CN1491357A - Electronic tongue as ozone detector - Google Patents

Electronic tongue as ozone detector Download PDF

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Publication number
CN1491357A
CN1491357A CNA018227694A CN01822769A CN1491357A CN 1491357 A CN1491357 A CN 1491357A CN A018227694 A CNA018227694 A CN A018227694A CN 01822769 A CN01822769 A CN 01822769A CN 1491357 A CN1491357 A CN 1491357A
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electrode
electronic tongue
ozone
working electrode
concentration
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F・温奎斯特
F·温奎斯特
癖蠢
C·赫格贝里
甲-吕尔克尔
C·克兰兹－吕尔克尔
吮蠢
K·埃克贝里
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Otre AB
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Otre AB
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Priority claimed from EP00128297A external-priority patent/EP1219957A1/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G01N27/4045—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0039—O3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Medicinal Chemistry (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Abstract

An electronic tongue for the detection of ozone is based on voltammetry, and comprises at least one working electrode (12) and a counter electrode (16), wherein the working electrode(s) is(are) made of one or more transition metals or Au, or alloys thereof, or alloys thereof with other metals. The data processing is made by multivariate analysis. The sensor can be implemented on-line or in-line in a processing plant where it is desirable to monitor and control ozone levels, e.g. sterilization and purification plants.

Description

Electronic tongue as ozone detector
The present invention relates to the detecting device of so-called electronic tongue, more particularly, relate to based on Electrochemical Detection, be used for the existence of tracer liquid sample ozone and the electronic tongue of measuring its concentration.
Background of invention
Being controlled at parts per million (ppm) (ppm) scope to level of ozone interior is a very important instrument for materials disinfection, for example uses in ozone abatement apparatus and the utensil to be harmful to and unwanted species in the medicine preparation.Ozone is a kind of material of killing such as the excellent properties of microorganism entities such as virus, bacterium, spore and fungi that has.Because ozone has had toxicity to these entities when low concentration (ppm scope), therefore needing can real-time online control and measurement ozone.For various types of equipment and technology (for example medical equipment, Food ﹠ Drink process equipment) and the cleaning under agricultural and feeding environment, to sterilize and sterilization, this method has very high value.This method also can be used for measuring the oxidation situation of organic material in exploitation and manufacturing microelectronic product and production method.
The ozone detector of prior art is based on many distinct methods.Majority method requires to use certain type reagent, that is to say, perhaps must extract sample to measure the ozone or the contaminated system of having to wherein from system.The latter is unacceptable for the water sterilization of for example medical usage.Spectroscopic methodology can not cause that these disturb, but needs the system of quite expensive complexity.And these systems need provide window on light path, and the drifting problem that will cause in time takes place to block window.
Disclose a kind of electronic tongue of the electric pulse based on pulse protocol in WO99/13325, described pulse protocol comprises sequentially with different amplitudes and is added to a plurality of pulses on the electrode.Described electric pulse can be selected from potential pulse or current impulse.The response signal of gained is as the input of the pattern recognition program of the concentration of the result who is used to explain and exports indication sample desirable characteristics in the computer, for example analyte, pH etc.Analysis is based on multiplex method, for example PCA (principal component analysis (PCA)).The brief description of PCA can be consulted the article " An electronictongue based on voltammetry " of F.Winquist etc., Analytica Chimica Acta, 357 (1997) 21-31.Described article and described WO openly all are included in herein as a reference.
Summary of the invention
The present invention proposes the new application of the above-mentioned type electronic tongue, promptly be used for the existence of tracer liquid sample ozone and measure its concentration.
Electronic tongue of the present invention defines in claim 1.
The system that comprises electronic tongue of the present invention defines in claim 11.
Electronic tongue of the present invention is based on Voltammetry, and based on the concrete selection to the metal or alloy that is used for working electrode.
Advantage of the present invention is that system is simple, long-term stability.Particularly, drive system under the situation of reference electrode might do not had.Therefore come any pollution risk of supervisory system just not exist by means of leaking electrolyte from reference electrode.Nor need to regularly replace reference electrode again.Otherwise overall cost need be regularly carried out and further increase in this replacing.
Brief description
Below in conjunction with accompanying drawing the present invention is elaborated, in the accompanying drawing:
Fig. 1 illustrates and utilizes model experiment device of the present invention;
Fig. 2 illustrates the embodiment of the sensor device that comprises notion of the present invention;
Fig. 3 illustrates and can be used for pulse train of the present invention;
Fig. 4 illustrates the PCA curve that typical ozone is measured;
Fig. 5 illustrates the relation between the concentration value of determining according to the present invention measurement and expection;
Fig. 6 a-d illustrates the PCA curve of measuring with different single electrodes;
Fig. 7 illustrates the PCA curve of measuring based on four electrode sensors of making electrode with different metals;
Fig. 8 illustrates another embodiment according to sensor of the present invention;
Fig. 9 illustrates the another embodiment according to sensor of the present invention;
Figure 10 is illustrated in the implementation that uses sensor of the present invention in the sterilizing equipment decontaminating apparatus;
Figure 11 is the graphic extension of LAPV ladder; And
Figure 12-the 18th illustrates the chart of the measurement result of utilizing a plurality of electronic tongue.
DETAILED DESCRIPTION OF THE PREFERRED
In the present invention, " electronic tongue " speech is meant the device that comprises at least one sensing element, and its response is handled with multiplex method when being subjected to sample stimulus." sensing element " can be a kind of of multiple device, for example, but is not limited to, and the electrode of redox reaction takes place on its surface.
Refer now to one and utilize the embodiment of voltammertry system that the present invention is described, the device of described type is shown in Fig. 1.Described device comprises a sampling receptacle 2 that comprises sample, and the ozone concentration of sample has to be determined.This container can be silent oscillation or be designed to flow cell that what use is the static cell that has magnetic stirring apparatus 4 in the experiment of following explanation.Sensor device 6 immerses in the sample liquids.The embodiment of sensor device is shown in Fig. 2, and it comprises it being bar-shaped supporting member 8 basically, wherein is built-in with many wire or metal needle 10, and its ends exposed outside.The end that tinsel exposes forms the working electrode 12 of sensor device.Supporting member is the most handy to guarantee have the material of excellent sealing to make between the material that tinsel and tinsel be placed in one, to eliminate in measurement because the interference that leak of liquid causes between propping material and the tinsel.A kind of suitable material is a dental material, and the commercial goods is called Komposit TM, Filtek TMZ250 can be by 3M Svenska, and Sweden buys.Certainly can provide other material of suitable sealing property also can use.
Ag/AgCl (KCl 3M) electrode can be used as reference electrode, but other conventional reference electrode that industry is known can use too.
Measurement mechanism can have several methods to realize.Can adopt the three-electrode system of standard, i.e. working electrode, auxiliary (counter) electrode and reference electrode.Perhaps, can only use reference electrode and working electrode.
But should be pointed out that and do not use any reference electrode the present invention also can fine work.So, in a preferred embodiment, use two electrode assemblies with working electrode and auxiliary electrode.Current potential is controlled with the software of electronics and/or control module (as voltage stabilizer).
Shown among the embodiment of (Fig. 2), sensor device comprises 6 working electrodes 12 making with different materials.But number of electrodes is not strict, can be from single electrode to dozens of even more a plurality of electrode.The outside linking number that only is subjected in principle to need to do limits.If there are hundreds of electrodes to be connected with external device (ED), very difficulty does not have this possibility though should not get rid of.The material of making electrode can be from Rh, Pt, Au, Os, Ru, Ni, Ti, Re and their alloy or with the alloy of other metal in select one or more.Any metal that can produce required effect can use certainly.
Tinsel passes supporting member 8, comes out and is connected to electrical lead 14 from the other end.As auxiliary electrode 16 (counter electrode), a stainless-steel tube tight enclosing is lived bar-shaped supporting member.If realizing device of the present invention or system itself is that for example stainless steel is made, crust of the device just can be used as counter electrode.Other material is made auxiliary electrode and also can be considered, Pt for example, Au.Electrical lead 18 also is connected to auxiliary electrode.Electrical lead from all electrodes all is connected on the voltage stabilizer 20.Working electrode connects by relay box 22, is connected to two electrodes configurations (no reference electrode) or three electrodes configurations (reference electrode is arranged) respectively to allow each working electrode.
(Lund Sweden) measures for ISKRA, Chemel AB by the voltage stabilizer MA 5410 that connects by interface for electric current or electric current transient response.With time constant is that 0.3 second electronic filter is added on the voltage stabilizer with the smoothingtime transient response.Come control system with a PC, for example timing that begins of pulse, operational relay box, measure electric current transient response and storage data.Use is with Labview TMThe computer program that (National Instrument) writes defines the voltage on the electronic tongue, the control sampling frequency, and be defined in the data point of storing in the data matrix.
In experiment discussed below, measure sequence and add two kinds of voltages on the electronic tongue and two kinds of electrochemically cleaning processes are formed by being added in.Certainly it should be understood that this is an exemplary sequence, in fact can use any pulse (amplitude, duration etc.) combination, as long as can obtain useful results.As for pulse shape, many available selections are arranged, for example square/rectangular pulse (as in following example), sawtooth wave, sine wave, etc.And four electrodes (Au, Ir, Pt, Ph) sensor device have been used.The sequence of using in the described experiment following (as shown in Figure 3):
A: electrochemically cleaning
When beginning, described process on working electrode, adds 1.5V positive potential 0.5 second.Added the 2.1V negative potential then 0.5 second.Last potential setting is 0V 2 seconds.The all working electrode is repeated this process.
B: large-amplitude pulse voltammertry (LAPV)
When beginning, the LAPV process on first working electrode, adds-2.1V current potential 0.5 second.Then current potential is dropped to 0V, kept 0.5 second.Add negative potential again, but than first current potential high 300mV, and kept 0.5 second, and then be 0 potential setting.This sequence continues to carry out up to finally reaching maximum potential+2.1V.
C: electrochemically cleaning
Repeat the same process of A.
D: ladder voltammertry
Add on working electrode-the 2.1V current potential, described current potential was kept 0.5 second, progressively improved current potential then, improved 300mV at every turn, up to finally reaching maximum potential+2.1V.
Each working electrode in the sensor device is repeated whole A-D sequence, and promptly four electrodes in the embodiment shown are defined as one-period.
The main points of measuring are according to the response curve that the result as the potential pulse program produces current value to be taken a sample.Measure sequence and be divided into 57 steps, the duration of each step is 500ms.Speed with 1000Hz is taken a sample to current value, so 500 numerical value of each step generation, wherein selects 19 and is stored in the data matrix.The selection of data point can be adapted to concrete condition, and is not strict to the method.Only need to count to reduce to rational number.But reasonable number can have nothing in common with each other to each situation.In some cases, 4 of possibilities are just enough, and may need about 100 other situation.So, in above-mentioned example,, there is 19 * 57=1083 numerical value to be stored in the matrix for each electrode, for four electrodes, amount to and produce and stored 4332 measurement numerical value.
Adopt multivariate method to carry out data processing, particularly used so-called principal component analysis (PCA), below make brief description with reference to Fig. 4-7.
For the example of four different operating electrodes of above-mentioned employing, measurement comprises carries out a pulse train to each electrode, and produces the data matrix with 4332 numerical value.Described matrix can be regarded as a point in 4332 dimension spaces.Carry out once new measurement then, produce new matrix, the final matrix stack representing many points in 4332 dimension spaces that produces with 4332 numerical value.Table 1 illustrates 147 all data sampling experiments of measuring, and will go through, and Fig. 4 is the diagrammatic representation of table 1 data.
Table 1
Cycle O 3Concentration (ppm) Temperature ℃ Cycle O 3Concentration (ppm) Temperature ℃ Cycle O 3Concentration (ppm) Temperature ℃ Cycle O 3Concentration (ppm) Temperature ℃
1 0 31 48 3.0-2.9 32 95 2.9-3.0 31 142 0.8-0.9 32
2 0 31 49 3.0-2.9 32 96 2.9-3.0 31 143 0.9 32
3 0 31 50 3.0-2.9 32 97 2.9-3.0 31 144 0.9 32
4 0 31 51 3.0-2.9 32 98 2.9-3.0 31 145 2.4-2.9 32
5 0 31 52 3.0-2.9 32 99 2.9-3.0 31 146 2.9-3.0 32
6 0 31 53 3.0-2.9 32 100 2.9-3.0 31 147 2.9-3.0 32
7 0 31 54 3.0-2.9 32 101 2.9-3.0 31 148
8 0 31 55 3.0-2.9 32 102 2.9-3.0 31 149
9 0 31 56 3.0-2.9 32 103 31 150
10 0 31 57 3.0-2.9 32 104 2.0 31 151
11 0 31 58 2.5-1.9 32 105 31 152
12 0 31 59 1.9-1.6 32 106 31 153
13 0.7-2.2 31 60 1.6-1.3 32 107 1.5 31 154
14 2.2-2.6 31 61 1.1-1.0 32 108 31 155
15 2.6-2.8 31 62 1.0-0.9 32 109 31 156
16 2.9 31 63 0.9-0.8 32 110 1.2 31 157
17 2.9 31 64 0.8-0.7 32 111 31 158
18 31 65 0.7 32 112 1.0 31 159
19 3.0-2.9 32 66 0.7-0.6 32 113 31 160
20 32 67 0.6-0.5 32 114 31 161
21 32 68 0.5 32 115 0.8 31 162
22 3.0-2.9 32 69 0.5 32 116 31 163
23 3.0-2.9 32 70 0.5-0.4 32 117 0.7 31 164
24 3.0-2.9 32 71 0.4 32 118 0.6 31 165
25 3.0-2.9 32 72 0.4-0.3 32 119 31 166
26 3.0-2.9 32 73 0.3 32 120 31 167
27 3.0-2.9 32 74 0.3 32 121 0.5 31 168
28 3.0-2.9 32 75 0.3-0.2 32 122 31 169
29 3.0-2.9 32 76 0.2 32 123 31 170
30 3.0-2.9 32 77 0.2 32 124 0.4 31 171
31 3.0-2.9 32 78 0.2-0.1 32 125 172
32 3.0-2.9 32 79 0.1 32 126 173
33 3.0-2.9 32 80 0.1-0 32 127 0.3 32 174
34 3.0-2.9 32 81 0.1-0 32 128 32 175
35 3.0-2.9 32 82 0 32 129 32 176
36 3.0-2.9 32 83 0 32 130 0.2 32 177
37 3.0-2.9 32 84 0 32 131 32 178
38 3.0-2.9 32 85 0 32 132 32 179
39 3.0-2.9 32 86 0 32 133 0.1 32 180
40 3.0-2.9 32 87 0 32 134 32 181
41 3.0-2.9 32 88 1.7-2.7 32 135 32 182
42 3.0-2.9 32 89 2.7-2.9 32 136 0.1 32 183
43 3.0-2.9 32 90 2.8-3.0 32 137 0.1-0 32 184
44 3.0-2.9 32 91 138 32 185
45 3.0-2.9 32 92 2.9-3.0 31 139 0.1-0 32 186
46 3.0-2.9 32 93 2.9-3.0 31 140 0 32 187
47 3.0-2.9 32 94 2.9-3.0 31 141 0 32 188
Table 1 can think to represent 147 points of 4332 dimension spaces.Data are used PCA relate to the direction of finding out data deviation maximum in the described space.This is a vector in 4332 dimension spaces, is called first principal component PC1.Subsequently, with the maximum deviation on the direction of first principal component quadrature, also be a vector certainly, be called Second principal component, PC2 (also can calculate other major component, all explain) up to most observationss.So just form a new matrix of being determined by major component, and data set can greatly reduce, this will decide according to the importance of major component.In many cases, can be compressed to and have only two dimension.So, two vectors, PC1 and PC2 have defined a two-dimensional space, and it makes the maximization of raw observation deviation.147 points of 4332 dimension spaces project on the plane that is covered by PC1 and PC2 now, thereby produce figure shown in Figure 4.
In measuring sequence, the ozone concentration of system changes, or dynamically increases ozone generator concentration, perhaps decomposes in time by ozone and makes the concentration decay.Table 1 has clearly illustrated these variations.In cycle #1-12 concentration is 0ppm.Increase gradually and maintain about 3ppm in cycle #13-18 concentration at cycle #22-57.Allow density loss at cycle #58-81 then, #82-84 drops to 0ppm to the cycle.At cycle #88-91 concentration is increased then, be increased to about 3ppm to cycle #92-102, and descend (#103-139).At cycle #142-147 concentration is increased.
As can be seen, measurement can be divided into relevant with the different conditions (for example different concentration, density loss cycle etc.) of system not on the same group.The figure of Fig. 4 based on measurement result be used for setting up the Data Analysis Model of ozone concentration.When this model is used for the system of unknown ozone concentration measured, just can predict concentration.
For described model is remained valid, draw predicted value with respect to the given value half interval contour.Described curve is shown in Fig. 5.The correlativity of the two is fine as can be seen.
Fig. 6 a-6d illustrates and utilizes above-mentioned pulse train A-D, with one group of measurement result that the PCA curve representation is done each electrode of four kinds of different metals, below makes brief description.
Can know and find out, have qualitative difference between each experiment, be apparent that the figure (Fig. 6 d) that represents Rh has bigger deviation in other direction of Y direction ratio most.Described deviation can be used to make up model, is particularly useful for determining ozone concentration.
In another experiment shown in Figure 7, figure has comprised the measurement data of all four electrodes.The electrode pair curve made from Rh plays a major role as can be seen.
If model obtains according to " training data " and measures with the sensor that four kinds of different metals are arranged, so, though the metal of result's proof " ozone special use " (is gone up the Au in the example, Ir, Pt) role is less, but the combination property of four electrode sensors is better than Rh single electrode.Its preferable performance is reflected in the corresponding PLS curve related coefficient preferably.Reason is that in the intrinsic data compression process of PCA " the white nose " in the data is inoperative, and any important information, no matter its size all can have a positive effect, so net result will be improved.
In above-mentioned measurement.The current potential of pulse train-2.1V and+change between the 2.1V.But also can select other to be used for described measurement at interval, also can optimize sweep interval.Particularly might be only the negative potential scope (for example, 0 to-3.0V) in work just enough because the oxidation-reduction potential that may react that relates to ozone is all at negative potential.
Experiment shows that conductance is quite important for result's quality, and conductance is high more, and measurement result is good more.Therefore best energy measurement conductance can be added ionic species and be regulated conductance when allowing in system.Do unlikelyly for airtight on-line system like this, nor wish to do like this, particularly the system that is being used for sterilizing.When making conductivity measurement, on same supporting member, also near the working electrode of electronic tongue, dispose two extra electrodes.
The embodiment of the sensor device of above-mentioned discussion only is a kind of in many possible configurations of working electrode.Another kind of method of making the device with a plurality of electrodes is shown in Fig. 8, and way provides the flat board of the image plane support component 24 of a pottery or other inert material, above the parallel strip 26 of deposit different metal.If a dull and stereotyped end immerses the medium that comprises ozone, the part of each bonding jumper is all contacted with medium, the other end of each bonding jumper is connected to potentiostat, and is identical with the connected mode of above-mentioned bar-shaped sensor device.
The design of another kind of sensor device is shown in Fig. 9, is a part that electrode strip 28 is integrated in the circulating line of using as for example disinfecting process on one section tube wall 30.Bonding jumper can insert in the tube wall of a certain section pipe, at least one end of each bonding jumper straight-through electric connection line 32 is arranged, so that provide and being connected of suitable external unit (for example potentiostat).
Practical structures and configuration that those skilled in the art can be imagined the electrode that is used for sensor device of the present invention can have multiple other changes and change, and all these changes and change all should belong within the scope of claims.
One big advantage of detecting device of the present invention and measuring system be exactly it be applicable to on-line measurement ozone, for example in antipollution sterilization of needs or cleaning equipment.Figure 10 shows the synoptic diagram of this application.
Therefore, shown in cleaning system comprise process chamber 34, it comprises apparatus to be sterilized, surgical apparatus etc. for example, or himself be exactly a device, for example dialysis apparatus etc.There is the feedback pipe material 36 of inlet 38 to be tightly connected with process chamber.Output channel 40 will send out processing with gas ozoniferous or the liquid crossed.Certainly in some applications can recycle feedback pipe material (not shown).Control module 46 of the present invention can be connected to ozone sensor 42,44 and determine when the sterilisation level that reaches required with the control sensor and according to their output, if reach, just adjust level of ozone in the feedback material.
As shown in the figure, the present invention can be used as the ozone detection system, is preferably in the fluid circulation system that needs the monitoring ozone concentration as online or direct insertion detection system.Described system is based on voltammertry and comprise that at least one is used in working electrode and a counter electrode that the material discussed in the sensor device is made.Electrode is connected on the programmable pulse generator, and described programmable pulse generator can be added to described working electrode one at a time with predetermined excitation pulse sequence.Described system also comprises pen recorder, be used for writing down described working electrode to adding pulse train respond and the output that produces.Sampler is set is used at interval described output valve being taken a sample with preset time, sampling numerical value is stored in the matrix store.Have a processing unit to be used for described data matrix is done multivariate analysis, and display device is used to show the result of described multivariate analysis.
Followingly provide the example that some are measured with different electronic tongue with reference to chart.
Calibration curve
In order to study the drift of built-in amperometric measurement sensor in the ozone generator 13, carried out proofreading and correct experiment at work.Three other measurement results of branch (is four times to calibration curve 1) constitute the basis of a calibration curve.Selection has the multiple spot working curve of three repetitions and the wavelength of 260nm.Standard model is that ozone concentration is 1,1.5,2 and the deionized water of 3ppm.With deionized water solution for referencial use.Details are asked for an interview following chart.
The spectral measurement record
Calibration curve No.1,000829
?O 3Concentration (ppm) ?1Abs ?2Abs ?3Abs ?4Abs ?MWAbs
?1 ?0.066 ?0.059 ?0.06 ?0.065 ?0.063
?1.5 ?0.091 ?0.084 ?0.09 ?0.087 ?0.088
?2 ?0.128 ?0.113 ?0.113 ?0.13 ?0.121
?3 ?0.186 ?0.164 ?0.164 ?0.191 ?0.176
y＝0.059x+0.0028
Related coefficient=99.73%
Calibration curve No.2,000925
?O 3Concentration (ppm) ?1Abs ?2Abs ?3Abs ?MWAbs
?1 ?0.061 ?0.064 ?0.06 ?0.063
?1.5 ?0.094 ?0.087 ?0.091 ?0.088
?2 ?0.112 ?0.122 ?0.118 ?0.121
?3 ?0.156 ?0.180 ?0.194 ?0.176
y＝0.057x+0.0048
Related coefficient=99.99%
Calibration curve No.3,001011
?O 3Concentration (ppm) ?1Abs ?2Abs ?3Abs ?MWAbs
?1 ?0.07 ?0.057 ?0.059 ?0.062
?1.5 ?0.108 ?0.094 ?0.099 ?0.1
?2 ?0.126 ?0.137 ?0.136 ?0.133
?3 ?0.203 ?0.196 ?0.189 ?0.196
y＝0.066x+0.0017
Related coefficient=99.90%
Calibration curve No.4,001108
?O 3Concentration (ppm) ?1Abs ?2Abs ?3Abs ?MWAbs
?1 ?0.068 ?0.068 ?0.063 ?0.066
?1.5 ?0.102 ?0.102 ?0.096 ?0.1
?2 ?0.125 ?0.126 ?0.124 ?0.125
?3 ?0.181 ?0.195 ?0.181 ?0.186
y＝0.059x+0.0087
Related coefficient=99.92%
Calibration curve No.5,001206
O 3Concentration (ppm) ?1Abs ?2Abs ?3Abs ?MWAbs
?1 ?0.071 ?0.064 ?0.076 ?0.070
?1.5 ?0.088 ?0.091 ?0.091 ?0.09
?2 ?0.114 ?0.123 ?0.124 ?0.120
?3 ?0.166 ?0.168 ?0.180 ?0.171
y＝0.051x+0.017
Related coefficient=99.83%
Measurement sequence (seeing Figure 11) adds two kinds of voltages in the following order by (Labview is available from National Instrument) and uses two electrochemically cleaning processes and form on electronic tongue:
1) electrochemically cleaning process
The electrochemically cleaning process of electrode added the 1.5V positive voltage 0.5 second when beginning.Add the same time of 1.5V negative potential (0.5 second) then.Then voltage is set at 0V2 second.
2)LAPV
Add when LAPV begins-the 2.1V current potential, voltage is made as 0V then.Increase current potential 300mV then, restart described sequence.Continue to carry out finally reaching maximum potential+2.1V up to voltage.
3) electrochemically cleaning process
See above-mentioned 1).
4) ladder
Voltage begins to be-2.1V, and 300mV then is up to finally reaching maximum potential.
Described measurement sequence is added in earlier on the spun gold, is added in iridium then successively, on platinum and the rubidium silk, is defined as a circulation.Measure sequence and be divided into for 57 steps, the time in each step is 500ms.With the 1000Hz sampling frequency current value is taken a sample.Per step produces 500 sample values, and wherein 19 (key words) are stored in the data matrix.Each working electrode has 19 * 57=1083 numerical value to be stored in the data matrix.All four working electrodes produce 4 * 1083=4332 measured value.Institute adds current potential, sampling frequency, and selected data point is by following table as seen.
Electronic tongue is measured configuration
Period: 200
Time between circulation: 0 minute
No.Propes：4
Sample/step: 495
Aq speed: 1000 sample/seconds
Number of steps: 57
Each step time: 500ms
Number of keyword: 19
Data point/OK: 4332
Output data Output data Key word
?1.500 ?1.500 ?25
?-1.500 ?0.000 ?50
?0.000 ?1.800 ?75
?0.000 ?0.000 ?100
?0.000 ?2.100 ?125
?0.000 ?-1.500 ?150
?-2.100 ?0.000 ?175
?0.000 ?0.000 ?200
?-1.900 ?0.000 ?225
?0.000 ?0.000 ?250
?-1.500 ?-2.100 ?275
?0.000 ?-1.800 ?300
?-1.200 ?-1.500 ?325
?0.000 ?-1.200 ?350
?-0.900 ?-0.900 ?375
?0.000 ?-0.600 ?400
?-0.600 ?-0.300 ?425
?0.000 ?0.000 ?450
?-0.300 ?0.000 ?475
?0.000 ?0.300
?0.000 ?0.600
?0.300 ?0.900
?0.000 ?1.200
?0.600 ?1.500
?0.000 ?1.800
?0.900 ?2.100
?1.200 ?0.000
?0.000 ?0.000
At experimental session, ozone concentration manually changes from 0-3ppm in six open architecture tests.Use auto-programming to change ozone concentration then.To each circulation, ozone concentration and relevant temperature are used manual and automatic record respectively in measurement.
In six open architecture tests, respectively to the hot ozone generator of cold-peace, water quality, new or old packing, and conductance has been done research.Experimental data sees also following table.More detailed experimental data sees also following table and Figure 12-18.
Experimental record (Figure 12) with electronic tongue 000919
The deionized water that experiment 1 usefulness is new (just having prepared before the beginning), packaging ring 1 and cold ozone generator.
Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation ?O 3Concentration (ppm) Temperature ℃
?1 ?0 ?20 ?35 ?1.0-0.9 ?25 ?69
?2 ?0 ?20 ?36 ?0.9-1.0 ?25 ?70
?3 ?0 ?20 ?37 ?0.9-1.0 ?25 ?71
?4 ?0 ?21 ?38 ?0.9-1.0 ?25 ?72 *
?5 ?0 ?21 ?39 * ?0.9-1.0 ?25 ?73 ?2.9-3.0 ?31
?6 ?0 ?21 ?40 ?1.9-2.0 ?25 ?74 ?2.9-3.0 ?31
?7 ?0 ?21 ?41 ?2.0-1.9 ?25 ?75 ?2.9-3.0 ?31
?8 ?0 ?21 ?42 ?1.9-2.0 ?25 ?76 ?2.9-3.0 ?31
?9 ?0 ?21 ?43 ?2.0 ?25 ?77 ?2.9-3.0 ?31.5
?10 ?0 ?22 ?44 ?2.0-1.9 ?25 ?78 ?2.9-3.0 ?32
?11 ?0 ?22 ?45 ?1.9 ?25 ?79 ?3.0-2.9 ?32
?12 ?0 ?22 ?46 ?2.0-1.9 ?25 ?80 ?3.0-2.9 ?32
?13 ?0 ?22 ?47 ?2.0-1.9 ?25 ?81 ?3.0-2.9 ?32
?14 ?0 ?22 ?48 ?2.0-1.9 ?25 ?82 ?2.9-3.0 ?32
?15 ?0 ?22 ?49 ?1.9-2.0 ?25 ?83 ?3.0-2.9 ?32
?16 ?0 ?23 ?50 ?1.9-2.0 ?25 ?84 ?2.9-3.0 ?32
?17 ?0 ?23 ?51 ?2.0 ?25.5 ?85 ?2.9-3.0 ?32
?18 * ?0 ?23 ?52 ?1.9-2.0 ?26 ?86 ?2.9 ?32
?19 ?1.4-1.7 ?23 ?53 ?1.9-2.0 ?26 ?87 ?2.9 ?32
?20 ?1.7-1.6 ?23 ?54 ?1.9-2.0 ?26 ?88 ?2.9-3.0 ?32
?21 ?1.6-1.4 ?23 ?55 ?1.9-2.0 ?26 ?89 ?2.9-3.0 ?32
?22 ?1.2-1.1 ?23 ?56 ?1.9-2.0 ?26 ?90 * ?2.9 ?32
?23 ?1.1-1.0 ?23.5 ?57 ?1.9-2.0 ?26 ?91 ?2.1-1.8 ?32
?24 ?1.0-1.1 ?24 ?58 ?92 ?1.8-1.5 ?32
?25 ?1.0-0.9 ?24 ?59 ?93 ?1.5-1.4 ?32
?26 ?0.9 ?24 ?60 ?94 ?1.0-0.9 ?32
?27 ?0.9-1.0 ?24 ?61 ?95 ?0.9-0.8 ?32
?28 ?1.0 ?24 ?62 ?96 ?0.8-0.7 ?32
?29 ?1.0 ?24 ?63 ?97 ?0.5-0.4 ?32
?30 ?1.0 ?24 ?64 ?98 ?0.4-0.3 ?32
?31 ?1.0 ?24 ?65 ?99 ?0.3-0.2 ?32
?32 ?1.0-0.9 ?24.5 ?66 ?100 ?0.1-0 ?32
?33 ?1.0 ?25 ?67 ?101 ?0 ?32
?34 ?1.0-1.1 ?25 ?68 ?102 ?0 ?32
*Ozone concentration shown in circulation back manually change.
Per the 3rd circulation (1,4,7 etc.) and data point in the electrochemically cleaning are all got rid of outside data analysis.
Experimental record (Figure 13) with electronic tongue 000920
The deionized water that experiment 2 usefulness are new (just having prepared before the preheating), the ozone generator of packaging ring 1 and temperature.
Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?1 ?0 ?33 ?40 ?1.9-2.0 ?32 ?79 ?2.9-3.0 ?32
?2 ?0 ?33 ?41 ?1.9-2.0 ?32 ?80 ?3.0 ?32
?3 ?0 ?33 ?42 ?1.9-2.0 ?32 ?81 ?3.0-2.9 ?32
?4 ?0 ?33 ?43 ?0.9-2.0 ?32 ?82 ?2.9-3.0 ?32
??5 ??0 ??33 ??44 ??0.9-2.0 ??32 ??83 ??3.0-2.9 ??32
??6 ??0 ??33 ??45 ??0.9-2.1 ??32 ??84 ??3.0-2.9 ??32
??7 ??0 ??33 ??46 ??2.0 ??32 ??85 ??3.0-2.9 ??32
??8 ??0 ??33 ??47 ??2.0-1.9 ??32 ??86 ??2.9-3.0 ??32
??9 ??0 ??33 ??48 ??1.9-2.0 ??32 ??87 ??2.9-3.0 ??32
??10 ??0 ??33 ??49 ??1.9-2.0 ??32 ??88 ??2.9-3.0 ??32
??11 ??0 ??33 ??50 ??2.0 ??32 ??89 ??2.9-3.0 ??32
??12 ??0 ??33 ??51 ??2.0-1.9 ??32 ??90 ??2.9-3.0 ??32
??13 ??0 ??33 ??52 ??2.0-1.9 ??32 ??91 ??2.9-3.0 ??32
??14 ??0 ??33 ??53 ??2.0 ??32 ??92 ??2.9-3.0
??15 ??0 ??33 ??54 ??1.9-2.1 ??32 ??93 ??2.9-3.0 ??31
??16 ??0 ??33 ??55 ??2.0 ??32 ??94 ??2.9-3.0 ??31
??17 ??0 ??33 ??56 ??2.0 ??32 ??95 ??2.9-3.0 ??31
??18 * ??0 ??33 ??57 ??2.0 ??32 ??96 * ??2.9-3.0 ??31
??19 ??0.5-0.8 ??33 ??58 ??97 ??2.3-2.1 ??31
??20 ??0.8-0.9 ??33 ??59 ??98 ??2.1-1.8 ??31
??21 ??0.9-1.0 ??33 ??60 ??99 ??1.8-1.6 ??31
??22 ??0.9-1.0 ??33 ??61 ??100 ??1.3-1.2 ??31
??23 ??1.0-0.9 ??33 ??62 ??101 ??1.2-1.1 ??31
??24 ??1.0-0.9 ??32.5 ??63 ??102 ??1.1-1.0 ??31
??25 ??1.0-0.9 ??32 ??64 ??103 ??0.8 ??31
??26 ??0.9-1.0 ??32 ??65 ??104 ??0.8-0.7 ??31
??27 ??0.9-1.0 ??32 ??66 ??105 ??0.7-0.6 ??31
??28 ??0.9-1.0 ??32 ??67 ??106 ??0.5 ??31
??29 ??0.9-1.0 ??32 ??68 ??107 ??0.5-0.4 ??31
??30 ??0.9-1.0 ??32 ??69 ??108 ??0.4 ??31
??31 ??0.9-1.0 ??32 ??70 ??109 ??0.3 ??31
??32 ??0.9-1.0 ??32 ??71 ??110 ??0.3-0.2 ??31
??33 ??1.0-0.9 ??32 ??72 ??111 ??0.2 ??31
??34 ??0.9-1.0 ??32 ??73 ??112 ??0.1 ??31
??35 ??0.9-1.0 ??32 ??74 ??113 ??0.1 ??31
??36 ??0.9-1.0 ??32 ??75 ??114 ??0.1 ??31
??37 ??0.9-1.0 ??32 ??76 ??115 ??0-0.1 ??31
??38 ??0.9-1.0 ??32 ??77 ??116 ??0 ??31
??39 * ??0.9-1.0 ??32 ??78 * ??117 ??0 ??31
*Ozone concentration shown in circulation back manually change.
Per the 3rd circulation (1,4,7 etc.) and data point in the electrochemically cleaning are all got rid of outside data analysis.
Experimental record with electronic tongue 000926
The new milli-q water of experiment 4 usefulness (preheating has just prepared before with beginning before), the ozone generator of packaging ring 1 and temperature.
Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?1 ?0 ?34 ?45 ?89
?2 ?0 ?34 ?46 ?90
?3 ?0 ?34 ?47 ?91
?4 ?0 ?34 ?48 ?92
?5 ?0 ?34 ?49 ?93 ?2.9-3.0 ?32
?6 ?0 ?34 ?50 ?94 ?2.5-2.1 ?32
?7 ?0 ?34 ?51 ?95 ?2.1-1.6 ?32
?8 ?0 ?34 ?52 ?96 ?1.6-1.3 ?32
?9 ?0 ?34 ?53 ?97 ?1.0-0.8 ?32
?10 ?0 ?34 ?54 ?98 ?0.8-0.7 ?32
?11 ?0 ?34 ?55 ?99 ?0.7-0.6 ?32
?12 * ?0 ?34 ?56 ?32 ?100 ?0.5 ?32
?13 ?0-0.5 ?33.5 ?57 * ?32 ?101 ?0.4 ?32
?14 ?0.5-1.0 ?33 ?58 ?2.6 ?32 ?102 ?0.4-0.3 ?32
?15 ?1.0-1.6 ?33 ?59 ?103 ?0.3-0.2 ?32
?16 ?2.0-2.3 ?33 ?60 ?104 ?0.2-0.1 ?32
?17 ?2.3 ?33 ?61 ?105 ?0.1 ?32
?18 ?2.3-2.4 ?33 ?62 ?106 ?0.1-0 ?32
?19 ?2.4-2.5 ?33 ?63 ?107 ?0 ?32
?20 ?2.5 ?33 ?64 ?108 ?0 ?32
?21 ?2.6 ?33 ?65 ?109 ?0 ?32
?22 ?66 ?110 ?0 ?32
?23 ?2.7 ?33 ?67 ?111 ?0 ?32
?24 ?2.7 ?33 ?68 ?112 ?0 ?32
?25 ?69 ?113 ?0 ?32
?26 ?70 ?114 * ?0 ?32
?27 ?71 ?115 ?0.7-0.9 ?32
?28 ?72 * ?0 ?32 ?116 ?0.9-1.0 ?32
?29 ?73 ?117 ?0.9-1.0 ?32
?30 ?74 ?118 ?0.9-1.0 ?32
?31 ?75 ?2.9 ?32 ?119 ?1.0 ?32
?32 ?76 ?120 * ?1.0 ?32
?33 ?77 ?121 ?1.0-1.8 ?32
?34 ?78 ?122 ?1.8-2.0 ?32
?35 ?79 ?123 ?1.9-2.0 ?32
?36 ?80 ?124 ?1.9-2.0 ?32
?37 ?81 ?125 ?1.9-2.0 ?32
?38 ?82 ?126 * ?1.9-2.0 ?32
?39 ?83 ?127 ?2.8-2.9 ?32
?40 ?84 ?128 ?2.9-3.0 ?32
?41 ?85 ?129 ?2.9-3.0 ?32
?42 ?86 ?130 ?2.9-3.0 ?32
?43 ?87 ?131 ?2.9-3.0 ?32
?44 ?88 ?132 ?2.9-3.0 ?32
*Ozone concentration shown in circulation back manually change.
Per the 3rd circulation (1,4,7 etc.) and data point in the electrochemically cleaning are all got rid of outside data analysis.
Experimental record (Figure 15) with electronic tongue 000927
The new milli-q water of experiment 5 usefulness (preheating has just prepared before with beginning before), the ozone generator of packaging ring 1 and temperature.Also carry out conductivity measurement.
Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?1 ?0 ?31 ?43 ?0.2 ?32 ?88
?2 ?0 ?31 ?44 ?0.2 ?32 ?89
?3 ?0 ?31 ?45 ?0.2 ?32 ?90
?Cond ?1.6μS ?46 ?0.2 ?32 ?91
?4 ?0 ?31 ?47 ?0.1 ?32 ?92
?5 ?0 ?31 ?48 ?0.1 ?32 ?93
?6 * ?0 ?31 ?49 ?0.1 ?32 ?94
?7 ?0.3-1.7 ?31 ?50 ?95
?8 ?1.7-2.3 ?31 ?51 ?0 ?32 ?96
?9 ?2.3-2.6 ?31 ?52 ?97
?10 ?2.7-2.8 ?31 ?53 ?98
?11 ?2.8-2.9 ?31 ?54 ?99
?12 ?2.9 ?31 ?55 ?100
?Cond ?4.5μS ?56 ?101
?13 ?2.9-3.0 ?31 ?57 ?102
?14 ?2.9-3.0 ?31 ?58 ?103
?15 ?2.9-3.0 ?31 ?59 ?0 ?32 ?104
?16 ?2.9-3.0 ?31 ?60 ?105
?17 ?2.9-3.0 ?31 ?Cond ?7.6μS ?106
?18 ?2.9-3.0 ?31 ?61 ?0 ?32 ?107
?Cond ?7.3μS ?62 ?108 * ?33
?19 ?2.9-3.0 ?31 ?63 * ?109 ?33
?20 ?2.9-3.0 ?31 ?64 ?110 ?1.9-1.4 ?32
?21 * ?2.9-3.0 ?31 ?65 ?2.3-2.8 ?32 ?111 ?1.4-1.2 ?32
?22 ?2.4-1.7 ?31 ?66 ?2.8-2.9 ?32 ?Cond ?18.4μS
?23 ?1.7-1.4 ?31 ?67 ?112 ?1.0-0.9 ?32
?24 ?1.4-1.1 ?31 ?68 ?113 ?0.9-0.8 ?32
?25 ?1.0-0.9 ?31 ?69 ?114 ?0.8-0.7 ?32
?26 ?0.9-0.8 ?31 ?70 ?115 ?0.7 ?32
?27 ?0.8 ?31 ?71 ?116 ?0.7 ?32
?Cond ?9.1μS ?72 ?117 ?0.7 ?32
?28 ?0.7-0.6 ?31 ?73 ?118 ?0.6 ?32
?29 ?0.7-0.6 ?31 ?74 ?119 ?0.6 ?32
?30 ?0.6 ?31 ?75 ?120 * ?0.6 ?32
?31 ?0.6 ?31 ?76 ?121 ?0.5 ?32
?32 ?0.6-0.5 ?31 ?77 ?122 ?0.5 ?32
?33 ?0.5 ?31 ?78 ?123 ?0.5 ?31
?34 ?0.5 ?31 ?79 ?124 ?0.4 ?31
?35 ?0.5-0.4 ?31 ?80 ?125 ?0.4 ?31
?36 ?0.4 ?31 ?81 ?126 ?0.4 ?31
?37 ?0.4 ?31 ?82 ?127 ?0.3 ?31
?38 ?0.4 ?31 ?83 ?128 ?0.3 ?31
?39 ?0.4-0.3 ?31 ?84 ?129 ?0.3 ?31
?40 ?0.3 ?32 ?85 ?130 ?0.3-0.2 ?31
?41 ?0.3 ?32 ?86 ?131 ?0.2
?42 ?0.3 ?32 ?87 ?132 ?0.2
Circulation ??O 3Concentration (ppm) Temperature ℃ Circulation ??O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
??133 ??0.2 ??32 ??140 ??0.1 ??32 ??146 ??2.8-2.9 ??31
??134 ??0.2-0.1 ??32 ??141 * ??0.1 ??32 ??147 ??2.9-3.0 ??31
??135 ??0.2-0.1 ??32 ??142 ??0.5-0.9 ??32 ??148 ??31
??136 ??16.9μS ??143 ??0.9-1.0 ??32 ??149 ??31
??137 ??0.1 ??32 ??144 * ??1.0 ??32 ??150 ??1.8-1.6 ??31
??138 ??0.1 ??32 ??Cond ??15.6μS
??139 ??0.1 ??32 ??145 ??2.3-2.8 ??31
*Ozone concentration shown in circulation back manually change.
The Cond=conductance
Per the 3rd circulation (1,4,7 etc.) and data point in the electrochemically cleaning are all got rid of outside data analysis.
Experimental record (Figure 16) with electronic tongue 001002
The new milli-q water of experiment 6 usefulness (preheating has just prepared before with beginning before), the ozone generator of packaging ring 2 and temperature.Also carry out conductivity measurement.
Circulation O 3Concentration (ppm) Temperature ℃ Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?1 ?0 ?32 ?44 ?0.4-0.3 ?32 ?88 ?1.2-2.6 ?26
?2 ?0 ?32 ?45 ?0.4-0.3 ?32 ?89 ?2.6-3.0 ?26
?3 ?0 ?32 ?46 ?0.3 ?32 ?90 ?2.9-3.0 ?26
?Cond ?2.4μS ?47 ?0.3 ?32 ?91 ?2.9-3.0 ?26
?4 ?0 ?32 ?48 ?0.2-0.3 ?32 ?92 ?2.9-3.0 ?26
?5 ?0 ?32 ?49 ?0.2 ?32 ?93 ?26
?6 * ?0 ?32 ?50 ?0.2 ?32 ?94
?7 ?0.3-1.2 ?32 ?51 ?0.2-0.1 ?32 ?95
?8 ?1.2-2.3 ?32 ?Cond ?7.9μS ?96
?9 ?2.3-2.7 ?32 ?52 ?0.1 ?32 ?97
?10 ?2.8-2.9 ?32 ?53 ?0.1 ?32 ?98 ?2.9-3.0 ?26
?11 ?2.9 ?32 ?54 ?99
?12 ?2.9-3.0 ?32 ?55 ?100
?Cond ?3.9μS ?56 ?101
?13 ?2.9-3.0 ?32 ?57 ?102 ?2.9-3.0 ?26
?14 ?2.9-3.0 ?32 ?58 ?Cond ?8.2μS
?15 ?2.9-3.0 ?32 ?59 ?103
?16 ?2.9-3.0 ?32 ?60 ?104
?17 ?2.9-3.0 ?32 ?61 ?105 ?26
?18 ?2.9-3.0 ?32 ?62 ?106
?19 ?5.8μS ?32 ?63 * ?107 ?2.9-3.0 ?26
?20 ?2.9-3.0 ?32 ?64 ?108
?21 * ?2.9-3.0 ?32 ?65 ?109 ?2.9-3.0 ?26
?22 ?32 ?66 ?110 ?26
?23 ?1.8-1.5 ?32 ?67 ?Cond ?9.4μS
?24 ?1.5-1.3 ?32 ?68 ?111 ?2.9-3.0 ?26
?25 ?1.2-1.1 ?32 ?69 ?112 ?2.9-3.0 ?26
?26 ?1.0-1.1 ?32 ?70 ?113
?27 ?1.0 ?32 ?71 ?114 * ?2.9-3.0 ?26
?Cond ?7.9μS ?72 ?115 ?26
?28 ?0.9 ?32 ?73 ?116 ?26
?29 ?0.9 ?32 ?74 ?117 ?26
?30 ?0.8 ?32 ?75 ?118 ?26
?31 ?0.5-0.7 ?32 ?76 ?119 ?1.7-1.6 ?26
?32 ?0.7 ?32 ?77 ?120 ?1.6-1.5 ?26
?33 ?0.7 ?32 ?78 ?121 ?26
?34 ?0.6 ?32 ?79 ?122 ?26
?35 ?0.6 ?32 ?80 ?123 ?26
?36 ?0.6 ?32 ?81 ?124 ?26
?37 ?0.6-0.5 ?32 ?82 ?125
?38 ?0.5 ?32 ?83 ?126 ?1.2 ?26
?39 ?0.5 ?32 ?84 ?127
?40 ?0.5-0.4 ?32 ?85 ?128
?41 ?0.4 ?32 ?86 ?129 ?1.0
?42 ?0.4 ?32 ?87 * ?130
?43 ?0.4 ?32 ?Cond ?5.1μS ?131 ?0.9 ?26
Circulation ?O 3Concentration (ppn) Temperature ℃ Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?132 ?137 ?142
?133 ?138 ?0.7 ?25 ?143 ?0.5 ?25
?134 ?0.8 ?139 ?144
?135 ?140 ?145 ?0.4 ?25
?136 ?0.7 ?25 ?141 ?0.6 ?25 ?146 ?0.4 ?25
*Ozone concentration shown in circulation back manually change.
The Cond=conductance
Per the 3rd circulation (1,4,7 etc.) and data point in the electrochemically cleaning are all got rid of outside data analysis.
Experimental record (Figure 17) with electronic tongue 001013
The new milli-q water of experiment 7 usefulness (just having prepared before the beginning), packaging ring 2 and cold ozone generator.
Circulation ??O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?2 ?0.04 ?22.6 ?71 ?2.97 ?31.8 ?135 ?1.02 ?32.8
?3 ?0.04 ?22.6 ?72 ?2.93 ?31.8 ?137 ?1.00 ?32.8
?5 ?0.04 ?22.6 ?75 ?2.98 ?31.8 ?138 ?0.99 ?32.8
?6 ?0.04 ?22.6 ?77 ?2.97 ?31.8 ?140 ?0.97 ?32.8
?8 ?0.04 ?22.6 ?89 ?0.35 ?32.8 ?141 ?0.98 ?32.8
?9 ?0.05 ?22.6 ?90 ?0.29 ?32.8 ?143 ?0.98 ?32.8
?11 ?0.04 ?23.6 ?92 ?0.13 ?32.8 ?146 ?1.97 ?32.8
?14 ?2.90 ?23.6 ?93 ?0.10 ?32.8 ?147 ?1.97 ?32.8
?17 ?2.99 ?23.6 ?95 ?0.03 ?32.8 ?149 ?2.02 ?32.8
?18 ?3.01 ?23.6 ?96 ?0.03 ?32.8 ?150 ?2.02 ?32.8
?23 ?3.00 ?24.6 ?98 ?0.03 ?32.8 ?152 ?1.99 ?32.8
?24 ?2.94 ?24.6 ?99 ?0.03 ?32.8 ?155 ?2.00 ?32.8
?26 ?2.99 ?24.6 ?104 ?3.01 ?32.8 ?156 ?2.02 ?32.8
?27 ?3.03 ?24.6 ?105 ?3.01 ?32.8 ?158 ?1.97 ?32.8
?32 ?2.98 ?25.7 ?107 ?2.97 ?32.8 ?159 ?1.97 ?32.8
?33 ?2.97 ?25.7 ?108 ?2.98 ?32.8 ?161 ?1.98 ?32.8
?47 ?0.73 ?26.7 ?110 ?3.00 ?32.8 ?162 ?2.00 ?32.8
?48 ?0.67 ?26.7 ?111 ?2.98 ?32.8 ?164 ?1.97 32.8
?50 ?0.52 ?26.7 ?113 ?2.99 ?32.8 ?165 ?2.00 ?32.8
?51 ?0.47 ?26.7 ?114 ?2.99 ?32.8 ?168 ?3.02 ?32.8
?53 ?0.34 ?26.7 ?116 ?2.96 ?32.8 ?170 ?2.99 ?32.8
?54 ?0.29 ?26.7 ?117 ?2.96 ?32.8 ?171 ?2.99 ?32.8
?59 ?2.99 ?30.8 ?119 ?2.95 ?32.8 ?174 ?2.96 ?32.8
?60 ?3.00 ?30.8 ?120 ?2.96 ?32.8 ?176 ?3.01 ?32.8
?62 ?2.96 ?30.8 ?128 ?1.00 ?32.8 ?177 ?2.98 ?32.8
?63 ?2.97 ?30.8 ?129 ?0.97 ?32.8 ?179 ?3.02 ?32.8
?66 ?2.97 ?31.8 ?131 ?0.96 ?32.8 ?183 ?3.02 ?33.6
?68 ?2.97 ?31.8 ?132 ?0.97 ?32.8 ?185 ?2.98 ?33.9
?69 ?2.91 ?31.8 ?134 ?0.98 ?32.8 ?186 ?2.97 ?33.9
*Ozone concentration shown in circulation back manually change.
Per the 3rd circulation (1,4,7 etc.) in the electrochemically cleaning (going up not included in the table), concentration difference is all got rid of outside data analysis greater than circulation (going up not included in the table) and the data point of 0.1ppm.
The ozone generator auto-programming
?O 3Concentration (ppm) Time (branch)
?0 ?30
?3 ?60
?0 ?60
?3 ?60
?0 ?60
?3 ?60
?1 ?60
?2 ?60
?3 ?60
Experimental record (Figure 18) with electronic tongue 001014
The new milli-q water of experiment 8 usefulness (just having prepared before the beginning), packaging ring 2 and cold ozone generator.
Circulation O 3Concentration (ppm) Temperature ℃ Circulation ?O 3Concentration (ppm) Temperature ℃ Circulation O 3Concentration (ppm) Temperature ℃
?3 ?0.02 ?21.3 ?74 ?2.92 ?30.8 ?149 ?1.99 ?32.8
?5 ?0.03 ?20.5 ?77 ?2.98 ?31.8 ?150 ?1.99 ?32.8
?6 ?0.05 ?21.5 ?78 ?3.02 ?31.8 ?152 ?2.00 ?32.8
?8 ?0.05 ?21.5 ?80 ?3.00 ?31.8 ?153 ?2.02 ?32.8
?9 ?0.05 ?21.5 ?92 ?0.70 ?31.8 ?155 ?2.01 ?32.8
?11 ?0.06 ?21.5 ?96 ?0.41 ?31.8 ?158 ?1.97 ?32.8
?12 ?0.07 ?21.5 ?98 ?0.32 ?31.8 ?159 ?1.98 ?32.8
?42 ?1.47 ?25.7 ?99 ?0.25 ?31.8 ?161 ?2.00 ?32.8
?45 ?1.21 ?25.7 ?101 ?0.19 ?31.8 ?162 ?2.01 ?32.8
?47 ?1.08 ?25.7 ?111 ?3.00 ?32.8 ?164 ?1.99 ?32.8
?48 ?0.99 ?25.7 ?113 ?2.98 ?32.8 ?165 ?2.00 ?32.8
?50 ?0.90 ?25.7 ?114 ?3.00 ?32.8 ?167 ?2.00 ?32.8
?51 ?0.81 ?25.7 ?116 ?2.95 ?32.8 ?168 ?1.99 ?32.8
?53 ?0.72 ?25.7 ?117 ?2.98 ?32.8 ?173 ?3.03 ?32.8
?54 ?0.64 ?25.7 ?119 ?2.96 ?32.8 ?176 ?3.00 ?32.8
?56 ?0.56 ?26.2 ?120 ?3.00 ?32.8 ?179 ?2.95 ?32.8
?57 ?0.48 ?26.7 ?122 ?2.95 ?32.8 ?180 ?2.97 ?32.8
?62 ?2.99 ?26.7 ?123 ?2.96 ?32.8 ?182 ?2.97 ?32.8
?63 ?2.90 ?26.7 ?135 ?0.98 ?32.8 ?183 ?2.98 ?32.8
?66 ?2.90 ?26.7 ?137 ?1.01 ?32.8 ?185 ?3.03 ?32.8
?69 ?2.95 ?30.8 ?140 ?0.99 ?32.8 ?188 ?2.96 ?32.8
?71 ?2.98 ?30.8 ?143 ?0.98 ?32.8
?72 ?2.96 ?30.8 ?144 ?1.00 ?32.8
*Ozone concentration shown in circulation back manually change.
Per the 3rd circulation (1,4,7 etc.) in the electrochemically cleaning (going up not included in the table), concentration difference is all got rid of outside data analysis greater than circulation (going up not included in the table) and the data point of 0.1ppm.

Claims (13)

1. electronic tongue that is used to detect ozone based on voltammertry, it comprises at least one working electrode and counter electrode, wherein, described working electrode is by Rh, Pt, Au, Os, Ru, Ni, Ti, Re or their alloy or with the alloy of other metal in one or more make.
2. electronic tongue as claimed in claim 1 is characterized in that having two or more working electrodes.
3. electronic tongue as claimed in claim 1 is characterized in that: described working electrode number is 4-6, preferably 4.
4. as claim 2 or 3 described electronic tongue, it is characterized in that: described electrode is made by different materials.
5. each described electronic tongue as in the above-mentioned claim is characterized in that comprising bar-shaped supporting member, described each electrode embeds like this in the described supporting member, make that the surface portion of each electrode is exposed to outside.
6. as each described electronic tongue in the above-mentioned claim, it is characterized in that being included in the auxiliary electrode of being arranged to the ring electrode form of described supporting member periphery.
7. as each described electronic tongue among the claim 1-4, it is characterized in that comprising inert material, the basic planar plate members of pottery for example, described each working electrode is arranged on the described basic planar plate members with the form of bonding jumper.
8. as each described electronic tongue among the claim 1-4, it is characterized in that:
Described working electrode and described counter electrode are arranged in the section of a pipe, form to need the existence therein of monitoring ozone or the part of the circulation system of the treating apparatus of concentration; And
Described each electrode has the straight-through electric connection line that passes described segment of tube at least one end of each electrode, is used to be connected to external unit.
9. as each described electronic tongue in the above-mentioned claim, it is characterized in that comprising the auxiliary electrode that is used to measure conductance.
10. as each described electronic tongue in the above-mentioned claim, it is characterized in that: described working electrode is made with Rh.
11. the ozone detection system based on voltammertry is used for the existence and/or the concentration of tracer liquid sample ozone, described system comprises:
At least one working electrode (12) made from the alloy of one or more transition metal or Au or their alloy or they and other metal;
Counter electrode (16);
Programmable pulse generator (20), it can be added to described working electrode (12) with predetermined excitation pulse sequence;
Pen recorder is used to write down the output signal that described working electrode produces with the described pulse train that applies;
Sampler is used for preset time at interval to described output signal sampling;
Storer is used for described sampling value is stored in matrix;
Processing unit (PC) is used for described data matrix is carried out multivariate analysis; And
Display device is used to show the result of described multivariate analysis.
12. ozone detection system as claimed in claim 11 is characterized in that: described working electrode is made with Rh.
13. as claim 11 or 12 described ozone detection systems, it is characterized in that: described electrode is arranged in the treating apparatus in online mode.
CNA018227694A 2000-12-22 2001-12-20 Electronic tongue as ozone detector Pending CN1491357A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP00128297A EP1219957A1 (en) 2000-12-22 2000-12-22 Electronic tongue as ozone detector
EP00128297.9 2000-12-22
SE01003656 2001-02-06
SE0100365A SE0100365D0 (en) 2000-12-22 2001-02-06 Electronic tongue as an ozone detector
US27004601P 2001-02-20 2001-02-20
US60/270,046 2001-02-20

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CN1491357A true CN1491357A (en) 2004-04-21

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CA (1) CA2431836A1 (en)
NO (1) NO20032856D0 (en)
TW (1) TW552415B (en)
WO (1) WO2002052254A1 (en)

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CN100507539C (en) * 2007-03-29 2009-07-01 浙江大学 Method for producing taste sense transducer containing electroconductive polymer
CN100507537C (en) * 2007-03-28 2009-07-01 浙江大学 Method for producing taste sense transducer containing electroconductive polymer
CN100510730C (en) * 2006-08-04 2009-07-08 南昌大学 Polypyrrole-PVC membrane decorative taste sensor array and detecting method
CN101957342A (en) * 2009-07-20 2011-01-26 杭州晟迈智能科技有限公司 Volt-ampere electronic tongue
CN102692436A (en) * 2012-06-11 2012-09-26 浙江工商大学 Electrochemical detection method
CN111796000A (en) * 2020-07-07 2020-10-20 王垚 Miniaturized ozone monitor based on gas-sensitive semiconductor and monitoring method

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CN100510730C (en) * 2006-08-04 2009-07-08 南昌大学 Polypyrrole-PVC membrane decorative taste sensor array and detecting method
CN100507538C (en) * 2007-03-28 2009-07-01 浙江大学 Method for producing taste sense transducer containing polymer-carbon black
CN100507537C (en) * 2007-03-28 2009-07-01 浙江大学 Method for producing taste sense transducer containing electroconductive polymer
CN100507539C (en) * 2007-03-29 2009-07-01 浙江大学 Method for producing taste sense transducer containing electroconductive polymer
WO2009033370A1 (en) * 2007-09-10 2009-03-19 The University Of Hong Kong Electronic tongue sensor
CN101836107B (en) * 2007-09-10 2013-04-10 香港大学 Electronic tongue sensor
CN101957342A (en) * 2009-07-20 2011-01-26 杭州晟迈智能科技有限公司 Volt-ampere electronic tongue
CN102692436A (en) * 2012-06-11 2012-09-26 浙江工商大学 Electrochemical detection method
CN111796000A (en) * 2020-07-07 2020-10-20 王垚 Miniaturized ozone monitor based on gas-sensitive semiconductor and monitoring method

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TW552415B (en) 2003-09-11
WO2002052254A1 (en) 2002-07-04
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CA2431836A1 (en) 2002-07-04
NO20032856D0 (en) 2003-06-20

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