CN104515794B - PH/ORP sensors - Google Patents
PH/ORP sensors Download PDFInfo
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- CN104515794B CN104515794B CN201510003932.6A CN201510003932A CN104515794B CN 104515794 B CN104515794 B CN 104515794B CN 201510003932 A CN201510003932 A CN 201510003932A CN 104515794 B CN104515794 B CN 104515794B
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Abstract
The present invention proposes a kind of PH/ORP sensors, including：Shell, normal electrode, measuring electrode, it is grounded salt bridge and voltage comparator, shell is internally formed accommodation space, liquid border is provided with shell, normal electrode includes terminals and sensing end, the sensing end of normal electrode is arranged in the first reference liquid, measuring electrode includes terminals and sensing end, the sensing end of measuring electrode stretches out shell to place it in detected solution, one end of ground connection salt bridge is connected with liquid border, voltage comparator includes first input end, second input, ground voltage input and output end, first input end connects the terminals of normal electrode, second input connects the terminals of measuring electrode, the other end of ground voltage input connection ground connection salt bridge.The PH/ORP sensors of the present invention measure the current potential of detected solution using difference method, are not influenceed by liquid junctionpotential change, can more accurate stable the PH/ORP values for measuring detected solution.
Description
Technical field
The present invention relates to a kind of electrochemical sensor, more particularly to a kind of PH/ORP sensors.
Background technology
ORP (Oxidation-Reduction Potential, oxidation-reduction potential) values and pH value are reflection solution situations
Important indicator.Traditional PH/ORP sensors are to be made up of a measuring electrode with a reference electrode, according to oxidationreduction
Method measures detected solution electrode potential, and reflects the H+ number of ions in detected solution, so as to obtain the pH value of detected solution.
This traditional PH/ORP sensors, its measuring electrode and reference electrode are coated in the Ag and AgCl of solid-state respectively
Ag silk tables face and the formation of KCI solution redox system, i.e. AgCl+e=Ag++Cl-.However, this traditional PH/ORP sensings
Device there are problems that：
1st, in temperature change, the reaction balance between reference electrode and reference solution can change, and cause liquid-solid flat
Weighing apparatus is slow, therefore response of the sensor to the temperature change of detected solution is slower.
2nd, in heating, the solid-state AgCI that is coated on Ag silks is soluble, come off, thus have impact on the accuracy of measured value.
3, when the detected solution high to some organic components is measured, reference solution and tested is used as on sensor
The liquid border of solution connection member is easily contaminated, fouling is even blocked, and causes liquid junction electrical resistance to increase, and current potential is unstable during measurement
It is fixed, influence measurement accuracy.Moreover, because the container (retort or pipeline) of detected solution is generally connected with ground
, a loop can be formed by the earth terminal of container, because electric current flows through reference electrode, cause reference electrode to polarize, cause
Measurement error, can not be measured at all when serious.
The content of the invention
It is an object of the invention to provide a kind of PH/ORP sensors, changed with solving existing PH/ORP sensor for temperature
Response speed it is slow and the problem of easily polluted by detected solution and influence measurement accuracy.
The present invention proposes a kind of PH/ORP sensors, including：Shell, normal electrode, measuring electrode, ground connection salt bridge and electricity
Press comparator.Shell, it is internally formed on the accommodation space for accommodating the first reference liquid, shell and is provided with for connecting first
The liquid border of reference liquid and outside detected solution；Normal electrode, it includes terminals and for sensing the change of effects of ion number
Sensing end, the sensing end of normal electrode is arranged in the first reference liquid；Measuring electrode, it includes terminals and molten for sensing
The sensing end of liquid intermediate ion number change, the sensing end of measuring electrode stretches out shell to place it in detected solution；It is grounded salt bridge,
Its one end is connected with liquid border；Voltage comparator, it include first input end, the second input, ground voltage input and
Output end, first input end connects the terminals of normal electrode, and the second input connects the terminals of measuring electrode, ground voltage
The other end of input connection ground connection salt bridge.
According to the PH/ORP sensors described in present pre-ferred embodiments, normal electrode and/or measuring electrode are further wrapped
Include：Seal pipe and electrode conductor.Seal pipe, it is provided with PH sensitive membranes to constitute the sensing end of normal electrode, is marked with inside it
The second reference liquid for transmitting electron ion；Electrode conductor, its one end is stretched into the second reference liquid of seal pipe, and the other end is from close
Stretched out in tube sealing using the terminals as normal electrode.
According to the PH/ORP sensors described in present pre-ferred embodiments, the electrode of normal electrode and/or measuring electrode is led
Body is platinum filament.
According to the PH/ORP sensors described in present pre-ferred embodiments, ground connection salt bridge is platinum filament.
According to the PH/ORP sensors described in present pre-ferred embodiments, the first reference liquid buffers for 3mol/L potassium chloride
Solution.
According to the PH/ORP sensors described in present pre-ferred embodiments, voltage comparator is differential operational amplifier, its
Output end connects voltage measuring apparatus.
According to the PH/ORP sensors described in present pre-ferred embodiments, the material of shell uses glass or polyphenylene sulfide.
Relative to prior art, the beneficial effects of the invention are as follows：
1st, PH/ORP sensors of the invention measure the current potential of detected solution using difference method, not by liquid junctionpotential
Change influence, the reference electrode polarization problem without tradition PH/ORP sensors, can more accurate stable reflection detected solution
PH/ORP values so that PH/ORP sensors of the invention are particularly suitable for use in the poor detected solution of water body, such as to belt current
Electroplate liquid, alcohol, hydrocarbon, aromatic compound, lipid, ketone and other chemical substances in PH/ORP values survey
Amount, to measurement of the pH value in means of flue gas desulfurization of power plant lime slurry etc..
2nd, PH/ORP sensors of the invention, by the reduction in ground connection salt bridge to measurement influence degree, so as to greatly increase
The service life of liquid border material, namely the number of times for changing liquid border material is reduced, reduce the maintenance time of sensor
And downtime.
3rd, PH/ORP sensors of the invention, measuring electrode and/or normal electrode are sensed by PH sensitive membranes, so
Redox reaction is carried out by the second reference liquid and electrode conductor afterwards, realizes that current potential liquid-liquid is transmitted, relative to traditional PH/
The mode of ORP sensor current potentials solid-liquid transmission, was saved in measurement process in the time needed for chemical reaction, therefore measurement
Electrochemical equilibrium will soon be reached, influence of the temperature change to measurement response speed is greatly reduced, can be promptly and accurately
Reflect the PH/ORP values of detected solution.
Certainly, any product for implementing the application it is not absolutely required to while reaching all the above advantage.
Brief description of the drawings
Fig. 1 is a kind of structure chart of PH/ORP sensors of the embodiment of the present invention；
Fig. 2 is a kind of application principle figure of PH/ORP sensors of the embodiment of the present invention；
Fig. 3 is a kind of normal electrode of the embodiment of the present invention or the structure chart of measuring electrode.
Embodiment
For the present invention foregoing and other technology contents, feature and effect, in the following preferable reality coordinated with reference to schema
Applying during example is described in detail to be clearly presented.By the explanation of embodiment, when predetermined mesh can be reached to the present invention
The technological means taken and effect be able to more deeply and it is specific understand, but institute's accompanying drawings are only to provide with reference to saying
It is bright to be used, not for being any limitation as to the present invention.
Fig. 1 is referred to, it is a kind of structure chart of PH/ORP sensors of the embodiment of the present invention.This PH/ORP sensor bag
Include shell 1, normal electrode 2, measuring electrode 3, ground connection salt bridge 4 and voltage comparator 5.
The material of shell 1 can use glass or polyphenylene sulfide (PHenylenesulfide, PPS).Shell 1 is internally formed
The first reference liquid 6 is marked with one accommodation space, accommodation space.In the present embodiment, the described preferred 3mol/L of the first reference liquid 6
KCL cushioning liquid.The lower end of shell 1 is additionally provided with a liquid border 7, and liquid border 7 is used to connecting the in working sensor
One reference liquid 6 and detected solution, liquid border 7 require that infiltration capacity is stable, can use core.
Normal electrode 2 includes sensing end 21 and terminals 22.Sensing end 21 is arranged in the first reference liquid 6, for sensing
The intermediate ion number of first reference liquid 6 changes.
The structure of measuring electrode 3 is similar with normal electrode 2, same to include sensing end 31 and terminals 32, measuring electrode 3
Sensing end 31 is stretched out so that it can be placed in detected solution from shell 1.
One end of ground connection salt bridge 4 is connected with liquid border 7, and is stretched out by liquid border 7 from shell 1.In the present embodiment, connect
The preferred platinum filament of material of ground salt bridge 4, such as platinum filament of platinum content 99.9%.
Voltage comparator 5 includes first input end 51, the second input 52, ground voltage input 53 and output end
54.First input end 51 connects the terminals 22 of normal electrode 2, and the second input 52 connects the terminals 32 of measuring electrode 3, connect
The other end 42 of the connection ground connection salt bridge of ground voltage input 53.
Voltage comparator 5 is used for the current potential constituted to measuring electrode 3 with ground connection salt bridge 4 and normal electrode 2 and ground connection salt
The current potential that bridge 4 is constituted is compared, and then can obtain the electrode potential and number of ions of detected solution.In the present embodiment, electricity
The preferred differential operational amplifier of comparator 5 is pressed, its output end connects voltage measuring apparatus to measure output voltage.
Fig. 2 is referred to, it is a kind of application principle figure of PH/ORP sensors of the embodiment of the present invention.PH/ORP sensors
It is placed in the container for being marked with detected solution, and measuring electrode 3 is in detected solution 8.In the present embodiment, voltage comparator 5
Using 1NA116 operational amplifiers, it is configured according to operational amplifier, the current potential that it can be made directly to export detected solution：
Current potential-normal potential=detected solution current potential is measured, i.e.,：
(G1+E0)-(G2+E0)=Δ E................................. (1)
Wherein, G1 is the current potential that measuring electrode 3 is measured, and G2 is the current potential that normal electrode 2 is measured, and E0 is ground connection salt bridge
4 current potential (i.e. the current potential of liquid border 7).Application by the present embodiment to PH/ORP sensors, can be directly obtained tested molten
The current potential of liquid 8, and then the pH value and ORP value of detected solution 8 can also be obtained.
And it is visible according to formula (1), the present embodiment measures the current potential of detected solution using difference method, not by liquid border
Current potential E0 change influence, the reference electrode polarization problem without tradition PH/ORP sensors, can more accurate stable reflection
The PH/ORP values of detected solution.So that the PH/ORP sensors of the present invention are particularly suitable for use in the poor detected solution of water body, such as
To the PH/ in the electroplate liquid of belt current, alcohol, hydrocarbon, aromatic compound, lipid, ketone and other chemical substances
ORP value is measured, to measurement of the pH value in means of flue gas desulfurization of power plant lime slurry etc..Moreover, different from tradition PH/ORP sensors
The potential measurement mode of closed cycle circuit, by the reduction of 4 pairs of measurement influence degrees of ground connection salt bridge, so as to considerably increase liquid
The service life of border material, namely the number of times for changing liquid border material is reduced, reduce the maintenance time of sensor and stop
The machine time.
Present invention further teaches normal electrode or a kind of special structure of measuring electrode, sensor can be greatly shortened in survey
Response speed during amount.By taking normal electrode as an example, Fig. 3 is referred to, this normal electrode 2 includes seal pipe 23 and electrode conductor 24.
The main body of seal pipe 23 can be glassware, and one end of seal pipe 23 is sealed by sealing 26, and the other end of seal pipe 23 is set
There are PH sensitive membranes 25, this PH sensitive membrane 25 constitutes the sensing end 21 of normal electrode 2.PH sensitive membranes 25 are used for sensing the first reference
The pH value of liquid, PH sensitive membranes 25 can select suitable sensitive membrane, such as photochemical graft according to the first reference liquid.Sealing
The second reference liquid is marked with inside pipe 23, the second reference liquid can for example be used for quick according to PH using the reference liquid of liquor kalii iodide second
Feel the voltage change transmission electron ion on film 25.One end of electrode conductor 24 is stretched into the second reference liquid of seal pipe 23, another
End is stretched out from seal pipe 23 using the terminals 22 as normal electrode.The preferred platinum filament of electrode conductor 24 of the present embodiment, for example
The platinum filament of platinum content 99.9%, because platinum filament has very high chemical stability, can pass through oxygen by the second reference liquid well
The electron ion that change-reduction reaction transmission comes becomes the current potential output for being turned to normal electrode 2.
The present invention measuring electrode equally can also use with normal electrode identical structure as indicated at 3, herein no longer
Repeat.
By in this electrode structure as shown in Figure 3, measuring electrode measurement detected solution and normal electrode measurement first
When number of ions in reference liquid changes, all it is to be sensed by PH sensitive membranes, then passes through the second reference liquid and electrode conductor
Current potential transmission is carried out, is substantially measured, is sensed relative to traditional PH/ORP using the electron ion transmission between liquid-liquid
Device utilizes the electron ion transfer mode between solid-liquid, is saved in measurement process in the time needed for chemical reaction, therefore measurement
Electrochemical equilibrium will soon be reached, influence of the temperature change to measurement response speed is greatly reduced, can be promptly and accurately
Reflect the PH/ORP values of detected solution.
Based on the response speed to detected solution temperature change, applicant proves PH/ORP sensors of the present invention by testing
Relative to the advantage of traditional PH/ORP sensors：
A. temperature rises：First by PH/ORP sensors of the present invention and conventional Ag/AgCI system PH/ORP sensors from 25
DEG C the cushioning liquid of PH 4.01 in take out, be put into 75 DEG C of the cushioning liquid of PH 4.13.PH/ORP sensors of the present invention are in wink
Between can reach PH 4.13 in 75 DEG C of theoretical value, and need could be close to theoretical value at the 5th minute for conventional PH/ORP sensors.
B. temperature drop：Above two sensorses are put back into 25 DEG C of 4.01 cushioning liquid again, PH/ORP of the present invention is passed
Sensor reached PH 4.01 in 30 seconds, and routine PH PH/ORP sensors obtain inaccurate reading.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people
Member, is not departing from the range of technical scheme, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the technical spirit pair according to the present invention without departing from technical scheme content
Any simple modification, equivalent variations and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (6)
1. a kind of PH/ORP sensors, it is characterised in that including：
One shell, it is internally formed on the accommodation space for accommodating the first reference liquid, the shell and is provided with for connecting first
One liquid border of reference liquid and outside detected solution；
One normal electrode, it includes a terminals and the sensing end for sensing the change of effects of ion number, the normal electrode
The sensing end be arranged in first reference liquid；
One measuring electrode, it includes a terminals and the sensing end for sensing the change of effects of ion number, the measuring electrode
The sensing end shell is stretched out to place it in detected solution；
One ground connection salt bridge, its one end is connected with the liquid border；
One voltage comparator, it includes a first input end, one second input, a ground voltage input and an output
End, the first input end connects the terminals of the normal electrode, and second input connects the terminals of the measuring electrode, and this connects
Ground voltage input connects the other end of the ground connection salt bridge；
The normal electrode includes seal pipe and electrode conductor；One end of seal pipe is sealed by sealing, the other end of seal pipe
PH sensitive membranes are provided with, this PH sensitive membrane constitutes the sensing end of normal electrode, the pH value for sensing the first reference liquid, described close
The second reference liquid, second reference liquid are marked with inside tube sealing to be used to transmit electron ion according to the voltage change in PH sensitive membranes；Institute
The one end for stating electrode conductor is stretched into the second reference liquid, and the other end is stretched out from seal pipe using the terminals as normal electrode.
2. PH/ORP sensors as claimed in claim 1, it is characterised in that the electricity of the normal electrode and/or measuring electrode
Pole conductor is platinum filament.
3. PH/ORP sensors as claimed in claim 1, it is characterised in that the ground connection salt bridge is platinum filament.
4. PH/ORP sensors as claimed in claim 1, it is characterised in that first reference liquid delays for 3mol/L potassium chloride
Rush solution.
5. PH/ORP sensors as claimed in claim 1, it is characterised in that the voltage comparator is differential operational amplifier,
Its output end connects voltage measuring apparatus.
6. PH/ORP sensors as claimed in claim 1, it is characterised in that the material of the shell uses glass or polyphenylene sulfide
Ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510003932.6A CN104515794B (en) | 2015-01-06 | 2015-01-06 | PH/ORP sensors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510003932.6A CN104515794B (en) | 2015-01-06 | 2015-01-06 | PH/ORP sensors |
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| CN104515794A CN104515794A (en) | 2015-04-15 |
| CN104515794B true CN104515794B (en) | 2017-10-24 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109477811B (en) * | 2016-06-16 | 2021-05-07 | 哈希公司 | Chlorine, Oxidation Reduction Potential (ORP) and pH measurement 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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|---|---|---|---|---|
| CN85201405U (en) * | 1985-04-10 | 1986-05-14 | 上海市轻工业研究所 | Ph and orp sensor |
| JPH10213562A (en) * | 1997-01-28 | 1998-08-11 | Kasahara Rika Kogyo Kk | Ph, orp, and water temperature measuring electrode |
| JP2002048753A (en) * | 2000-08-03 | 2002-02-15 | Aqua Science:Kk | Aging evaluation method for organism, food items or various kinds of water and its device |
| EP0777122B1 (en) * | 1995-12-07 | 2002-04-10 | Elsag International N.V. | Electrochemical Sensor |
| JP2003042996A (en) * | 2001-07-25 | 2003-02-13 | Dkk Toa Corp | Depressurization preventing tool for pressure type combined electrode |
| CN2650126Y (en) * | 2003-09-29 | 2004-10-20 | 上海精密科学仪器有限公司 | Composite electrode for measuring pH value |
| CN101135662A (en) * | 2006-08-30 | 2008-03-05 | 梅特勒-托利多仪器（上海）有限公司 | Electric potential analyse electric pole measuring method and apparatus |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9513248B2 (en) * | 2012-09-30 | 2016-12-06 | Invensys Systems, Inc. | Potentiometric sensor |
-
2015
- 2015-01-06 CN CN201510003932.6A patent/CN104515794B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2002048753A (en) * | 2000-08-03 | 2002-02-15 | Aqua Science:Kk | Aging evaluation method for organism, food items or various kinds of water and its device |
| JP2003042996A (en) * | 2001-07-25 | 2003-02-13 | Dkk Toa Corp | Depressurization preventing tool for pressure type combined electrode |
| CN2650126Y (en) * | 2003-09-29 | 2004-10-20 | 上海精密科学仪器有限公司 | Composite electrode for measuring pH value |
| CN101135662A (en) * | 2006-08-30 | 2008-03-05 | 梅特勒-托利多仪器（上海）有限公司 | Electric potential analyse electric pole measuring method and apparatus |
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