is all connected with ground usually, a loop can be formed by the earth terminal of container, because electric current flows through contrast electrode, cause contrast electrode to polarize, cause measuring error, cannot measure time serious at all.
Summary of the invention
The object of this invention is to provide a kind of PH/ORP sensor, the slow and easy problem affecting measurement accuracy by detected solution pollutes with the response speed solving the change of existing PH/ORP sensor for temperature.
The present invention proposes a kind of PH/ORP sensor, comprising: shell, normal electrode, potential electrode, ground connection salt bridge and voltage comparator.Shell, its inner accommodation space formed for holding the first reference liquid, shell is provided with Ye Jie circle for connecting the first reference liquid and outside detected solution; Normal electrode, it comprises terminals and the sense terminals for sensing the change of effects of ion number, and the sense terminals of normal electrode is arranged in the first reference liquid; Potential electrode, it comprises terminals and the sense terminals for sensing the change of effects of ion number, and the sense terminals of potential electrode is stretched out shell and is placed in detected solution to make it; Ground connection salt bridge, its one end is connected with Ye Jie circle; Voltage comparator, it comprises first input end, the second input end, ground voltage input end and output terminal, the terminals of first input end connection standard electrode, the second input end connects the terminals of potential electrode, and ground voltage input end connects the other end of ground connection salt bridge.
According to the PH/ORP sensor described in present pre-ferred embodiments, normal electrode and/or potential electrode comprise further: sealed tube and electrode conductor.Sealed tube, it is provided with PH sensitive membrane to form the sense terminals of normal electrode, and its inside is marked with for transmitting electro-ionic second reference liquid; Electrode conductor, its one end is stretched in the second reference liquid of sealed tube, and the other end stretches out using the terminals as normal electrode from sealed tube.
According to the PH/ORP sensor described in present pre-ferred embodiments, the electrode conductor of normal electrode and/or potential electrode is platinum filament.
According to the PH/ORP sensor described in present pre-ferred embodiments, ground connection salt bridge is platinum filament.
According to the PH/ORP sensor described in present pre-ferred embodiments, the first reference liquid is the potassium chloride buffer solution of 3mol.
According to the PH/ORP sensor described in present pre-ferred embodiments, voltage comparator is differential operational amplifier, and its output terminal connects voltage measuring apparatus.
According to the PH/ORP sensor described in present pre-ferred embodiments, the material of shell adopts glass or polyphenylene sulfide.
Relative to prior art, the invention has the beneficial effects as follows:
1, PH/ORP sensor of the present invention utilizes difference method to measure the current potential of detected solution, not by liquid junctionpotential variable effect, there is no the contrast electrode polarization problem of conventional P H/ORP sensor, can the PH/ORP value of the more reflection detected solution of accurate stable, PH/ORP sensor of the present invention is made to be specially adapted to the poor detected solution of water body, such as to the electroplate liquid of belt current, alcohol, hydrocarbon, aromatics, lipid, ketone is measured with the PH/ORP value in other chemical substances, to the measurement etc. of the pH value in means of flue gas desulfurization of power plant lime slurry.
2, PH/ORP sensor of the present invention, mat to measuring the reduction of influence degree, thus considerably increases the serviceable life of Ye Jie circle material in ground connection salt bridge, also namely decreases the number of times changing Ye Jie circle material, decreases maintenance time and the stop time of sensor.
3, PH/ORP sensor of the present invention, potential electrode and/or normal electrode are sensed by PH sensitive membrane, then redox reaction is carried out by the second reference liquid and electrode conductor, realize current potential liquid-liquid transmission, relative to the mode that traditional PH/ORP sensor current potential solid-liquid transmits, the time needed for chemical reaction is saved in measuring process, therefore electrochemical equilibrium can be reached soon in measuring, greatly reduce temperature variation to the impact of measuring response speed, promptly and accurately can reflect the PH/ORP value of detected solution.
Certainly, the arbitrary product implementing the application might not need to reach above-described all advantages simultaneously.
Accompanying drawing explanation
Fig. 1 is the structural drawing of a kind of PH/ORP sensor of the embodiment of the present invention;
Fig. 2 is the application principle figure of a kind of PH/ORP sensor of the embodiment of the present invention;
Fig. 3 is a kind of normal electrode of the embodiment of the present invention or the structural drawing of potential electrode.
Embodiment
Aforementioned and other technology contents, Characteristic for the present invention, can clearly present in following cooperation describes in detail with reference to graphic preferred embodiment.By the explanation of embodiment, when can to the present invention for the technological means reaching predetermined object and take and effect be able to more deeply and concrete understanding, however institute's accompanying drawings be only to provide with reference to and the use of explanation, be not used for being limited the present invention.
Refer to Fig. 1, it is the structural drawing of a kind of PH/ORP sensor of the embodiment of the present invention.This PH/ORP sensor comprises shell 1, normal electrode 2, potential electrode 3, ground connection salt bridge 4 and voltage comparator 5.
The material of shell 1 can adopt glass or polyphenylene sulfide (PHenylenesulfide, PPS).Shell 1 inside forms an accommodation space, is marked with the first reference liquid 6 in accommodation space.In the present embodiment, the KCL buffer solution of the preferred 3mol of the first described reference liquid 6.The lower end of shell 1 is also provided with Ge Yejie circle 7, Ye Jie circle 7 for connecting the first reference liquid 6 and detected solution when working sensor, and Ye Jie circle 7 requires that infiltration capacity is stablized, and can adopt core.
Normal electrode 2 comprises sense terminals 21 and terminals 22.Sense terminals 21 is arranged in the first reference liquid 6, for sensing the first reference liquid 6 intermediate ion number change.
Structure and the normal electrode 2 of potential electrode 3 are similar, comprise sense terminals 31 and terminals 32 equally, and the sense terminals 31 of potential electrode 3 stretches out to make it be placed in detected solution from shell 1.
One end of ground connection salt bridge 4 is connected with Ye Jie circle 7, and is stretched out from shell 1 by Ye Jie circle 7.In the present embodiment, the preferred platinum filament of material of ground connection salt bridge 4, the such as platinum filament of platinum content 99.9%.
Voltage comparator 5 comprises first input end 51, second input end 52, ground voltage input end 53 and output terminal 54.Terminals 22, second input end 52 of first input end 51 connection standard electrode 2 connects the terminals 32 of potential electrode 3, and ground voltage input end 53 connects the other end 42 of ground connection salt bridge.
The current potential that voltage comparator 5 forms for the current potential that forms potential electrode 3 and ground connection salt bridge 4 and normal electrode 2 and ground connection salt bridge 4 is compared, and then can obtain electrode potential and the number of ions of detected solution.In the present embodiment, voltage comparator 5 is differential operational amplifier preferably, and its output terminal connects voltage measuring apparatus to measure output voltage.
Refer to Fig. 2, it is the application principle figure of a kind of PH/ORP sensor of the embodiment of the present invention.PH/ORP sensor is placed in the container being marked with detected solution, and potential electrode 3 is in detected solution 8.In the present embodiment, voltage comparator 5 adopts 1NA116 operational amplifier, arranges according to operational amplifier, and it can be made directly to export the current potential of detected solution:
Measure current potential-normal potential=detected solution current potential, that is:
(G1+E0)-(G2+E0)＝ΔE.................................(1)
Wherein, G1 is the current potential that potential electrode 3 measures, and G2 is the current potential that normal electrode 2 measures, and E0 is the current potential (current potential of Ji Yejie circle 7) of ground connection salt bridge 4.By the application of the present embodiment to PH/ORP sensor, directly can obtain detected solution 8 current potential, and then also can obtain pH value and the ORP value of detected solution 8.
And it is visible according to formula (1), the present embodiment utilizes difference method to measure the current potential of detected solution, by the variable effect of liquid junctionpotential E0, there is no the contrast electrode polarization problem of conventional P H/ORP sensor, can the PH/ORP value of the more reflection detected solution of accurate stable.PH/ORP sensor of the present invention is made to be specially adapted to the poor detected solution of water body, such as the PH/ORP value in the electroplate liquid of belt current, alcohol, hydrocarbon, aromatics, lipid, ketone and other chemical substances is measured, to the measurement etc. of the pH value in means of flue gas desulfurization of power plant lime slurry.And; be different from the potential measurement mode of conventional P H/ORP sensor closed cycle circuit; mat in ground connection salt bridge 4 to measuring the reduction of influence degree; thus considerably increase the serviceable life of Ye Jie circle material; also namely decrease the number of times changing Ye Jie circle material, decrease maintenance time and the stop time of sensor.
Present invention further teaches the special structure of one of normal electrode or potential electrode, greatly can shortening the response speed of sensor when measuring.For normal electrode, refer to Fig. 3, this normal electrode 2 comprises sealed tube 23 and electrode conductor 24.Sealed tube 23 main body can be glassware, and one end of sealed tube 23 is sealed by sealing 26, and the other end of sealed tube 23 is provided with PH sensitive membrane 25, and this PH sensitive membrane 25 constitutes the sense terminals 21 of normal electrode 2.PH sensitive membrane 25 is used for the pH value of sensing first reference liquid, and PH sensitive membrane 25 can select suitable sensitive membrane according to the first reference liquid, such as photochemical graft.Sealed tube 23 inside is marked with the second reference liquid, and the second reference liquid such as can adopt liquor kalii iodide
second reference liquid is used for transmitting electron ion according to the change in voltage in PH sensitive membrane 25.One end of electrode conductor 24 is stretched in the second reference liquid of sealed tube 23, and the other end stretches out using the terminals 22 as normal electrode from sealed tube 23.The electrode conductor 24 preferably platinum filament of the present embodiment, the such as platinum filament of platinum content 99.9%, because platinum filament has very high chemical stability, can well the current potential that the second reference liquid is changed as normal electrode 2 by the electron ion that oxidation-reduction reaction transmit be exported.
Potential electrode of the present invention equally also can adopt the structure identical with normal electrode as indicated at 3, does not repeat them here.
Mat is in this electrode structure as shown in Figure 3, when potential electrode measurement detected solution and normal electrode measure the number of ions change in the first reference liquid, all sensed by PH sensitive membrane, then current potential transmission is carried out by the second reference liquid and electrode conductor, in fact utilize the electron ion transmission between liquid-liquid to measure, the electron ion transfer mode between solid-liquid is utilized relative to traditional PH/ORP sensor, the time needed for chemical reaction is saved in measuring process, therefore electrochemical equilibrium can be reached soon in measuring, greatly reduce temperature variation to the impact of measuring response speed, promptly and accurately can reflect the PH/ORP value of detected solution.
Based on the response speed to detected solution temperature variation, applicant proves the advantage of PH/ORP sensor of the present invention relative to conventional P H/ORP sensor by test:
A. temperature rises: first PH/ORP sensor of the present invention and the PH 4.01 of conventional Ag/AgCI system PH/ORP sensor from 25 DEG C are taken out buffer solution, put into PH 4.13 buffer solution of 75 DEG C.PH/ORP sensor of the present invention can reach PH 4.13 in theoretical value 75 DEG C in moment, and the PH/ORP sensor of routine needs could close to theoretical value at the 5th minute.
B. temperature declines: be put back in 4.01 buffer solution of 25 DEG C by above two sensors again, PH/ORP sensor of the present invention reached PH 4.01 in 30 seconds, and the PH/ORP sensor of conventional PH obtains inaccurate reading.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical scheme, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical scheme content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. a PH/ORP sensor, is characterized in that, comprising:
One shell, its inner accommodation space formed for holding the first reference liquid, this shell is provided with Ye Jie circle for connecting the first reference liquid and outside detected solution;
One normal electrode, it comprises terminals and the sense terminals for sensing the change of effects of ion number, and this sense terminals of this normal electrode is arranged in this first reference liquid;
One potential electrode, it comprises terminals and the sense terminals for sensing the change of effects of ion number, and this sense terminals of this potential electrode is stretched out this shell and is placed in detected solution to make it;
One ground connection salt bridge, its one end is connected with this Ye Jie circle;
One voltage comparator, it comprises a first input end, one second input end, a ground voltage input end and an output terminal, this first input end connects the terminals of this normal electrode, this the second input end connects the terminals of this potential electrode, and this ground voltage input end connects the other end of this ground connection salt bridge.
2. PH/ORP sensor as claimed in claim 1, it is characterized in that, this normal electrode and/or potential electrode comprise further:
One sealed tube, it is provided with a PH sensitive membrane to form the sense terminals of this normal electrode, and its inside is marked with for transmitting electro-ionic second reference liquid;
One electrode conductor, its one end is stretched in the second reference liquid of sealing pipe, and the other end stretches out using the terminals as this normal electrode from sealing pipe.
3. PH/ORP sensor as claimed in claim 2, it is characterized in that, this electrode conductor of this normal electrode and/or potential electrode is platinum filament.
4. PH/ORP sensor as claimed in claim 1, it is characterized in that, this ground connection salt bridge is platinum filament.
5. PH/ORP sensor as claimed in claim 1, it is characterized in that, this first reference liquid is the potassium chloride buffer solution of 3mol.
6. PH/ORP sensor as claimed in claim 1, it is characterized in that, this voltage comparator is differential operational amplifier, and its output terminal connects voltage measuring apparatus.
7. PH/ORP sensor as claimed in claim 1, is characterized in that, the material of this shell adopts glass or polyphenylene sulfide.
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| CN201510003932.6A CN104515794B (en) | 2015-01-06 | 2015-01-06 | PH/ORP sensors |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477811A (en) * | 2016-06-16 | 2019-03-15 | 哈希公司 | Chlorine, oxidation-reduction potential (ORP) and PH measure probe |
| CN113390675A (en) * | 2021-06-05 | 2021-09-14 | 安徽科力德能源环境科技有限公司 | Special sampling device of wet flue gas desulfurization thick liquid oxidation analysis appearance |
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| JPH10213562A (en) * | 1997-01-28 | 1998-08-11 | Kasahara Rika Kogyo Kk | Ph, orp, and water temperature measuring electrode |
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| US20140090978A1 (en) * | 2012-09-30 | 2014-04-03 | Invensys Systems Inc. | Potentiometric sensor |
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| CN85201405U (en) * | 1985-04-10 | 1986-05-14 | 上海市轻工业研究所 | Ph and orp sensor |
| EP0777122B1 (en) * | 1995-12-07 | 2002-04-10 | Elsag International N.V. | Electrochemical Sensor |
| JPH10213562A (en) * | 1997-01-28 | 1998-08-11 | Kasahara Rika Kogyo Kk | Ph, orp, and water temperature measuring electrode |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477811A (en) * | 2016-06-16 | 2019-03-15 | 哈希公司 | Chlorine, oxidation-reduction potential (ORP) and PH measure probe |
| CN113390675A (en) * | 2021-06-05 | 2021-09-14 | 安徽科力德能源环境科技有限公司 | Special sampling device of wet flue gas desulfurization thick liquid oxidation analysis appearance |
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| CN104515794B (en) | 2017-10-24 |
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