CN104237336A - Nitrite sensor - Google Patents
Nitrite sensor Download PDFInfo
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- CN104237336A CN104237336A CN201410469282.XA CN201410469282A CN104237336A CN 104237336 A CN104237336 A CN 104237336A CN 201410469282 A CN201410469282 A CN 201410469282A CN 104237336 A CN104237336 A CN 104237336A
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 title claims abstract description 59
- 230000005284 excitation Effects 0.000 claims abstract description 15
- 230000005764 inhibitory process Effects 0.000 claims description 55
- 238000001914 filtration Methods 0.000 claims description 13
- 230000007274 generation of a signal involved in cell-cell signaling Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 230000003321 amplification Effects 0.000 claims description 11
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 11
- 229940005654 nitrite ion Drugs 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000009434 installation Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000009422 external insulation Methods 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005259 measurement Methods 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention provides a nitrite sensor which comprises electrode connection wires, an electrode mounting disk, a reference electrode, an auxiliary electrode, a working electrode, a common-mode rejection electrode, an electrode excitation circuit, a control circuit, an electrode signal protection circuit and an electrode signal processing circuit, wherein the common-mode rejection electrode is additionally arranged in the sensor, so that a common-mode signal is generated; the electrode signal processing circuit is used for culling the common-mode signal to obtain a differential-mode signal generated by oxidization of nitrite; the differential-mode signal is amplified to acquire a voltage signal on a required level; finally, the amplified voltage signal is filtered and output. The nitrite sensor provided by the invention can be used for measuring nitrite and physically compensating changes of temperature and conductivity of a solution to be detected and interference of other ions in the solution on the sensor without software calculation, so that the measurement precision and stability are improved, and continuous on-line measurement on the concentration of nitrite in water can be carried out.
Description
Technical field
The invention belongs to technical field of sensor measurement, especially relate to a kind of nitrite sensor.
Background technology
Nitrite is the general name of a class mineral compound, is present in nature and industrial various water body and curing food widely, as underground water, surface water, aquaculture pond, potable water, seawater, industrial waste water and sausage, pickles etc.Normal used as food additives in commercial production, to improve food taste, color and luster extend its shelf-life.Nitrite is a kind of noxious material, to human body, the toxic effect of aquatic organism.Nitrite sensor is the sensor measuring its concentration of aqueous solution.When applying stable pumping signal to nitrite ion electrodes selective, nitrite can in electrode surface generation oxidation reaction, and oxidation reaction can discharge electronics, electrode is collected these d/d electronics and is collected and define electric current, namely forms the output signal of electrode.And the reaction release speed of electronics is directly proportional to the concentration of nitrite in solution, thus, the output signal of electrode is also directly proportional to the nitrite concentration in solution, the electrochemical measurement principle of Here it is nitrite.
Along with blowdown in China's aquaculture in recent years and environmental protection controls the demand to nitrite detection technique, its measuring method is also towards low detection limit and high precision direction development.
Used nitrite measuring technique is primarily of photometry and electrochemical process two kinds.Wherein photometry measures by detecting the react chemiluminescence of generation, the concentration of mode to nitrite in solution of discoloration effect of nitrite absorbance or its and other material.The method needs to use reagent or carry out enrichment to improve the obvious degree of solution colour change to solute mostly.The colourimetry that patent disclosed in U.S. Patent number 8003399 uses.The method uses the mode of nitrite indicator colour developing to detect nitrite.But the method can not on-line checkingi, and need to consume reagent.By electrochemical process, three electrode measurement modes mostly are to the technology that nitrite concentration detects now.The selectivity of electrode, the change of environment temperature, the measurement change of electrical conductivity of solution and the interference etc. of other ions all can affect the accuracy of three electrode measurement methods.This patent has set forth a kind of nitrite detecting sensor of four electric pole types, can reduce temperature, conductivity and other ion pairs preferably and measure the adverse effect produced, improve the accuracy measured.
Summary of the invention
For Shortcomings in prior art, the invention provides a kind of can realize carrying out Measurement accuracy to nitrite concentration and possess physically to temperature, conductivity, ion interference carry out self-compensating can the nitrite sensor of on-line monitoring.
The present invention realizes above-mentioned technical purpose by following technological means.
A kind of nitrite sensor, comprises electrode connecting line, contrast electrode, auxiliary electrode, working electrode, common mode inhibition electrode, electrode excitation circuit, electrode signal protection circuit, electrode signal treatment circuit and control circuit.Described electrode excitation circuit comprises constant voltage signal generation module, reference electrode potential control module, auxiliary electrode electromotive force control module, working electrode potential control module and common mode inhibition electrode potential control module, wherein the input end of reference electrode potential control module is connected by electrode connecting line with contrast electrode, the input end of constant voltage signal generation module is connected with the output terminal of control circuit, the output terminal of reference electrode potential control module is connected with the input end of auxiliary electrode electromotive force control module respectively with the output terminal of constant voltage signal generation module, the output terminal of auxiliary electrode electromotive force control module is connected by electrode connecting line with auxiliary electrode, working electrode potential control module is connected by electrode connecting line with working electrode, common mode inhibition electrode potential control module is connected by electrode connecting line with common mode inhibition electrode.The input end of electrode signal protection circuit is connected with the output terminal of control circuit, and the output terminal of electrode signal protection circuit is connected by electrode connecting line with working electrode and common mode inhibition electrode respectively.Electrode signal treatment circuit comprises common-mode signal and rejects module, difference mode signal amplification module, difference mode signal filtration module, wherein the input end of common-mode signal rejecting module is connected by electrode connecting line with working electrode and common mode inhibition electrode respectively, the output terminal of signal rejecting module is connected with the input end of difference mode signal amplification module altogether, the output terminal of difference mode signal amplification module is connected with the input end of difference mode signal filtration module, signal exports through the output terminal of difference mode signal filtration module, and the output of control circuit is also connected with electrode signal treatment circuit.
Further, described sensor comprises electrode mounting disc, a through hole is provided with at the circle centre position of electrode mounting disc, three through holes are provided with on the installation loop wire that the described center of circle is concentric, contrast electrode is installed in the through hole of the circle centre position of electrode mounting disc, auxiliary electrode, working electrode and common mode inhibition electrode are loaded in three through holes on installation loop wire respectively, and auxiliary electrode through hole is equal to the distance of common mode inhibition electrode through hole to the Distance geometry auxiliary electrode through hole of working electrode through hole.
Further, working electrode and common mode inhibition electrode electrode connecting line used are shielded cable.
Further, described common mode inhibition electrode and working electrode include electrode end cap, electrode basement, the outer overlay film of electrode, the external insulation layer, external shielding layer, inner insulating layer and the interior signals layer that are connected with shielded cable is respectively followed successively by from outside to inside in described electrode end cap, one end of interior signals layer extends downward in electrode basement along the axle center of electrode basement, at the outer overlay film of electrode basement outer cladding electrode.
Further, described working electrode is Nitrite Ion-selective Electrode, is the carbon paste electrode of chitosan-modified, the film modified glass-carbon electrode of Co MCM-41-PVA or Ni/Mg/Fe ternary hydrotalcite decorating carbon paste electrode.
Further, described common mode inhibition electrode is platinum electrode, and contrast electrode is saturated calomel electrode, and auxiliary electrode is platinum electrode.
Further, described sensor also comprises shell, upper cover, sensor cable, shell and upper cover are threaded by electrode mounting disc, sensor cable is through the through hole being positioned at the upper cover center of circle, and between sensor cable and upper cover, be provided with the first O-ring seal, between upper cover and electrode mounting disc, be provided with the second O-ring seal, between electrode mounting disc and contrast electrode, auxiliary electrode, working electrode, common mode inhibition electrode, be provided with the 3rd O-ring seal.
Further, described shell is without bottom structure, arranges a vent port in shell upper close to electrode mounting disc place, and the side of shell is provided with side through hole.
By setting up common mode inhibition electrode in the sensor, form common-mode signal, and reject common-mode signal by electrode signal treatment circuit, reduce sensor to the susceptibility of solution temperature, conductivity and other ions, obtain purer differential mode nitrite-oxidizing electric current; Use shielded cable to connect working electrode and common mode inhibition electrode, the weak current that guard electrode produces, suppresses it to run off, and reduces the change of ambient humidity, temperature and wire insulation layer resistivity to the impact of this signal; Auxiliary electrode is equal to the distance of working electrode and common mode inhibition electrode, makes the electric current that formed between auxiliary electrode with working electrode equal with the electric current that formed between auxiliary electrode with common mode inhibition electrode; Auxiliary electrode, working electrode, common mode inhibition electrode are identical with the distance of contrast electrode, make to be that the potential reference that benchmark is set up produces identical effect on other three electrodes with contrast electrode; Excitation control circuit in the not excitation of used time cut out to electrode, can reduce the consumption of power consumption and electrode pair nitrite, makes nitrite be diffused into electrode district thus reach the due concentration of solution; Electrode signal protection circuit coordinates shielding line to use, the weak current produced with guard electrode; Use rubber gasket to make sensor have waterproof effect when mounted, the content of nitrite measuring required depth of water place can be immersed in the water; The vent port that sensor outer housing is arranged, when sensor is immersed in the water, internal gas can be got rid of, and prevents the generation of gas cavity.
Accompanying drawing explanation
Fig. 1 is the electrode system schematic diagram of an embodiment of nitrite sensor of the present invention.
Fig. 2 is the upward view of the nitrite sensor electrode system shown in Fig. 1.
Fig. 3 is the circuit theory diagrams of nitrite sensor of the present invention.
Fig. 4 is the structural representation of common mode inhibition electrode and working electrode.
Fig. 5 is the structural representation of nitrite sensor of the present invention.
Fig. 6 is the decomposing schematic representation of nitrite sensor of the present invention.
Description of reference numerals is as follows:
1-electrode connecting line, the mounting disc of 2-electrode, 3-contrast electrode, 4-auxiliary electrode, 5-working electrode, 6-common mode inhibition electrode, 7-installs loop wire, 8-electrode excitation circuit, 9-control circuit, 10-electrode signal protection circuit, 11-electrode signal treatment circuit, 12-constant voltage signal generation module, 13-reference electrode potential control module, 14-auxiliary electrode electromotive force control module, 15-working electrode potential control module, 16-common mode inhibition electrode potential control module, 17-common-mode signal rejects module, 18-difference mode signal amplification module, 19-difference mode signal filtration module, 20-external insulation layer, 21-external shielding layer, 22-inner insulating layer, signals layer in 23-, 24-electrode installs screw thread, 25-electrode basement, the outer overlay film of 26-electrode, 27-sensor cable, 28-upper cover, 29-shell, 30-vent port, 31-first O-ring seal, 32-second O-ring seal, 33-the 3rd O-ring seal, 34-side through hole.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
As depicted in figs. 1 and 2, the electrode system of the nitrite sensor of the present embodiment comprises: electrode connecting line 1, electrode mounting disc 2, contrast electrode 3, auxiliary electrode 4, working electrode 5, common mode inhibition electrode 6 and installation loop wire 7, a through hole is provided with at the circle centre position of electrode mounting disc 2, three through holes are provided with on the installation loop wire 7 that the described center of circle is concentric, described contrast electrode 3 is loaded in the through hole of the circle centre position of electrode mounting disc 2, auxiliary electrode 4, working electrode 5 and common mode inhibition electrode 6 are loaded in three through holes on installation loop wire 7 respectively, auxiliary electrode 4 through hole is equal to the distance of common mode inhibition electrode 6 through hole to Distance geometry auxiliary electrode 4 through hole of working electrode 5 through hole.Electrode connecting line 1 is for connecting electrode and excitation metering circuit thereof, and wherein working electrode 5 and common mode inhibition electrode 6 connecting line used are shielded cable.Contrast electrode 3 adopts saturated calomel electrode, and its surface electrochemical reaction does not occur, for the electromotive force of solution to be measured of sampling; Auxiliary electrode 4 is platinum electrode, matches, provide electric current needed for electrochemical reaction with working electrode 5 and common mode inhibition electrode 6; Working electrode 5, for Nitrite Ion-selective Electrode, it can be the one in Chitin Containing Carbon Paste Electrode, the film modified glass-carbon electrode of Co MCM-41-PVA or Ni/Mg/Fe ternary hydrotalcite decorating carbon paste electrode, optionally make nitrite, on its surface, oxidation reaction occur, collect the electronics of reaction transfer, forming reactions electric current; Common mode inhibition electrode 6 is platinum electrode, does not react with nitrite ion, produces common mode current signal when working electrode 5 works.
Working electrode 5 described in the present embodiment and the structure of common mode inhibition electrode 6 are as shown in Figure 4, include electrode end cap, electrode basement 25, the outer overlay film 26 of electrode, be followed successively by the external insulation layer 20, external shielding layer 21, inner insulating layer 22 and the interior signals layer 23 that are connected with shielded cable respectively in described electrode end cap from outside to inside, one end of described interior signals layer 23 extends downward in electrode basement 25 along the axle center of electrode basement 25.External insulation layer 20 is in order to isolated screen layer and the external world, and external shielding layer 21 is in order to protect the weak current of internal signal layers, and inner insulating layer 22 is in order to isolated interior signals layer and external shielding layer; Interior signals layer 23 is used for the current signal of carry electrode; Electrode basement 25 contacts with solution to be measured, and conduction electron also electrochemical reaction occurs.At the outer overlay film 26 of electrode basement 25 outer cladding electrode, outside electrode, electrode between overlay film 26 and electrode end cap, is had screw thread 24 to be installed, in order to be fixed in electrode mounting disc by electrode.
As shown in Figure 5 and Figure 6, the nitrite sensor of the present embodiment also comprises sensor cable 27, upper cover 28 and shell 29, be placed in sensor cable 27 with four electrode connecting lines 1 of Electrode connection, sensor cable 27 is with the waterproof connector of internal thread, the circle centre position of upper cover 28 is provided with one with the through hole of outer silk, connector is threaded with upper cover 28, to reach waterproof effect after being inserted in the first O-ring seal 31; Shell 29 and upper cover 28 are threaded with electrode mounting disc 2 by the second O-ring seal 32; Between electrode mounting disc 2 and contrast electrode 3, auxiliary electrode 4, working electrode 5, common mode inhibition electrode 6, be provided with the 3rd O-ring seal 33, when sensor is immersed in the water, aqueous solution can not immerse wiring place of electrode interior; Leave vent port 30 on shell 29 top close to electrode mounting disc 2 place, the air being trapped in its inside when sensor can be made to immerse aqueous solution flows out, and prevents the generation of gas cavity; Shell 29 is without bottom structure, and the side of shell is provided with side through hole 34, aqueous solution can be flowed freely into and flow out its electrode zone.
As shown in Figure 3, the Circuits System of the nitrite sensor of the present embodiment comprises: electrode excitation circuit 8, control circuit 9, electrode signal protection circuit 10 and electrode signal treatment circuit 11.Electrode excitation circuit 8 comprises constant voltage signal generation module 12, reference electrode potential control module 13, auxiliary electrode electromotive force control module 14, working electrode potential control module 15 and common mode inhibition electrode potential control module 16, the input end of reference electrode potential control module 13 is connected by electrode connecting line 1 with contrast electrode 3, the input end of described constant voltage signal generation module 12 is connected with the output terminal of control circuit 9, the output terminal of reference electrode potential control module 13 is connected with the input end of auxiliary electrode electromotive force control module 14 respectively with the output terminal of constant voltage signal generation module 12, the output terminal of auxiliary electrode electromotive force control module 14 is connected by electrode connecting line 1 with auxiliary electrode 4, working electrode potential control module 15 is connected by electrode connecting line 1 with working electrode 5, common mode inhibition electrode potential control module 16 is connected by electrode connecting line 1 with common mode inhibition electrode 6.The input end of described electrode signal protection circuit 10 is connected with the output terminal of control circuit 9, and the output terminal of electrode signal protection circuit 10 is connected by electrode connecting line 1 with working electrode 5 and common mode inhibition electrode 6 respectively.Described electrode signal treatment circuit 11 comprises common-mode signal and rejects module 17, difference mode signal amplification module 18, difference mode signal filtration module 19, the input end that common-mode signal rejects module 17 is connected by electrode connecting line 1 with working electrode 5 and common mode inhibition electrode 6 respectively, the output terminal that common-mode signal rejects module 17 is connected with the input end of difference mode signal amplification module 18, the output terminal of described difference mode signal amplification module 18 is connected with the input end of difference mode signal filtration module 19, signal exports through the output terminal of difference mode signal filtration module 19, the output terminal of control circuit 9 is also connected with telecommunication signal treatment circuit 11.
Principle of work and the course of work of the nitrite sensor described in the present embodiment are as follows:
Described sensor is placed in nitrite solution to be measured; signal inputs to control circuit 9 by circuit interface, control circuit 9 and electrode excitation circuit 8, is connected with power supply (not shown) between electrode signal protection circuit 10 and electrode signal treatment circuit 11.The open and close of sensor excitation signal can be controlled by power supply, to close while exciting circuit also by closed electrode signal protection circuit 10 and electrode signal treatment circuit 11 and turning electrode excitation signal, suppress the generation of electrode polarization.
When control circuit 9 is opened, constant voltage signal generation module 12 produces stable voltage, as the benchmark that electrode potential controls, the electromotive force of reference electrode potential control module 13 sample water solution, auxiliary electrode electromotive force control module 14 receives the signal from reference electrode potential control module 13 and constant voltage signal generation module 12, by controlling the electromotive force of auxiliary electrode 4 to make the electromotive force of the electromotive force of aqueous solution and contrast electrode gesture control module 13 reach the setting value of circuit; Working electrode potential control module 15, for controlling the electromotive force of working electrode 5, makes the electric potential difference of itself and aqueous solution be the Optimum Excitation voltage of electrode; Common mode inhibition electrode potential control module 16, controls the electromotive force of common mode inhibition electrode 6, makes it equal with the electromotive force of working electrode 5.Electrode signal protection circuit 10 drives the external shielding layer 21 of working electrode 5 and common mode inhibition electrode 6 with stronger driving force, makes its electromotive force equal respectively at the electromotive force of respective electrode, to prevent the loss of electrode weak current.
Ideally, working electrode 5 only produces following chemical reaction:
2NO
2 -+H
2O-2e
-→HNO
2+NO
3 -+H
+ (1)
Nitrite ion loses electronics becomes nitrate ion, and working electrode 5 is collected these electronics and collected formation electric current I
n, this electric current characterizes the speed that this chemical reaction carries out, and it is relevant with the concentration of solution Nitrite ion.But, due to the imperfection of electrodes selective, cause this working electrode 5 place except there is the chemical reaction described in formula (1), also following chemical reaction can occur:
X
n--me
-＝X
(n-m)- (2)
Other particles X in solution
n-lose m electronics, form X
(n-m)-.The electronics that this reaction discharges also can collected by working electrode 5, and these electrons form electric current I
x.In addition, due between working electrode 5 and contrast electrode 3, and there is electric potential difference U and conductance G between working electrode 5 and auxiliary electrode 4, therefore, working electrode 5 also can produce the electric current I formed by electric potential difference U and conductance G
g=GU.Thus, total current I working electrode 5 produced
wR=I
n+ I
x+ I
g, wherein useful signal is only I
n, and I
xby the impact of the kind of other interfering ion in solution, concentration and temperature, I
gthe impact of concentration and temperature is closed, therefore the electric current I that obtains of working electrode 5 by solion
wRcontaining two parts interference current, and interference current is subject to the kind of other interfering ion in solution, concentration, temperature and ion to close the impact of concentration.Thus these influence factors have impact on the measuring accuracy of working electrode 5.
In the present embodiment, due to the effect of common mode inhibition electrode 6 pairs of nitrite ion non-catalyst oxidations, the reaction with the formula described in (1) can not occur.But the reaction described in formula (2) still can occur, namely can generation current I on common mode inhibition electrode 6
x, and I
xthe impact of the same kind by other interfering ion in solution, concentration and temperature, and I on its influence degree and working electrode 5
xinfluence degree be identical.Same, due to the effect of electric potential difference U and conductance G, common mode inhibition electrode 6 also can form electric current I
g, and it closes the impact of concentration and temperature equally by solion.Thus, electric current common mode inhibition electrode 6 formed has I
cR=I
x+ I
g.So, there is I
wE-I
cR=I
nnamely the interference current produced by other ionic oxide formation in solution and conductivity is namely eliminated with the electric current that the electric current on working electrode 5 deducts on common mode inhibition electrode 6, obtain the electric current produced due to nitrite ion oxidation, namely this electric current characterizes the concentration level of solution Nitrite ion.
The signal returned from working electrode 5 and common mode inhibition electrode 6 is input to common-mode signal rejecting module 17, common-mode signal is rejected module 17 from the signal that working electrode 5 returns, is deducted the signal that common mode inhibition electrode 6 returns, thus obtains the difference mode signal that nitrite-oxidizing produces; Difference mode signal amplifies through difference mode signal amplification module 18, obtains the voltage signal of required rank; Carry out filtering through difference mode signal filtration module 19 to the voltage signal amplified again, a final generation DC voltage is to reflect the concentration of the nitrite detected by sensor, and its cutoff frequency is set to 10Hz, to reject Hz noise as far as possible.The output signal that sensor is finally produced by difference mode signal filtration module 19 is low-resistance signal, can directly use secondary instrument or Chip Microcomputer A/D C to carry out sampled measurements, to reach the object of automatic on-line monitoring.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (8)
1. nitrite sensor, is characterized in that, comprising:
Electrode connecting line (1), contrast electrode (3), auxiliary electrode (4), working electrode (5), common mode inhibition electrode (6), electrode excitation circuit (8), electrode signal protection circuit (10), electrode signal treatment circuit (11) and control circuit (9);
Described electrode excitation circuit (8) comprises constant voltage signal generation module (12), reference electrode potential control module (13), auxiliary electrode electromotive force control module (14), working electrode potential control module (15) and common mode inhibition electrode potential control module (16);
The input end of described reference electrode potential control module (13) is connected by electrode connecting line (1) with contrast electrode (3), the input end of described constant voltage signal generation module (12) is connected with the output terminal of control circuit (9), the output terminal of reference electrode potential control module (13) is connected with the input end of auxiliary electrode electromotive force control module (14) respectively with the output terminal of constant voltage signal generation module (12), the output terminal of auxiliary electrode electromotive force control module (14) is connected by electrode connecting line (1) with auxiliary electrode (4), working electrode potential control module (15) is connected by electrode connecting line (1) with working electrode (5), common mode inhibition electrode potential control module (16) is connected by electrode connecting line (1) with common mode inhibition electrode (6),
The input end of described electrode signal protection circuit (10) is connected with the output terminal of control circuit (9), and the output terminal of electrode signal protection circuit (10) is connected by electrode connecting line (1) with working electrode (5) and common mode inhibition electrode (6) respectively;
Described electrode signal treatment circuit (11) comprises common-mode signal and rejects module (17), difference mode signal amplification module (18), difference mode signal filtration module (19), the input end that described common-mode signal rejects module (17) is connected by electrode connecting line (1) with working electrode (5) and common mode inhibition electrode (6) respectively, the output terminal that described common-mode signal rejects module (17) is connected with the input end of difference mode signal amplification module (18), the output terminal of described difference mode signal amplification module (18) is connected with the input end of difference mode signal filtration module (19), signal exports through the output terminal of difference mode signal filtration module (19), the output terminal of described control circuit (9) is also connected with electrode signal treatment circuit (11).
2. nitrite sensor according to claim 1, is characterized in that:
Also comprise electrode mounting disc (2), a through hole is provided with at the circle centre position of described electrode mounting disc (2), three through holes are provided with on the installation loop wire (7) that the described center of circle is concentric, described contrast electrode (3) is installed in the through hole of the circle centre position of electrode mounting disc (2), auxiliary electrode (4), working electrode (5) and common mode inhibition electrode (6) are loaded in three through holes in installation loop wire (7) respectively, auxiliary electrode (4) through hole is equal to the distance of common mode inhibition electrode (6) through hole to Distance geometry auxiliary electrode (4) through hole of working electrode (5) through hole.
3. nitrite sensor according to claim 1, is characterized in that:
Described working electrode (5) and common mode inhibition electrode (6) electrode connecting line (1) used are shielded cable.
4. nitrite sensor according to claim 3, is characterized in that:
Described common mode inhibition electrode (6) and working electrode (5) include electrode end cap, electrode basement (25), the outer overlay film (26) of electrode, the external insulation layer (20), external shielding layer (21), inner insulating layer (22) and the interior signals layer (23) that are connected with shielded cable is respectively followed successively by from outside to inside in described electrode end cap, one end of described interior signals layer (23) extends downward in electrode basement (25) along the axle center of electrode basement (25), at the outer overlay film (26) of electrode basement (25) outer cladding electrode.
5. nitrite sensor according to claim 4, is characterized in that:
Described working electrode (5) is Nitrite Ion-selective Electrode, is the carbon paste electrode of chitosan-modified, the film modified glass-carbon electrode of Co MCM-41-PVA or Ni/Mg/Fe ternary hydrotalcite decorating carbon paste electrode.
6. nitrite sensor according to claim 4, is characterized in that:
Described common mode inhibition electrode (6) is platinum electrode, and described contrast electrode (3) is saturated calomel electrode, and described auxiliary electrode (4) is platinum electrode.
7. nitrite sensor according to claim 4, is characterized in that:
Also comprise shell (29), upper cover (28), sensor cable (27), described shell (29) and upper cover (28) are threaded by electrode mounting disc (2), sensor cable (27) is through the through hole being positioned at upper cover (28) center of circle, and the first O-ring seal (31) is provided with between sensor cable (27) and upper cover (28), the second O-ring seal (32) is provided with between upper cover (28) and electrode mounting disc (2), at electrode mounting disc (2) and contrast electrode (3), auxiliary electrode (4), working electrode (5), the 3rd O-ring seal (33) is provided with between common mode inhibition electrode (6).
8. nitrite sensor according to claim 7, is characterized in that:
Described shell (29) is without bottom structure, on shell (29) top, one vent port (30) is set close to electrode mounting disc (2) place, the side of shell (29) is provided with side through hole (34).
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| CN108107101A (en) * | 2017-12-12 | 2018-06-01 | 中国科学院合肥物质科学研究院 | A kind of three-dimensional carbon cloth/ferronickel stratiform hydroxide nano piece composite material and its application |
| CN110220956A (en) * | 2019-07-02 | 2019-09-10 | 中国科学院生物物理研究所 | A kind of fructose non-enzymatic electrochemical sensor and its detection method |
| CN110887945A (en) * | 2019-12-16 | 2020-03-17 | 南京奇崛电子科技有限公司 | Multi-parameter water quality sensor |
| CN114689673A (en) * | 2022-03-09 | 2022-07-01 | 浙江科技学院 | Low-cost water body nitrite concentration rapid detection system and method |
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| CN104237336B (en) | 2017-02-22 |
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